Alloy 625

Materials Horizons: From Nature to Nanomaterials
Jung Bahadur Singh
Alloy 625
Microstructure, Properties and
Performance
Materials Horizons: From Nature
to Nanomaterials
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Jung Bahadur Singh
Alloy 625
Microstructure, Properties and Performance
Jung Bahadur Singh
Mechanical Metallurgy Division
Bhabha Atomic Research Centre
Mumbai, Maharashtra, India
ISSN 2524-5384 ISSN 2524-5392 (electronic)

Materials Horizons: From Nature to Nanomaterials
ISBN 978-981-19-1561-1 ISBN 978-981-19-1562-8 (eBook)
https://doi.org/10.1007/978-981-19-1562-8
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Singapore
Knowing is not understanding. There is a
great difference between knowing and
understanding: you can know a lot about
something and not really understand it.
Charles F. Kettering
Dedicated to
My Father Sardar Harbans Singh and
all who lost their lives during the COVID-19
Pandemic
Foreword
The materials research at the Department of Atomic Energy (DAE) plays a vital
role in providing sustaining support to the Indian nuclear program and developing
advanced technologies for DAE applications. Materials Group of Bhabha Atomic
Research Centre (BARC) encompasses all aspects of materials development from
ore to component. It has a proactive research program for in-depth analysis of mate-
rial studies using advanced characterization techniques and to establish structure–
property correlations for the trouble-free operation of DAE plants. India Heavy Water
Plants based on mono-thermal NH3 -H2 exchange process use Alloy 625 tubes for
cracking partially deuterium (D) enriched ammonia (N(H,D)3 ) gas into a mixture of
(H,D)2 and N2 gases.
Besides its use in the nuclear industry, Alloy 625 is often used in chemical
processing, power, aerospace, and automobile industries owing to its unique combi-
nation of high strength, excellent fabricability and weldability, and outstanding
corrosion resistance. The alloy undergoes significant microstructural modifications
during long-term thermal exposure at intermediate temperatures. It develops complex
microstructures by precipitating several competing intermetallic phases and carbides
in the disordered nickel matrix. These microstructural changes harden the alloy and
significantly reduce its ductility and toughness, often below the codal requirements.
There is an extensive literature in peer-reviewed journals and conference proceed-
ings dealing with various aspects of alloy’s properties and behavior. However, a
consolidation of these works is long overdue to bring all the data in an engineering
perspective for the study and assessment of structural damage and properties lost.
This book reflects the author’s lifetime understanding of the physical metallurgy of
and structure–properties correlations in Alloy 625 and other nickel-base superalloys
and associated model alloys. The book provides: (i) different types of microstructural
changes Alloy 625 undergoes at intermediate temperatures; (ii) properties deterio-
ration due to such microstructural changes; (iii) corrosion behavior of the alloy
in different environments; and (iv) criteria to assess the alloy damage for various
destructive and non-destructive testing during in-service inspection of plants.
The book is divided into eight chapters covering almost all aspects, ranging from
phase transformations, mechanical behavior, corrosion, damage mechanisms, etc.,
ix
x Foreword
of Alloy 625. The author has given a detailed description of these transformations
and their effects on alloy’s mechanical properties to fully understand their precipi-
tation behavior in the alloy. The author has brought the industrial data and literature
together for damage assessment of service exposed Alloy 625 components. All the
chapters are presented with a pedagogical introduction to metallurgical principles
necessary for understanding the subject. The selection of the book’s content is based
on peer-reviewed literature on Alloy 625, and successful applications of concepts
in resolving issues related to the failure and life-management of service exposed
tubular components. A distinguishing feature of the book is a chapter exclusively for
the life-management of Alloy 625 components. This monograph would prove to be
of excellent value for the safe and reliable operation and maintenance of Alloy 625
components and their life extensions.
The present book will be helpful to students, researchers, and industrial profes-
sionals interested in Alloy 625.
In my judgment, the author has done a commendable job while combining various
properties of Alloy 625 in this compendium. Such a compendium was missing
despite a large volume of the data in the literature. I compliment the author for
this achievement.
Dr. Ajit Kumar Mohanty

Director, Bhabha Atomic Research Centre
Member, Atomic Energy Commission
Mumbai, India
director@barc.gov.in
Preface
Ever since the introduction of Alloy 625 in the early 1960s, it continues to find several
applications in aerospace, automobile, chemical processing, oil refining and produc-
tion, marine, waste treatment, pulp and paper, power, and nuclear industries. The high
chromium and molybdenum concentrations in Alloy 625 provide superior resistance
to a wide range of corrosive environments. The alloy possesses excellent mechan-
ical properties in the intermediate temperature range. The excellent fabricability and
weldability of the alloy allow it to be easily fabricated into various products, like
thin-walled tubing, reaction vessels, distillation columns, heat exchangers, valves,
etc. The alloy commands nearly a 12% share of the nickel-base superalloys’ world
market of about 9 billion USD, growing at about 7% cumulative annual growth rate
in recent years.
The alloy undergoes significant microstructural modifications during prolonged
thermal exposure at intermediate temperatures. It precipitates multiple intermetallic
and carbide phases in the disordered nickel matrix, including the precipitation of
the Ni2 (Cr,Mo) phase whose precipitation in Alloy 625 was first reported in the
mid-1990s. The simultaneous precipitation of these phases develops a complex
microstructure and hardens the alloy. Increase in the alloy’s strength is accompanied
by a decrease in its ductility and toughness. There are numerous reports in peer-
reviewed journals and conference proceedings dealing with precipitation behavior
of these phases in Alloy 625 and their effects on alloy’s properties. Consolidating
these works is long overdue to bring all the data together.
The microstructural changes during service exposure have a direct bearing on
the mechanical properties, which often deteriorates below the components’ codal
requirements. Many critical components in various plants are likely to have operated
for long durations and even have outlived their designed life. Such components need
to be replaced regularly beyond their stipulated life. This compendium demonstrates
that it is possible to reverse the damaged microstructure and rejuvenate the lost
properties to codal requirements. The high cost of the alloy (about USD 26,000–
35,000 per ton) makes it technically and economically justifiable to rejuvenate service
spent components for utilizing them for a second service cycle.
xi
xii Preface
A primary objective of the book is to bring all the results and literature together
in one place, which can be used for the practice of damage assessment of the
service exposed Alloy 625 components. This book is a first of its kind on Alloy
625, containing a compilation of the knowledge on the microstructural, mechanical
properties and corrosion behavior of Alloy 625 since its development.
The selection of the book’s content is based mainly on peer-reviewed literature
on Alloy 625 and successful applications of concepts in resolving failure-analysis
and rejuvenation issues of industrial processing plants. This knowledge would also
be an excellent value concerning the safety, reliability, operation and maintenance
of components and their life extensions in existing plants.
The book is divided into eight chapters. Chapter 1 gives a brief account of the
importance of superalloys and their classifications, production, product forms and
the market outlook, and the importance of Alloy 625 in a general manner. Chapter 2
briefly describes crystallographic aspects of various phases in Alloy 625 and lays
a foundation for understanding their identification and evolution. The following
two chapters deal with the precipitation of multiple phases and their effects on the
microstructure and mechanical properties of the alloy. The precipitation of inter-
metallic phases significantly increases the strength of Alloy 625. Still, the alloy’s
sluggish aging response constrains its exploitation to age-harden it in a commer-
cially viable manner. This led to the development of an age-hardenable variant of
Alloy 625, known as Alloy 625 PLUS, by adding extra titanium to increase alloy’s
precipitation response without compromising the corrosion resistance and welding
properties of Alloy 625. A separate chapter has been included on Alloy 625 PLUS to
compare it with Alloy 625. The fabrication and corrosion behavior of Alloy 625 are
discussed in individual chapters. The last chapter, on “Life Management of Alloy 625
Components”, primarily addresses various types of damages the alloy undergoes at
different temperatures and gives an account of properties’ deterioration due to such
microstructural changes.
In all the chapters, the reader is presented with a pedagogical introduction to
metallurgical principles for developing an understanding of the subject covered in
the chapter. An attempt is made to explain properties with illustrative examples. The
alloys are usually referred to by their generic names throughout the chapters, and
their compositions are mentioned in weight percent unless specified otherwise.
The book would guide engineers in the industry interested in using Alloy 625
for components’ design. The book would also be helpful for students in colleges
and universities pursuing advanced degrees in Materials Science and Engineering,
Mechanical Engineering and Chemical Engineering, and as an international reference
for lectures giving courses at both undergraduate and postgraduate levels.
Mumbai, India Jung Bahadur Singh

Acknowledgements
It is my pleasure to acknowledge the friends and colleagues who have been helpful,
directly or indirectly, in writing this book. This book is based on decades of physical
metallurgy and structure–properties relation studies on Alloy 625 at Bhabha Atomic
Research Centre (BARC), Mumbai. I am indebted to Late Drs. S. Banerjee and P.
Mukhopadhyay for introducing me to phase transformation studies in nickel-base
alloys after my joining the Materials Group of BARC. The pioneering work on the
physical metallurgy of Inconel 625 and Inconel 718 alloys by Dr. M. Sundararaman
laid the foundation for sustained activities on the structure–properties relationship
of nickel-base superalloys at BARC. I am indebted to Dr. M. Sundararaman for his
guidance on Inconel 625 and 718 alloys during the formative years of my research
career at BARC.
I have been extremely fortunate to interact with many senior scientists and bright
young colleagues during the course of my professional career. My sincere grati-
tude to my seniors and colleagues, Dr. S. Banerjee, Dr. P. Mukhopadhyay, Dr. M.
Sundararaman, Dr. U. D. Kulkarni, Dr. J. K. Chakravartty, Dr. G. K. Dey, Dr. Madan-
gopal Krishnan, Dr. D. Srivastava, Dr. R. Tewari, Dr. R. N. Singh, Dr. R. Kapoor, and
Dr. B. C. Maji. Even informal interactions and discussions with them have enriched
my understanding on physical metallurgy and structure–properties correlations. I
take this opportunity to thank my younger colleagues and students, Dr. Amit Verma,
Dr. K. V. Manikrishna, Dr. Shabana Khan, Smt. Malvika Karri, Shri. K. V. Ravikanth,
Shri. Nachiket Keskar, Shri. Kumar Sourabh, Shri. Akash Gandhi, and Shri. T. N.
Murty, who have given me many ideas and concepts that have helped this book. This
list is, by no means, complete.
Interactions with scientists abroad, particularly with Late Dr. Patrick Veyssière
and Dr. Georges Saada of ONERA, Châttilon, France, Drs. Alain Couret and Guy
Molénat of CEMES Toulouse, France, and Prof. Pascal Bellon of the University
of Illinois at Urban-Champaign, USA, have been immensely helpful in nurturing
understandings on many aspects of deformation behavior and phase transformations
in crystalline materials.
I am grateful to the authors of various publications that have helped build my
understanding and concepts on various topics covered in this book.
xiii
xiv Acknowledgements
I acknowledge my indebtedness to Heavy Water Board (HWB) for entrusting its

confidence in our group for resolving issues related to the performance, failure, and
service degradation of superalloy components of its processing plants. The R&D
support to HWB has given opportunities to investigate a large number of ammonia
cracker tubes with different service exposures. These investigations have provided
significant experience on the service degradation mechanisms and the extent of
degradations during industrial exposure of the alloy.
Kind permissions by publishers Springer Nature, Elsevier, The Minerals, Metals &
Materials Society, Scientific Electronic Library Online (SciELO) and by Dr.
Sundararaman for allowing to use their copyright materials in the preparation of
diagrams and figures are gratefully acknowledged.
I am grateful to Dr. Vivekanand Kain, Director, Materials Group, and Dr.
R.N. Singh, Head, Mechanical Metallurgy Division, for their constant support and
encouragement during the manuscript’s preparation.
The journey of preparing the book’s manuscript took about 14 months, and this
would not have been possible without the generous help of many friends and students.
I am grateful to Dr. Sundararaman, Dr. Madangopal Krishnan, Dr. Bikas Maji, Dr.
Amit Verma, Dr. K. V. Manikrishna, Dr. Rajeev Kapoor, Smt. Malvika Karri, and
Shri. Akash Gandhi for reviewing chapters critically for their technical consistency
and accuracy. Their valuable comments and suggestions have helped to improve
chapter’s presentation. I am also grateful to Dr. S. Khan, Smt. Malvika Karri, Shri.
K. V. Ravikanth, Shri. Akash Gandhi, and Shri. Kumar Sourabh for their substantial
help in preparing figures and plots.
My sincere thanks to Dr. A.K. Mohanty, Director, Bhabha Atomic Research
Centre, and Shri K.N. Vyas, Chairman, Atomic Energy Commission & Secretary,
Department of Atomic Energy of India, for their inspiration and permission to publish
this book.
I am thankful to the publisher, M/s Springer Nature, Singapore Pvt. Ltd., for
publishing the book. The thorough review of the manuscript by the Editor, Ms.
Priya Vyas and her team, is greatly appreciated.
The work on writing the book started during the challenging times of the COVID-
19 pandemic. This pandemic has presented an unprecedented challenge to public
health and led to a dramatic loss of human lives worldwide due to the virus and by
denying health care to patients unrelated to COVID-19. I dedicate this book to the
memory of my Father, Sardar Harbans Singh, and to all who lost their lives during
the COVID-19 pandemic.
Finally, I express my indebtedness to my wife and family for their encouragement
and understanding in reducing many of my responsibilities during the book’s writing,
which helped me focus on the writing with fewer distractions.
Jung Bahadur Singh

Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.1 High-Temperature Materials Called Superalloys . . . . . . . . . . . . . . . . 1
1.2 Journey of Superalloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.3 Alloying Additions in Superalloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.4 Types of Superalloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
1.4.1 Nickel-Base Superalloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
1.4.2 Iron-Base Superalloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
1.4.3 Cobalt-Base Superalloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
1.5 Melting and Consolidation of Superalloys . . . . . . . . . . . . . . . . . . . . . . 14
1.6 Product Forms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
1.7 Market Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
1.7.1 Major Drivers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
1.7.2 Market Size . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
1.7.3 Major Players and Tradenames . . . . . . . . . . . . . . . . . . . . . . . . 21
1.8 Alloy 625 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
1.9 Why a Book on Alloy 625? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
2 Phases in Alloy 625 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
2.1 Definitions of Phase, Crystal Structure and Solid-solution . . . . . . . . 29
2.2 Crystal Structures of Phases in Alloy 625 . . . . . . . . . . . . . . . . . . . . . . 30
2.2.1 Gamma (γ ) Phase . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
2.2.2 Gamma Double Prime (γ ) Phase . . . . . . . . . . . . . . . . . . . . . 32
2.2.3 Ni2 (Cr, Mo) Phase . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
2.2.4 Delta (δ) Phase . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
2.2.5 Carbide Phases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
2.2.6 Topologically Close-Packed Phases . . . . . . . . . . . . . . . . . . . . 38
2.3 Basic Concepts of Diffraction and Phase Identification . . . . . . . . . . . 39
2.3.1 Diffraction Behavior of Crystalline Solids
and the Bragg’s Law . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
2.3.2 The Reciprocal Lattice . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
xv
xvi Contents
2.3.3 The Ewald Sphere . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45

2.4 Lattice Correspondence Between Cubic and Non-cubic Phases . . . . 46
2.5 Identification of Phases in Alloy 625 . . . . . . . . . . . . . . . . . . . . . . . . . . 47
2.5.1 Identification of the γ Phase . . . . . . . . . . . . . . . . . . . . . . . . . 47
2.5.2 Identification of the Ni2 (Cr, Mo) Phase . . . . . . . . . . . . . . . . . 50
2.5.3 Identification of the δ Phase . . . . . . . . . . . . . . . . . . . . . . . . . . 52
2.5.4 Identification of Carbide Phases . . . . . . . . . . . . . . . . . . . . . . . 63
2.6 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
3 Physical Metallurgy of Alloy 625 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
3.1 Alloying Additions in Alloy 625 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
3.1.1 Nickel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
3.1.2 Chromium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
3.1.3 Molybdenum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
3.1.4 Tungsten . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
3.1.5 Niobium and Tantalum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
3.1.6 Iron . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
3.1.7 Aluminum and Titanium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
3.1.8 Carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
3.1.9 Nitrogen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
3.1.10 Sulfur . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
3.1.11 Phosphorus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
3.1.12 Grain Boundary Strengthening Elements . . . . . . . . . . . . . . . 75
3.1.13 Trace Elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
3.2 Characteristic Features of Phases in Alloy 625 . . . . . . . . . . . . . . . . . . 76
3.2.1 Gamma (γ ) Phase . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
3.2.2 Gamma Double Prime (γ ) Phase . . . . . . . . . . . . . . . . . . . . . 78
3.2.3 Delta (δ) Phase . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
3.2.4 Ni2 (Cr, Mo) Phase . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
3.2.5 Carbide Phases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
3.2.6 Topologically Close-Packed Phases . . . . . . . . . . . . . . . . . . . . 84
3.3 Solidification Behavior of Alloy 625 . . . . . . . . . . . . . . . . . . . . . . . . . . 84
3.4 Phase Transformations in Alloy 625 . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
3.5 Microstructural Evolution During Aging of Alloy 625 . . . . . . . . . . . 91
3.5.1 Precipitation of the γ Phase . . . . . . . . . . . . . . . . . . . . . . . . . 92
3.5.2 Precipitation of the δ Phase . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
3.5.3 Precipitation of the Ni2 (Cr, Mo) Phase . . . . . . . . . . . . . . . . . 97
3.5.4 Precipitation of the Carbide Phases . . . . . . . . . . . . . . . . . . . . 99
3.5.5 Precipitation of the TCP Phases . . . . . . . . . . . . . . . . . . . . . . . 101
3.5.6 Precipitation-Free Zones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
3.6 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
Contents xvii
4 Mechanical Behavior of Alloy 625 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111

4.1 Fundamentals of Plastic Deformation of Crystalline Solids . . . . . . . 111
4.1.1 Deformation by Slip . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
4.1.2 Deformation by Twinning . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
4.1.3 Deformation in Superlattice Compounds . . . . . . . . . . . . . . . 115
4.2 Deformation Crystallography of Hardening Phases in Alloy
625 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
4.2.1 γ Phase . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
4.2.2 δ Phase . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 122
4.2.3 Ni2 (Cr,Mo) Phase . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124
4.3 Strengthening of Alloy 625 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131
4.3.1 Solid-Solution Strengthening . . . . . . . . . . . . . . . . . . . . . . . . . 131
4.3.2 Precipitation Strengthening . . . . . . . . . . . . . . . . . . . . . . . . . . . 132
4.4 Deformation Micromechanisms in Alloy 625 . . . . . . . . . . . . . . . . . . . 136
4.4.1 Deformation of Particles by Shearing and Twinning . . . . . . 137
4.4.2 Effect of Particle Size on the Deformation Mode . . . . . . . . 138
4.5 Tensile Behavior of Alloy 625 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 140
4.5.1 Solution Annealed Alloy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 140
4.5.2 Age-Hardened Alloy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143
4.5.3 Work-Hardening Behavior . . . . . . . . . . . . . . . . . . . . . . . . . . . 151
4.6 Fatigue Behavior of Alloy 625 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152
4.7 Creep Behavior of Alloy 625 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159
4.8 Fracture Behavior of Alloy 625 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 165
4.9 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 169
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 169
5 Alloy 625 PLUS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175
5.1 Chemistry of Alloy 625 PLUS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175
5.2 Mechanical Properties of Alloy 625 PLUS . . . . . . . . . . . . . . . . . . . . . 177
5.3 Microstructure of Alloy 625 PLUS . . . . . . . . . . . . . . . . . . . . . . . . . . . . 181
5.4 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 187
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 187
6 Fabrication . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189
6.1 Hot Forming of Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189
6.1.1 Rate Controlling Phenomenon . . . . . . . . . . . . . . . . . . . . . . . . 190
6.1.2 Microstructural Changes during Hot Deformation . . . . . . . 191
6.1.3 Hot Working of Alloy 625 . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193
6.2 Heat Treatments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 196
6.2.1 Types of Heat Treatments . . . . . . . . . . . . . . . . . . . . . . . . . . . . 196
6.2.2 Prevention of Contamination . . . . . . . . . . . . . . . . . . . . . . . . . 200
6.2.3 Fuels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 201
6.2.4 Protective Atmosphere . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 201
6.3 Machining of Alloy 625 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 203
xviii Contents
6.3.1 Conventional Machining . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 203

6.3.2 Hot Machining of Alloy 625 . . . . . . . . . . . . . . . . . . . . . . . . . . 206
6.3.3 Non-conventional Machining . . . . . . . . . . . . . . . . . . . . . . . . . 207
6.4 Welding of Alloy 625 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 211
6.4.1 Common Welding Practices for Alloy 625 . . . . . . . . . . . . . . 211
6.4.2 Pre-welding Treatment of Alloy 625 . . . . . . . . . . . . . . . . . . . 214
6.4.3 Welding Metallurgy of Alloy 625 . . . . . . . . . . . . . . . . . . . . . 214
6.4.4 Mechanical Properties of Weldments . . . . . . . . . . . . . . . . . . 216
6.4.5 Weldability of Alloy 625 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217
6.4.6 Post Weld Heat Treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . 221
6.4.7 Welding Behavior of Alloy 625 PLUS . . . . . . . . . . . . . . . . . 224
6.5 Additive Manufacturing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225
6.5.1 Additive Manufacturing of Metals . . . . . . . . . . . . . . . . . . . . . 225
6.5.2 Additive Manufacturing of Alloy 625 . . . . . . . . . . . . . . . . . . 228
6.6 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 234
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 234
7 Corrosion Behavior of Alloy 625 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241
7.1 The Basic Concepts of Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 242
7.1.1 The Electrochemical Principle . . . . . . . . . . . . . . . . . . . . . . . . 242
7.1.2 Polarization and Passivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . 244
7.1.3 Corrosion Rate Expression . . . . . . . . . . . . . . . . . . . . . . . . . . . 245
7.2 Role of Alloying Elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 245
7.3 General Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 247
7.3.1 Hydrochloric Acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 247
7.3.2 Sulfuric Acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 248
7.3.3 Nitric Acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 249
7.3.4 Hydrofluoric Acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 251
7.3.5 Phosphoric Acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 252
7.3.6 Organic Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 254
7.3.7 Salts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 255
7.3.8 Seawater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 256
7.3.9 Alkaline Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 257
7.4 Localized Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 260
7.4.1 Pitting Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 261
7.4.2 Crevice Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 263
7.4.3 Intergranular Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 265
7.5 Corrosion in High Temperature Pressurized Waters . . . . . . . . . . . . . . 267
7.5.1 Acidic High-Temperature Waters . . . . . . . . . . . . . . . . . . . . . . 270
7.5.2 Neutral High-Temperature Waters . . . . . . . . . . . . . . . . . . . . . 272
7.5.3 Alkaline High-Temperature Waters . . . . . . . . . . . . . . . . . . . . 273
7.6 High-Temperature Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 273
7.6.1 Oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 273
7.6.2 Carburization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 275
Contents xix
7.6.3 Sulfidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 276

7.6.4 Halide Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 277
7.6.5 Molten Salt Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 279
7.7 Environmentally Assisted Cracking . . . . . . . . . . . . . . . . . . . . . . . . . . . 280
7.7.1 Stress-Corrosion Cracking . . . . . . . . . . . . . . . . . . . . . . . . . . . 281
7.7.2 Hydrogen Embrittlement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 282
7.7.3 Sulfide Stress Cracking . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 283
7.8 Corrosion Behavior of Alloy 625 PLUS . . . . . . . . . . . . . . . . . . . . . . . 285
7.9 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 287
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 288
8 Life Management of Alloy 625 Components . . . . . . . . . . . . . . . . . . . . . . . 293
8.1 Definitions of Damage, Failure, and Life . . . . . . . . . . . . . . . . . . . . . . . 294
8.2 Basic Philosophy of Life Management . . . . . . . . . . . . . . . . . . . . . . . . . 295
8.3 Damage Mechanisms in Alloy 625 During Service Exposure . . . . . 296
8.3.1 Microstructural Damage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 297
8.3.2 Structural Damage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 299
8.4 Damage Assessment in Alloy 625 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 299
8.4.1 Assessment Based on Extrapolation of Statistics
of Past Failures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 301
8.4.2 Assessment Based on Hardness . . . . . . . . . . . . . . . . . . . . . . . 301
8.4.3 Assessment Based on Microstructure Cataloging . . . . . . . . 302
8.4.4 Assessment of Damage by Ultrasonic Measurements . . . . . 303
8.4.5 Assessment Based on Bulk Creep Damage . . . . . . . . . . . . . 306
8.4.6 Assessment Based on Fracture Mechanics Analysis . . . . . . 307
8.4.7 Assessment Based on Microstructural Examination
of Cavitation Damage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 311
8.5 Life-Limiting Damage Criteria for Alloy 625 Components . . . . . . . 311
8.5.1 Maximum Hardness of 350 BHN . . . . . . . . . . . . . . . . . . . . . . 313
8.5.2 Minimum 10% Elongation at the Operating
Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 313
8.5.3 Maximum Microstructural Damage . . . . . . . . . . . . . . . . . . . . 313
8.5.4 Life Expenditure and Minimum Thickness Criteria
for the Creep Dominant Damage . . . . . . . . . . . . . . . . . . . . . . 315
8.5.5 Class D Damage for Creep Cavitation . . . . . . . . . . . . . . . . . . 315
8.6 Case Studies on the Performance of Alloy 625 Ammonia
Cracker Tubes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 315
8.6.1 Service Degradation of Tubes and Rejuvenation
of Lost Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 317
8.6.2 Failure of Tubes at a Temperature Less Than 550 °C . . . . . 320
8.6.3 Fish Mouth Opening of a Tube by Temperature
Excursion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 322
8.7 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 323
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 324
xx Contents
Appendix A: Superalloy Compositions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 327

Appendix B: Mechanical Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 337
Appendix C: Physical Properties of Alloy 625 . . . . . . . . . . . . . . . . . . . . . . . . 345
Appendix D: Metallography of Alloy 625 . . . . . . . . . . . . . . . . . . . . . . . . . . . . 349
Appendix E: Hardness Conversion Table . . . . . . . . . . . . . . . . . . . . . . . . . . . . 355
About the Author
Dr. Jung Bahadur Singh Head, Structure of Materials Section of the Mechan-
ical Metallurgy Division of Bhabha Atomic Research Centre (BARC), Mumbai,
is a leading expert in the areas of nickel-based superalloys and structure–properties
correlations. He joined BARC in 1991 after completing an advance course in nuclear
engineering with metallurgy as the specialization. He did his B.Tech. in Metallur-
gical Engineering from Indian Institute of Technology, Kanpur, in 1990, and obtained
a Ph.D. from Indian Institute of Technology, Bombay, in 2002. Dr. Singh has an
accomplished career demonstrating consistent success as a researcher and a teacher
and has made significant contributions in the fields of phase transformations and
deformation behavior of metallic systems. He has carried out decisive experiments
to advance the understanding of microstructural evolution and micro-mechanisms of
plasticity in advance alloys. He is Professor of Engineering Sciences, Homi Bhabha
National Institute (HBNI), Mumbai, and has taught courses related to “Physical
Metallurgy,” “Plasticity and Strengthening Mechanisms in Crystalline Materials,”
and “Materials characterization.” He has guided many students for their M.Tech. and
Ph.D. dissertations. He has been a visiting scientist to CEMES, Toulouse, France (in
2003 and in 2004), University of Illinois at Urbana-Champaign, USA (2005–2007),
Helmholtz-Zentrum Berlin, Berlin, Germany (2011), and Institut Laue Langevin
(ILL), Grenoble, France (2012).
xxi
Chapter 1
Introduction
The ever-increasing requirement for high-temperature strength and better corrosion-

resistant materials for increasingly higher operating temperatures and stresses in
the process industry always pushes the envelope for high-performance alloys. This
resulted in the development of a variety of compositionally complex alloys, often
called “superalloys”, containing various alloying elements, which impart required
mechanical and corrosion properties. At the same time, these alloys are very sensi-
tive to certain impurities that need to be controlled for desired properties. These
requirements entail special care during their melting and fabrication. The high-
performance alloys, such as Alloy 625, have excellent combinations of mechanical
strength and surface stability at high temperatures. Commercially, high-performance
alloys control a sizable market size, and their economic importance is reflected
in the continued research for their further development. This chapter gives an
overview of the development, manufacturing, applications and market outlook of
high-performance alloys.
1.1 High-Temperature Materials Called Superalloys
Superalloys are highly concentrated alloys, based on Group VIII A elements,

designed to meet material challenges of high temperature and aggressive environ-
ments of gas turbine engines or industries involved in the processing of metals,
chemical and nuclear waste. They exhibit excellent long-time strength and resistance
against creep, corrosion, oxidation and erosion at temperatures above 650 °C, along
with good surface stability. Superalloys have an austenite face-centered cubic (FCC)
matrix that contains several elements in various combinations to accord desired
properties. They may also contain second-phase particles to precipitate harden the
austenite matrix. Superalloys can be broadly classified into three broad categories,
namely, (i) iron-base superalloys; (ii) nickel-base superalloys, and; (iii) cobalt-base
superalloys.
© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2022 1
J. B. Singh, Alloy 625, Materials Horizons: From Nature to Nanomaterials,
https://doi.org/10.1007/978-981-19-1562-8_1
2 1 Introduction
At low temperatures, under static loading conditions, properties like yield strength
or ultimate tensile strength, which are measured over short-time intervals, are impor-
tant for the material. Other properties, such as modulus, crack growth rates, and
fracture toughness, are also important even though they are related to the strength
of the material. A component designed based on these properties would continue
to operate indefinitely within the designed operating conditions if no surface degra-
dation due to environmental damage occurs. At temperatures above about 0.5T m
(T m is melting temperature in Kelvin) and under dynamic loading conditions, time-
dependent material behaviors like creep or fatigue also become important. Thus,
creep strength or stress-rupture strength (also called rupture strength) of metal at
elevated temperatures is also as important as the yield and ultimate tensile strengths.
Similarly, fatigue strengths are also necessary under dynamic loading conditions,
along with the yield and ultimate tensile strengths.
Superalloys are excellent materials for high-temperature applications because of
their inherent strengths at elevated temperatures and phase stability [1]. All superal-
loys have the FCC crystal structure, even though iron and cobalt are body-centered
and hexagonal, respectively, at low-temperatures. They transform to the face-centered
cubic structure only at high temperatures. The addition of other elements stabilizes
the face-centered structure of the two elements even at room temperature. Nickel
has a face-centered cubic structure at all temperatures up to melting. Therefore, the
upper limit for using superalloys is not restricted by phase transformation reactions,
as observed in ferritic steels, which causes a sudden drop in their strengths. Another
advantage of the austenitic matrix is its extended solubility for many alloying solutes,
excellent ductility, and favorable characteristics for the precipitation strengthening
phases.
The upper limit of the use of solid-solution superalloys is governed by their
incipient melting temperatures. Incipient melting temperature is the temperature
when the alloy melts locally and is lower than the liquidus temperature. The upper-
temperature limit of precipitation-hardened alloys is governed by the solvus or
stability temperature of the hardening phase. Table 1.1 gives the typical upper-
temperature limit of using some wrought superalloys governed by the incipient
melting or solvus/dissolution temperature of the hardening phases [2–5]. The incip-
ient melting temperature and melting/solidification range of a superalloy is a func-
tion of its composition and prior processing. Superalloys, by their design, contain a
large number of solutes, especially transition elements, in high concentrations. The
transition elements often segregate during solidification to create non-equilibrium
composition phases that melt at temperatures lower than the equilibrium compo-
sition. Further, as these alloys melt over a wide temperature range, superalloys do
not melt at a specific temperature even in wrought conditions where the segregation
effect is negligible.
The high-temperature applications of superalloys include components for
aerospace and metal, chemical and nuclear processing industries that require high
resistance against heat, corrosion, or both. The significance of superalloys in the
modern industry can be gauged from their usage in aircraft gas turbine engines.
The total contribution of superalloys in aircraft gas turbine engines in 1950s was
1.1 High-Temperature Materials Called Superalloys 3
Table 1.1 Typical

Alloy Upper-temperature Temperature
upper-temperature limit of the
limit (°C) limiting behavior
usage of some wrought
superalloys restricted by their Hastelloy X 1250 Incipient melting
incipient melting temperature temperature
or solvus temperature of their Hastelloy 25 (L 1330 Incipient melting
hardening phases [2–5] 605) temperature
Inconel 617 1330 Incipient melting
temperature
Inconel 625 1290 Incipient melting
temperature
Inconel X750 1395 Incipient melting
temperature
A 286 855 Solvus of the γ
phase
Rene 95 1120 Solvus of the γ
phase
IN 100 1180–1200 Solvus of the γ
phase
U 700 1130–1150 Solvus of the γ
phase
Nimonic 80 A 960–980 Solvus of the γ
phase
Nimonic 90 1020–1060 Solvus of the γ
phase
phase
phase
Rene 41 1050–1070 Solvus of the γ
phase
Udimet 500 1050–1100 Solvus of the γ
phase
Waspaloy 1025–1040 Solvus of the γ
phase
Inconel 718 705 Stability of the γ
phase
Custom age 625+ 705 Stability of the γ
phase
Haynes 242 705 Solvus of the
Ni2 (Cr, Mo) phase
4 1 Introduction
Table 1.2 Typical applications of superalloys in different industries and systems [6]
Industry/system Components
Aircraft gas turbines Disks, combustion chambers, bolts, casings, shafts,
exhaust systems, cases, blades, vanes, burner cans,
afterburners, thrust reversers
Steam turbine power plants Bolts, blades, stack gas reheaters
Reciprocating engines Turbochargers, exhaust valves, hot plugs, valve seat
inserts
Metal processing Hot-work tools and dies, casting dies
Medical applications Dentistry uses, prosthetic devices
Space vehicles Aerodynamically heated skins, rocket engine parts
Heat-treating equipment Trays, fixtures, conveyor belts, baskets, fans, furnace
mufflers
Nuclear power systems Control rod drive mechanisms, valve stems, springs,
ducting
Chemical and petrochemical industries Bolts, fans, valves, reaction vessels, piping, pumps
Pollution control equipment Scrubbers
Coal gasification and liquefaction Heat exchangers, reheaters, piping
Metal processing mills Ovens, afterburners, exhaust fans
about 10% by weight 1 but had increased to 50% by 1985 [2]. Table 1.2 lists typical
applications of superalloys in different industries or systems [6].
1.2 Journey of Superalloys
The insatiable thirst for high-temperature strength and better corrosion-resistant

materials at increasingly higher operating temperatures and stresses has driven the
development of superalloys, powered primarily by jet engine technology. The devel-
opment of the stainless steel at the beginning of the twentieth century can be consid-
ered as the inception of the iron-base superalloys’ journey. The British patent for
Nichrome, a Ni–20Cr alloy, in 1918 served as a starting point for the development
of Ni–Cr based superalloys like Nimonics and Inconels [1, 2]. Bedford, Pilling, and
Merica produced a stronger Nichrome-based alloy, in 1929, by adding small amounts
of titanium and aluminum, which was patented as Nimonic 80. However, in 1951,
after the invention of electron microscopy, Taylor and Floyd unraveled the mystery
that the precipitation of the now well-known γ phase particles imparts Nimonic 80
a higher strength. Parallelly, a well-known cobalt-base alloy Vitallium, also known
as Haynes Stellite 31, used in dentistry, was adapted for turbocharger and gas turbine
1The compositions of the alloys throughout the book are mentioned in weight per cent (wt%),
unless specified otherwise.
1.2 Journey of Superalloys 5
applications. Besides, wrought S816 and cast X40 cobalt superalloys were intro-
duced for gas turbine blades and vanes applications. In the late 1940s, adding molyb-
denum in alloy M-252 increased its solid-solution strength significantly. This started
the more widespread use of refractory metals in nickel and iron-based superalloys
[1]. Many of the early nickel–iron- and cobalt-base superalloys acquired additional
strength by carbide phase particles’ dispersion.
However, the need for high-temperature superalloys was not realized until the
development of the aircraft gas turbine engines. Before gas turbine engines, the
highest turbine inlet temperature of 550 °C was within the temperature capabilities
of the stainless steel. The need for material with higher temperature capabilities was
felt only after the successful 1937 flight of Hans von Ohain’s turbine engine Heinkel
in Germany and an independent 1939 flight of Whittle’s engine in England. These
developments had increased the turbine inlet temperature of jet engines to 780 °C,
which was above the capability of conventional austenitic stainless steels. Stainless
steels were then modified heavily to increase their highest operating temperatures,
which led to the development of the first high-temperature superalloys, wrought Rex-
78 alloy, for gas turbine engines (GTEs) [7, 8]. The advancements in the superalloy
technology made rapid strides in the 1940s, driven by the developments from the
World War II.
After World War II, the story of superalloys was dominated by further improve-
ments and the invention of new alloys and new processes, driven first by the military
use of jet engines and then by industries that needed industrial gas turbines. The
alloy development virtually exploded in the ‘50s and ’60s, while the process devel-
opment in the ‘70s and ‘80s [7]. While the gas turbine engines prevailed upon the
superalloy technology, superalloys were also developed for various other applica-
tions like high-temperature helium reactors, heat exchangers, furnaces, sour gas well
equipment, etc.
The introduction of commercial vacuum melting technology in 1952 by Falih
N. Darmara for better compositional control accelerated the superalloys technology.
Both vacuum induction melting (VIM) and vacuum arc remelting (VAR) allowed
the charge to remain molten for more extended periods, providing more time for
degasification and removing volatile impurities. In addition, the two melting practices
allow time for sampling and adjusting the composition of the melt. Vacuum induction
melting also allows more effective use of beneficial trace elements, such as boron,
manganese, and silicon, as deoxidants, which improve high-temperature properties
[9]. A significant benefit of VIM was that it allowed the addition of much higher levels
of aluminum and titanium to the alloy, which led to the development of widespread
γ precipitation-hardened nickel-base superalloys. Without the practice of vacuum
melting and casting, these alloying elements would oxidize quickly, which renders
their addition as strengthening solutes ineffective and makes the alloy unfit for most
structural applications.
In 1962, H. Eiselstein patented a γ precipitate strengthened superalloy, Alloy
718, to cater for the needs of emerging jet engine technology. Alloy 718 replaced
the highly alloyed steels and nickel-based superalloys. This alloy has been the most
successful and versatile superalloy ever invented and rules the superalloy market
6 1 Introduction
Fig. 1.1 Turbine blade castings showing conventional a equiaxed, b directionally solidified, and c
single-crystal. Reprinted by permission from Springer Ref. [10]. Copyright (2018)
even after seven decades of its invention. The alloy is being used extensively in
the aerospace, power generation, and oil and gas industries for fabricating highly
engineered critical components exposed to hot corrosive environments.
By the 1970s, the superalloys had gained sufficient strength, creep resistance and
adequate environmental resistance. The focus of the superalloy development had
shifted to directional solidification and powder processing. One significant develop-
ment was the commercialization of the directional solidification process to produce
columnar and single crystal turbine blades (Fig. 1.1) [10]. The major breakthrough
came around 1979 with the growth of the first commercial single crystal of PWA-
1480 superalloy [11]. Single crystal blades have more creep life and permit their
use at higher temperatures than their polycrystalline counterparts. Oxide disper-
sion strengthened (ODS) alloys were developed almost simultaneously through the
powder-metallurgy route. Wrought γ strengthened ODS alloys generate usable
creep-rupture strength up to about 90% of the melting temperatures.
Later developments had seen a significant improvement in the properties of some
alloys, particularly Ni–Cr–Mo alloys. A noteworthy development was the invention
of a Ni–Cr–Mo precipitation-hardened alloy, Haynes 242 alloy, for gas turbine engine
applications [5]. Haynes 242, and its derivative Haynes 244, are age-hardenable
alloys hardened by the precipitation of Ni2 (Cr, Mo, W) phase [5, 12]. The Ni2 (Cr,
Mo, W) phase differed from the usually observed γ or γ hardening precipitates. In
addition, the compositions of some existing alloys like Alloy 718 and Alloy 625 were
modified for improvement in their properties. The modified alloys were commer-
cialized as ATI 718 Plus [13] and Custom Age 625 Plus [4] alloys. A very recent
development is the stabilization of the γ phase with a new composition, (Ni, Cr,
W)3 (Mo, Ti, Cr), in Ni–Cr–Mo–W–Ti alloys without the addition of niobium [14].
1.2 Journey of Superalloys 7
Fig. 1.2 A timeline of the developmental history of superalloys [1, 7]. Alloys arrow-marked with
phases (γ Ni3 (Al, Ti), γ Ni3 (Nb, Ti) or Ni2 (Cr, Mo) or indicate the commercial introduction of
age hardenable alloys with the precipitation of respective phases. All the alloys, except for the γ
Ni3 (Cr, Mo, Ti) strengthened alloys are commercial alloys. Details of commercial alloys are given
in Appendix A and B. The γ Ni3 (Cr, Mo, Ti) strengthened alloy is a recently developed alloy [14].
The γ (Ni, Cr, W)3 (Mo, Ti, Cr) has all the characteristic features of the γ Ni3 Nb
phase in niobium bearing nickel alloys. The advantage of the γ (Ni, Cr, W)3 (Mo, Ti,
Cr) phase is that it is stable up to about 850 °C, much higher than the stability of the
γ Ni3 Nb phase that transforms to the harmful δ phase at temperatures above 650 °C.
The invention of the (Ni, Cr, W)3 (Mo, Ti, Cr) hardened Ni–Cr–Mo alloys opens up
the possibility of a new series of γ hardenable alloys. A timeline for the development
of various types of superalloys is shown in Fig. 1.2.
1.3 Alloying Additions in Superalloys
Many elements in various combinations are added to superalloys to produce desired

properties. Some elements dissolve into the solid solution, while others may induce
the precipitation of second-phase particles during thermal exposure. In a solid solu-
tion, the alloying solute is distributed randomly within the host (solvent) matrix,
while a precipitate may have a phase different from the matrix. The role of alloying
elements and their influence on the stability of various phases depends strongly upon
the position of elements in the periodic table. Based on their positions, alloying
elements in superalloys can be categorized into three broad groups [1, 7, 15]: (i)
Solid-solution hardener; (ii) intermetallic hardening phase former, and (iii) grain-
boundary strengthener. The most common alloying additions that impart solid solu-
tion strengthening are chromium, aluminum, titanium, molybdenum, niobium, tung-
sten, etc. These solutes also stabilize the FCC structure of iron and cobalt solid solu-
tions in respective superalloys. Alloying elements such as chromium, molybdenum,
8 1 Introduction
niobium, tungsten, tantalum and titanium are also strong carbide formers, while
chromium and molybdenum promote the formation of borides too [1]. The second
group of elements are aluminum, titanium, niobium, and tantalum, which induce the
formation of ordered phase particles such as Ni3 (Al, Ti) (γ phase) and Ni3 (Nb, Ta,
Ti) (γ phase). These solutes are characterized by atomic radii greater than nickel.
The precipitation of such intermetallic phases generates a two-phase microstructure
containing coherent particles of the γ phase, γ phase, or both, which significantly
increase the alloy’s high-temperature strength and the resistance to creep deforma-
tion. Studies on the precipitation of another intermetallic phase with Ni2 (Cr, Mo, W)
stoichiometry in nickel alloys have led to the invention of Haynes 242 and 244 alloys
[4, 12]. The third group includes elements like boron, carbon, zirconium, hafnium,
etc. which strengthen grain boundaries apart from forming grain-boundary precipi-
tates. These elements have their atomic radii very different from the base element.
Minor additions of carbon and boron form carbides and borides, respectively. Typical
roles of major solutes in the three types of superalloys are given in Table 1.3.
Melting practices of superalloys invariably introduce some undesired tramp
elements like silicon, phosphorous, sulfur, oxygen, nitrogen, etc. which need to
be restricted to very low (parts-per-million) concentration levels. These elements
segregate at grain boundaries and embrittle the alloy if their concentration is not
restricted [7, 15]. Minor additions of some beneficial elements, like magnesium
and manganese, and reactive solutes like titanium and niobium, remove detrimental
effects by bonding with tramp elements. The bonding of manganese with sulfur to
form MnS and titanium with nitrogen to form TiN to remove sulfur and nitrogen
illustrates the beneficial roles of tramp elements.
Chromium and many other elements like aluminum, molybdenum, titanium and
tungsten also resist environmental degradation. Chromium promotes the formation
of the Cr2 O3 layer on external surfaces of alloys, while the addition of aluminum
enhances its oxidation resistance properties. Mo and W protect the Cr2 O3 layer under
various corrosive environments. Though Cr is the primary solute for hot corro-
sion resistance, the addition of titanium supplements its effect. Addition of rare
earth elements lanthanum, yttrium and cerium in small quantity also promotes high
temperature oxidation and corrosion resistance.
Even though elements like cobalt, chromium, molybdenum, tungsten, rhenium,
etc., are added for their favorable alloying qualities, they may sometimes form unde-
sirable topologically close-packed (TCP) phases (e.g., σ, μ, Laves, etc.) during
processing and thermal aging. The precipitation of the TCP phases has little effect
on yield strength of the alloy but may cause significant loss of corrosion resistance
and ductility because of their hard and brittle nature.
The addition of vanadium to superalloys also contributes to their solid solution
strengthening and precipitation hardening by carbide formation. However, its addi-
tion in superalloys is usually avoided because of its deleterious effects. Vanadium
promotes the formation of the embrittling sigma (σ) phase. Moreover, the beneficial
effects of chromium, molybdenum, and niobium at elevated temperatures outweigh
the advantages of vanadium. In addition, at temperatures above 690 °C, vanadium
may form V2 O5 in oxidizing atmospheres that weaken the protective film, leading
1.3 Alloying Additions in Superalloys 9
Table 1.3 Major roles of solutes in different types of superalloys [8, 15]
Element Iron-base Cobalt-base Nickel-base
Cr – Improves hot corrosion – M23 C6 and M7 C3 – M23 C6 and M7 C3
and oxidation resistance carbide precipitation carbide precipitation
– Solid-solution hardening – Improves hot corrosion – Improves hot corrosion
and oxidation resistance and oxidation resistance
– Promotes TCP phases – Moderate solid-solution
hardening
– Moderate increase in γ
volume fraction
– Tend to stabilize Ni2 Cr
phase in alloys
containing more than
20% Cr
– Promotes TCP phases
Al – Induces γ precipitation – Improves oxidation – Moderate solid-solution
– Retards formation of resistance hardening
hexagonal η Ni3 Ti phase – Forms intermetallic – Induces γ precipitation
β-CoAl – Improves oxidation
resistance
Ti – γ precipitation – TiC carbide precipitation – Moderate solid-solution
– TiC carbide – Formation of Co3 Ti hardening
precipitation intermetallic – γ precipitation
– Formation of Ni3 Ti with – TiC carbide precipitation
sufficient Ni – Retards the precipitation
– Reduces surface stability of Ni2 (Cr, Mo) phase
particles
Mo – Solid-solution hardening – Solid-solution hardening – High solid-solution
– Forms M6 C carbide – Forms Co3 Mo hardening
precipitates intermetallic precipitates – Moderate increase in γ
– Promotes TCP phases volume fraction
– M6 C and MC carbide
formation
– Promotes formation of
Ni2 (Cr, Mo) phase
particles
– Promotes σ and μ TCP
phases
W – Solid-solution hardening – Solid-solution hardening – High solid-solution
– M6 C carbide – Formation of Co3 W hardening
precipitation intermetallic – Moderate increase in γ
– Promotes TCP phases volume fraction
– M6 C carbide formation
– Increases density
– Promotes the formation
of Ni2 (Cr, Mo, W)
particles
– Promotes σ and μ TCP
phases
(continued)
10 1 Introduction
Table 1.3 (continued)

Ta – γ precipitation – MC and M6 C carbide – High solid-solution
– Forms TaC carbide precipitation hardening
precipitates – Formation of Co2 Ta – TaC carbide
intermetallic precipitation
– Reduces surface stability – Large increase in γ
volume fraction
– Improves oxidation
resistance
Nb – γ precipitation – MC and M6 C carbide – High solid-solution
– NbC carbide precipitation hardening
precipitation – Formation of Co2 Nb – Large increase in γ
– δ Ni3 Nb precipitation intermetallic volume fraction
– Reduces surface stability – NbC carbide formation
– γ precipitation
– δ Ni3 Nb precipitation
Re – – – Moderate solid-solution
hardening
– Increases γ /γ lattice
mismatch
– Retards coarsening
Fe – Not applicable – Improves workability – Decreases oxidation
resistance
– Promotes σ and Laves
TCP phases
– Improves workability
Co – – Not applicable – Raises γ solidus
temperature
– Moderate increase in γ
volume fraction in some
alloys
– Raises γ solvus
temperature
Ni – FCC matrix stabilizer – FCC stabilizer – Not applicable
– Inhibits TCP phase – Decreases hot corrosion
precipitation resistance
C – Carbide formation – Carbide formation – Carbide formation
– Stabilizes FCC matrix – Decreases ductility – Moderate solid-solution
hardening
B – Improves creep strength – Improves creep strength – Moderate solid-solution
and ductility and ductility hardening
– Retards formation of – Inhibits carbide
grain-boundary η Ni3 Ti coarsening
– Improves
grain-boundary strength
– Improves creep strength
and ductility
(continued)
1.3 Alloying Additions in Superalloys 11

Zr – Improves creep strength – ZrC carbide formation – Moderate solid-solution
and ductility – Improves creep strength hardening
– Retards formation of and ductility – Inhibits carbide
grain-boundary η Ni3 Ti – Reduces surface stability coarsening
– Improves
– Improves creep strength
and ductility
Hf – – – Improves creep strength
and ductility
– Improves
– HfC formation
– Promotes eutectic γ /γ
formation
V – Improve notch ductility – – Imparts extra passivation
at elevated temperatures to some alloys in the
– Improves hot workability certain liquid media
to catastrophic oxidation [16]. A limited number of superalloys that are known to

contain small amounts of vanadium are Ni-100 alloy and alloys like Hastelloy B and
Hastelloy C-276 (about 0.33% maximum) in which vanadium is added to impart
extra passivation in certain liquid media [16].
1.4 Types of Superalloys
Superalloys are categorized according to the nature of the base metal. This section
gives a brief overview of the three types and their classification based on the strength-
ening behavior. Producers of superalloys market them with tradenames. Some
commonly used tradenames are Inconel, Hastelloy, Rene, Waspaloy, Incoloy, CMSX
single crystal alloy, etc. Appendix A offers nominal compositions of commonly used
superalloys. Further, some alloys, like Inconel 718, Incoloy 903, etc. contain nickel
and iron contents in comparable amounts. Such alloys are also classified as iron-
nickel alloys. However, in the present text, the classification is restricted to the already
mentioned three categories (Sect. 1.1), and alloys containing comparable nickel and
iron amounts are classified as nickel-based or iron-based merely on the basis of the
higher of the two amount in their nominal compositions. The mechanical properties
of some selected superalloys are given in Appendix B.
12 1 Introduction
Table 1.4 Typical ranges of major alloying elements in different types of cast and wrought
superalloys
Element Range (%)
Ni-base Fe-base Co-base
Ni Balance 9–33 0–35
Fe 0–38 Balance 0–21
Co 0–29 0–20 Balance
Cr 0–30 0–22 19–30
Mo 0–28 0–3 0–10
W 0–14 0–3 0–25
Al 0–7 0–1 0–1
Ti 0–5 0–3 0–4
Nb 0–6.5 0–5 0–4
Ta 0–10 0–1 0–9
Re 0–6 – 0–2
1.4.1 Nickel-Base Superalloys
High stability of the austenite nickel phase allows the addition of large amounts
of various elements to tailor properties of alloys for a variety of applications. The
high concentrations of solutes in nickel-base superalloys make them complex but the
most exciting superalloys. They may contain up to 30% chromium, up to about 7%
aluminum and titanium together, 5–15% cobalt, and many other transition elements
like molybdenum, niobium, tungsten, etc. along with small amounts of boron, zirco-
nium, magnesium, and carbon. Typical ranges of major solutes in superalloys are
given in Table 1.4. The nickel-based superalloys can further be classified into two
broad categories, as illustrated in Fig. 1.3. The first category contains alloys strength-
ened by solid-solution hardening, while the second category corresponds to alloys
strengthened by the precipitation of intermetallic compounds of Ni3 X type in the
nickel solid solution (γ ) matrix. Alloys containing aluminum and titanium, such as
Waspaloy, Astroloy, U-700, Rene 80, etc. are strengthened by the precipitation of
γ phase particles of Ni3 (Al, Ti) stoichiometry, while niobium bearing alloy, like
Inconel 718 and Custom Age 625 Plus, are strengthened by the formation of γ
phase precipitates of Ni3 Nb stoichiometry. Some alloys, like Alloy 718 and Alloy
706 containing niobium as well as aluminum and titanium are strengthened by both
γ and γ phase particles. On the other hand, solid-solution hardened alloys, such
as Hastelloy N and Inconel 625, derive their strength from the side effects of major
solutes. The solid solution strengthened alloys may sometimes the precipitation of
carbide particles in the austenite matrix.
A large number of nickel superalloys like C-4, C-22, C-276, Haynes 242 Alloy
625, Hastelloy S, etc. can be further classified into Ni–Cr–Mo alloys for driving their
major properties, namely, strength and corrosion as well as oxidation resistance,
1.4 Types of Superalloys 13
Fig. 1.3 Classification of nickel-base superalloys
from chromium and molybdenum solutes (Appendix A). Amount of chromium and
molybdenum individually may vary significantly from one alloy to another but remain
5% < Cr < 33% and 5% < Mo < 25% such that they together contribute about 28% < Cr
+ Mo < 40%. Most of these alloys are designed as solid-solution strengthened. Still,
they often form Ni2 Y (Y=Cr, Mo) stoichiometry precipitates at temperatures ranging
from about 400 to 650 °C, which increases their mechanical strengths. The formation
of the Ni2 (Cr, Mo) phase in Ni–Cr–Mo alloys has drawn significant attention of
researchers on their hardening behavior in the last few decades. This has led to the
invention of a new series of Ni2 (Cr, Mo) precipitation-hardened Haynes 242 [5] and
Haynes 244 [12] alloys.
The significant advantages of nickel-base superalloys are that many of them can
be age-hardened by the precipitation of intermetallic γ , γ and Ni2 (Cr, Mo) phase
particles, and have a low propensity for the formation of TCP phases compared to
iron-base and cobalt-base superalloys. However, they are quite expensive. Nickel-
based superalloys are most widely used for the hottest parts of gas turbine engines as
blades, vanes, disks, etc. because they offer the highest strength and creep resistance
at high temperatures.
1.4.2 Iron-Base Superalloys
Iron-base superalloys have evolved from austenitic stainless steel. They contain more
than 20% nickel to stabilize the austenite phase and about 20% chromium to impart
sufficient corrosion resistance. Iron-base superalloys are mostly solid-solution hard-
ened, though a few of them can be precipitation-hardened that contained a high nickel
content. The strengthening in precipitation-hardened alloys is primarily achieved by
forming the γ or γ phase, although carbides and carbonitrides may also be present.
Alloys, like A286, that are strengthened by the γ particles, typically contain about
14 1 Introduction
25–35 wt% nickel, while alloys, like Incoloy 903, are strengthened by the precipita-
tion of γ phase particles and includes a minimum of 40% nickel. A small amount
of vanadium is sometimes added to iron-base alloys, e.g., in A286, to improve their
hot workability and notch ductility at elevated temperatures.
The advantages of iron-base superalloys are their low cost and good workability.
However, they have lower environmental resistance, lower strength at high temper-
atures and a higher propensity for forming TCP phases than nickel-base superal-
loys. Iron-base superalloys are suitable for applications that need high toughness at
low-temperature applications like rotor fan disks, turbine casings, etc.
1.4.3 Cobalt-Base Superalloys
Cobalt crystallizes as the hexagonal close-packed phase at lower temperatures and

transforms to the face-centered phase only at temperatures above 417 °C. A minimum
of 10% nickel is added in cobalt-base superalloys to stabilize the FCC structure at
all temperatures up to the melting point. Modern cobalt-base superalloys are charac-
terized by solid solution strengthening. Titanium addition induces the precipitation
of coherent, ordered Co3 Ti as a strengthening phase. During the late 1950s, two
commercial cobalt-base alloys, Jetalloys J-1570 and J-1650, containing the coherent
γ precipitates stabilized by about 28% nickel, were briefly popular as precipita-
tion strengthened alloys [1]. However, the rapid development of nickel-based γ
hardened alloys with superior mechanical properties and temperature stability led to
their premature demise. Cobalt-base alloys also form M23 C6 , M6 C, and MC carbide
precipitates as in nickel-base superalloys, which are often used to impart some precip-
itation hardening. In addition to carbides, the cobalt-base alloys tend to form TCP
phases like Co2 W and Co7 W6 .
The significant advantages of cobalt-base superalloys are their higher incipient
melting point and much superior hot corrosion resistance at high temperatures.
Besides, cobalt-base alloys can be melted in air or argon, unlike the vacuum melting
of nickel-base and iron-nickel-base alloys, which contain much higher amounts of
reactive alloying elements like aluminum and titanium. However, cobalt-base super-
alloys have a higher propensity to precipitate undesirable TCP phases than nickel-
base alloys. The strength of cobalt-base alloys is also limited compared to those
of precipitation strengthened nickel-base or iron-base alloys. Cobalt-base alloys are
suitable for applications like industrial gas turbine engines (GTEs), vanes, etc. where
creep-resistant at low stresses or hot corrosion resistance is required.
1.5 Melting and Consolidation of Superalloys
Superalloys are usually produced through double melting practice, employing mainly
vacuum induction melting (VIM) followed by either vacuum arc remelting (VAR) or
1.5 Melting and Consolidation of Superalloys 15
Fig. 1.4 Flow diagram of processes widely used to produce superalloy components
electro slag remelting (ESR) of the electrodes/ingots prepared by VIM. Figure 1.4
shows a flow chart of the processes used to produce superalloy products. Vacuum
induction melting is the primary melting step in the process route of wrought and
cast superalloys and near-net-shape products. Vacuum induction melting reduces
oxygen and nitrogen contents significantly in the alloy and dramatically improves
micro-cleanliness of the alloy with fewer oxides and nitrides in the final products.
Additionally, it removes high-vapor-pressure impurities like lead and bismuth that
may enter the alloy through the scrap circuit during the melting process. As a result,
the vacuum-melted superalloys have improved fatigue and stress-rupture properties.
The VIM, however, is costlier than the electric-arc furnace (EAF) or argon oxygen
decarburization (AOD) processes usually employed for the production of stainless
steel or other highly alloyed steels. The EAF or AOD processes are less preferred for
melting superalloys as alloys pick up large amounts of impurities and undesirable
elements during the melting.
The alloy ingots produced by EAF/AOD or VIM are subsequently remelted
by secondary melting techniques under controlled conditions. Many inclusions are
16 1 Introduction
removed by flotation or chemical and physical processes during secondary melting.

The two most common secondary remelting methods are vacuum arc remelting
(VAR) and electro slag remelting (ESR). The quality of ingots produced by the
two remelting processes is significantly different because of the differences in the
nature of impurities and defects created by the two processes and during subsequent
solidification.
In VAR, an electric arc between the electrode and the bottom of the crucible (the
stool) is set to melt the electrode, which drips into a water-cooled copper crucible
and progressively builds the ingot. Melting is usually done in vacuum, but the partial
pressure of argon or nitrogen is sometimes used to retain gas or high vapor-pressure
elements in the alloy. The exposure of small volumes of molten metal to high vacuum
removes harmful high-vapor-pressure elements, like lead and bismuth, that are not
removed entirely during VIM. At the same time, it may also considerably reduce the
concentration of the beneficial high-vapor-pressure elements such as magnesium.
However, VAR does not remove sulfur, requiring appropriate raw material during
the primary VIM process. The VAR significantly improves the chemical and physical
homogeneity of the remelted alloy. An added advantage of the VAR process is that
it inherently does not superheat the metal. This advantage of the VAR, coupled with
the very high heat extraction capability of the process, makes it a better choice
for economical manufacturing of the large diameter ingots of segregation-prone
superalloys.
The ESR process is different from the VAR process as remelting of the electrode
is done by not striking an arc under vacuum, but in the air by melting the electrode
immersed in a molten slag superheated by resistance heating. It, however, appears
similar to the VAR process as the ingot in both the processes is built up progressively
in a water-cooled mold by melting a consumable electrode. Heat in ESR is generated
by the electrical resistance of the slag that typically comprises CaF2 along with
Al2 O3 and CaO. The molten slag provides the heat source for melting the electrode
face. The metal drops pass through the molten slag, unlike the vacuum in VAR. The
exposure of the molten metal to the molten slag, while it gathers into droplets on
the electrode face and as it passes through the slag, reduces oxides incorporated in
the alloy. The advantage of the ESR is that it dramatically reduces the sulfur content
through a reaction of melt with the CaF2 . Besides, it reduces high-vapor-pressure
elements like magnesium to a lesser extent than that in VAR. An additional benefit
of the ESR process is its ability to cast the alloy into rectangular cross-section slabs,
which can be directly converted into plates and sheets, unlike the VAR products,
which are always round/cylindrical. However, the ESR process is inherently more
sensitive to the segregation of solutes than the VAR. As a result, the maximum size
of segregation free ESR-ingots is smaller than that of the ingots produced by vacuum
arc remelting.
Superalloys ingots are usually forged and rolled into sheets or various wrought
products and shapes. However, some highly alloyed superalloys, like IN-100, Rene
95, Stellite 31, etc. or oxide dispersion strengthened alloys, which are difficult or
impractical to produce by the conventional ingot metallurgy route involving melting,
casting and forging, are normally processed either by casting or by adopting a
1.5 Melting and Consolidation of Superalloys 17
powder-metallurgy route. In addition, the powder-metallurgy route produces billets

or preforms with closer control of microstructure with respect to grain size and chem-
ical homogeneity, which cannot be achieved in highly alloyed superalloys by the ingot
metallurgy route. Some powder-metallurgy processes can directly produce near-net
shaped products by rapid prototyping or additive manufacturing techniques. These
techniques lower the cost by reducing the weight of the expensive raw materials and
minimizing the number of secondary machining operations.
1.6 Product Forms
Superalloys are available in various wrought and cast product forms depending upon
their desired applications and compositions. Cast products are produced by directly
solidifying the liquid metal to the final product with a net or near-net shape. In
contrast, wrought products are made from the cast billets after subjecting them
to extensive thermomechanical deformations by processes like forging, rolling or
extrusion to achieve the desired final products or preforms.
The standard cast products are alloy ingots and billet for forgings and extrusions,
and slabs for rolling into plate and sheet. For some alloys, like Alloy 625, centrifugally
cast tubes are also available as per ASME Boiler and Pressure Vessel Code. Cast
products like airfoils (i.e., blades and vanes) are commonly used in the hot section
areas of gas turbines. Most castings are polycrystalline, but airfoils may be cast as
single crystals or directionally solidified castings (Fig. 1.1). In directionally solidified
castings, grains are grown parallel to each other, usually parallel to the longitudinal
axis of airfoils. Single and directionally solidified crystals are commonly used as jet
engine turbine blades. The limitations of cast products are their non-uniform grain
size and chemical inhomogeneity. The chemical inhomogeneity arises due to solute
segregation, a natural consequence of the solidification process.
Wrought alloys are more homogenous and ductile compared to cast alloys.
Thermomechanical processing of alloys removes the chemical inhomogeneity of
cast structures and produces uniform microstructure with optimum ductility for
processing and subsequent use. Typical wrought products are:
• Forged billets and bars of cylindrical, tapered and stepped cross-sections
• Rolled coils of round and rectangular cross-sections
• Hot-rolled plates and sheets
• Hot extruded and cold pilgered tubing
• Cold drawn bar, rod, coil and wire
• Cold-rolled sheet and strip in standard and precision gauge tolerance
These products can be broadly categorized into (i) preforms and (ii) final prod-
ucts. Preforms, like forged round and rectangular bars or tubes, are used to produce
different components, like gas turbine disks, gear components, struts, engine parts,
etc. of desired specifications or specific larger shapes, like cryogenic storage tank
18 1 Introduction
components, nuclear fuel element spacers, etc. for various applications. The manufac-
turing of these components exploits the superior ductility of the wrought material.
Final products, like cold pilgered tubing or forged gas turbine disks, are directly
used for desired applications. However, some highly alloyed compositions are not
amenable to appreciable deformation for forming or shaping into wrought products.
Such alloys are fabricated and used in the cast form.
Cast and wrought alloys may have significantly different properties, but both
have advantages. The fine-grained structure and compositional homogeneity of
wrought products give them uniform mechanical properties and corrosion resis-
tance. Forged products are therefore preferred for low-cycle fatigue applications at
low-to-intermediate temperatures like turbine disks. On the other hand, the coarse
grain structures of casting make them intrinsically stronger and have better creep
resistance than wrought structures at elevated temperatures. In addition, the compo-
sition of castings can be tailored effectively to the limits of alloy composition that
are rather difficult to forge at high temperatures. That is why nickel-base superalloy
castings are preferred for high-stress, high-temperature turbine blade applications
because of their highest creep-rupture strength at elevated temperatures.
As noted earlier, some superalloys of highly alloyed compositions, like IN-100,
Rene 95, are challenging to produce by the conventional route of melting, casting
and forging, because of difficulties associated with their castings or deformation.
Such alloys are usually processed by powder-metallurgy route to near-net-shape or
final forging. The advent of additively manufacturing technologies over the last two
decades is revolutionizing the manufacturing of complex structures, usually produced
by casting or forgings. Additive manufacturing, or 3D printing, is an innovative fabri-
cating technique in which three-dimensional structures are progressively built by
depositing layers of material. It allows the creation of complex three-dimensional
shapes and geometries like internal cavities and lattice structures. Traditional manu-
facturing techniques are more time-consuming, incapable or economically unviable
to achieve such desired geometries. Additive manufacturing also allows alloy compo-
sitions that cannot be used as cast or forged products. Recently, Oak Ridge National
Laboratory (ORNL) have invented a new high-strength nickel–cobalt superalloy that
can be 3D-printed to crack-free and defect-resistant components, which maintain
their material integrity at temperatures up to 90% of their melting point [17].
1.7 Market Outlook
The prominence of superalloys as high-performance alloys stems from their opera-

tional efficiency and reduced environmental emissions. They are used for applica-
tions in various complex processes and operations across a large spectrum of industry
sectors, like aerospace and defense, oil and gas, marine, etc. These industries demand
materials with extraordinary mechanical properties, corrosion resistance, or both.
The global market of iron-, nickel- and cobalt-base superalloys is valued at about
USD 10.6 Billion in 2020 and is expected to reach over USD 15 Billion by the end of
1.7 Market Outlook 19
2026, growing at a compound annual growth rate (CAGR) of 5.6% during 2021–2026
[18]. Of this market, the most significant chunk of about 80% comprises nickel-based
superalloys. The nickel superalloy market is expected to grow at a CAGR of 6.7%
to acquire a market value of over USD 10 Billion by 2025 [19].
1.7.1 Major Drivers
The increasing demands for speciality materials in energy, defense, marine, and other
sectors due to burgeoning population and economic developments are constantly
driving the superalloys market across the globe. The Asia–Pacific region has been
the largest and fastest-growing market in recent years, encompassing about 40%
share of the global market. The significant contributions to the growth come from
India, Japan, South Korea, and China. North America is the second-largest market
due to the growing demand in aerospace, defense, and marine industries, primarily in
the US. The European market is mainly driven by the rising demand in the automotive
industry, particularly for passenger cars.
Based on the applications, major industry segments that drive the global superalloy
markets can be classified as (i) aerospace and defense; (ii) power generation; (iii)
oil and gas; (iv) refinery; (v) chemical; and (vi) others, which includes industries
like marine, pulp and paper, etc. The aerospace and defense sector is among the
largest superalloys market (Fig. 1.5) . The surging production of commercial aircraft
and the growing application of superalloys in the automotive industry is driving
its market significantly. Nickel superalloys are primarily used for manufacturing
gas turbine engines and rocket components like turbine blades, disks, airframes,
Fig. 1.5 The market share, by volume (tons) and revenue, of major industries driving the global
nickel superalloy market [19]
20 1 Introduction
etc. Several developed and developing countries are investing heavily in defense and
space development and diversification to fulfill various national objectives of military
success and defense strategy, which, in turn, are boosting the productivity of other
sectors.
The energy sector is also driving the superalloys market well. The rising energy
crisis across the globe is enhancing the demand for power generation using nuclear
power plants. Technological advancements are pushing the limits of materials to
produce steam at even higher temperatures, as in supercritical thermal plants and gas-
based power plants. These plants are increasingly using nickel superalloys for various
applications like gas and steam turbines, heat exchangers, scrubbers, etc. Besides,
higher corrosion resistance and reduced macrofouling properties make nickel-based
superalloys attractive for many applications in nuclear power plants. Other factors
like gas drilling activities and rising oil prices across the globe, increasing production
of premium vehicles, etc. are also boosting the sales of superalloys.
1.7.2 Market Size
Nickel-based superalloys comprise about 80% of the global superalloys market. In

2017, the global nickel-based superalloys market accounted for about 6.64 Billion
USD. Segmenting the nickel superalloys market based on the type of alloys gives
a good insight into the dominant alloys in the global market. Based on the type
of alloys, the nickel superalloys can be divided into the following categories: (i)
Alloy 600/601/602; (ii) Alloy 625; (iii) Alloy 718; (iv) Alloy 825/925; (v) Hastelloy
276/C22/X; (vi) Waspaloy; and (vii) Others. Figure 1.6 depicts the global nickel
superalloys market by volume and revenue generation based on 2017 data [19].
Alloy 718 is the most widely used and takes over about 50% of the market share,
both by volume and revenue. Alloy 718 takes the cake by virtue of its excellent tensile
strength and creep-rupture properties in corrosive environments at high temperatures.
The highest market share of Alloy 718 is on account of its maximum consumption
by the aerospace and defense industry segment, which itself holds about 40% of the
global superalloy market share. The market of Alloy 625 is spread across various
industry segments. It controls about 12% market and is expected to grow at a CAGR
of about 7% during the next five years.
1.7 Market Outlook 21
Fig. 1.6 The global market share, by volume (tons) and by revenue, of nickel-base superalloys cate-
gorized as a Alloy 600/601/602; b Alloy 625; c Alloy 718; d Alloy 825/925; e Hastelloy 276/C22/X; f
Waspaloy; and g others [19]. Note the sectors mentioned as Alloy 600, 825, and Hastelloy represents
the contributions of Alloy 600/601/602, Alloy 825/925 and Hastelloy 276/C22/X, respectively
1.7.3 Major Players and Tradenames
Over the years, many superalloy producers have come and gone. Following is the
list of significant superalloy producers based in various markets across the globe:
i. Allegheny Technologies Inc. (US)
ii. AMG Advanced Metallurgical Group (The Netherlands)
iii. Aperam (Luxembourg)
iv. Beijing Cisri-Gaona Materials and Technology Co. Ltd. (China)
v. Carpenter Technology Corporation (US)
vi. Doncasters Group Ltd. (UK)
vii. Hitachi Metals, Ltd. (Japan)
viii. Mishra Dhatu Nigam Ltd. (India)
ix. Nippon Yakin Kogyo Co., Ltd. (Japan)
x. Sandvik (Sweden)
xi. Shanghai Huibei Superalloy Co. Ltd. (China)
xii. Shenyang Beiheng New Materials Co. Ltd. (China)
xiii. Special Metals Corporation (US)
xiv. Thyssenkrupp Aerospace Germany GmbH (Germany)
xv. VDM Metals (Germany)
These producers market their products under various trade names. The trade name
may change for a specific superalloy, but the alloy’s number often remains the same.
For instance, Alloy 625 is marketed as Inconel 625 and Haynes 625 by M/s Special
Metals Corporation and M/s Haynes International, respectively. Table 1.5 gives a list
of common tradenames for some producers.
22 1 Introduction
Table 1.5 A list of some

Superalloy producer Trademark names
well-known tradenames
Special Metals Corporation Incoloy, Inconel, Udimet,
Nimonic, Monel
Haynes International Hastelloy, Haynes, Ultimet
United Technologies Waspaloy
Allegheny Technologies Astroloy, René
Deloro Stellite, Inc. Stellite
Carpenter Technology Custom Age 625 Plus
Westinghouse Corporation Discaloy
Martin Marietta MAR-M
Corporation
Cannon-Muskegon CMSX
Corporation
The list is not comprehensive and gives some commonly used trade
names
1.8 Alloy 625
Alloy 625 is a nickel–chromium-molybdenum based alloy known for its unique

combination of high strength, excellent fabricability and weldability, and outstanding
corrosion resistance. It is one of the most versatile nickel-base superalloys and covers
about 12% of its global market share. Invented as a solid-solution strengthened
alloy by Inco Alloys International Inc. in the 1950s [20], the alloy was initially
designed to replace 316-grade stainless steel in supercritical steam power plants
for its metallurgical stability, i.e., no age-hardening during service. However, initial
work concentrated on the strengthening effects of major individual elements, i.e.,
chromium, molybdenum, niobium, aluminum and titanium, was not encouraging. On
the other hand, alloys containing various combinations of niobium and molybdenum
in alloys containing varying amounts of nickel exhibited a significant increase in their
room temperature yield strength when subjected to aging treatment at 704 °C for 16 h
(Fig. 1.7) [20]. This discovery shifted the developmental activities to another alloy,
Alloy 718, which later became the work-horse alloy of nickel-base superalloys.
After a hiatus, the development of Alloy 625 resumed with an alloy containing
about 60% Ni, 15% Cr, 3% Nb, 2% Mo, 0.5% Al and 0.5% Ti and the rest Fe
(designated as MS-2) [20]. However, by then, the intended market of Alloy 625 for
supercritical steam applications had vanished. Moreover, the MS-2 alloy was only a
little stronger than other existing alloys like Alloy 600. The amounts of chromium
and molybdenum were then increased to 22% and 9%, respectively to improve the
room temperature strength of the alloy. Fortunately, an increase in chromium and
molybdenum contents also significantly increased the corrosion resistance of the
alloy. Finally, a patent application was submitted in January 1962, and a US patent
(Patent No. 3,160,500) was granted to its inventors H. L. Eiselstein and J. Gadbut in
1.8 Alloy 625 23
Fig. 1.7 The effect of ageing treatment on room temperature yield strength of nickel alloys
containing different amounts of niobium and molybdenum and other elements like chromium,
aluminium, titanium and iron, as per the design of Alloy 625. The alloys were annealed at 1038 °C
for 1 h before the ageing treatment at 677–732 °C for 16 h, followed by air cooling [20]
December 1964. The composition of the alloy has changed slightly since then. The
present composition is given in Table A.3 of Appendix A.
Over the years, applications of the alloy have expanded to temperatures ranging
from cryogenic temperature to about 980 °C. The high concentrations of chromium
and molybdenum give the alloy its high solid solution strength and resistance against
uniform as well as localized corrosion (pitting and crevice) in non-oxidizing environ-
ments. About 4% niobium gives it high-temperature strength. Niobium also stabilizes
against intergranular corrosion and sensitization during welding. These elements
together create a high-performance alloy by imparting Alloy 625 high tensile, creep,
and rupture strength; outstanding fatigue and thermal-fatigue strength; resistance
against corrosion against oxidizing and reducing environments, resistance against
oxidation, sulfidation and carburization; and excellent weldability and brazeability.
The alloy can be readily fabricated by standard industrial processes and needs no
post-weld thermal treatment to maintain its corrosion resistance.
The versatile properties of Alloy 625 under a wide range of temperatures and
pressures make it a widely accepted material for applications in chemical and petro-
chemical industries, heavy water plants and marine engineering. The alloy is one of
the most commonly used offshore materials for upstream pipework in the oil and
gas industry and is compliant with NACE MR0175/ISO 15156-3 standard [21]. This
standard covers the use of materials in H2 S containing environments. It allows the
use of Alloy 625, in annealed or solution-annealed condition, in any combination of
temperature, partial pressure of H2 S, chloride concentration and in situ pH occurring
in production environments. Alloy 625 also has excellent resistance against pitting in
24 1 Introduction
pressurized high-temperature water (260–316 °C), making it useful for many applica-
tions for reactor-core and control rod components in nuclear water reactors. In recent
years, the alloy has been used to make exhausts for Formula 1 class racing cars [22].
The alloy is potentially useful for many more applications. It is being considered
a candidate material for applications in advanced reactor concepts because of its
high allowable design strength at elevated temperatures, especially between 650 and
760 °C. Table 1.6 gives a list of significant applications of Alloy 625 in different
industries.
A better understanding of the alloy during service exposures and the development
of new processing techniques have resulted in the introduction of new alloys, like
Alloy 625 LCF and Custom Age 625 Plus alloys, based on Alloy 625 by slightly
changing its composition. The LCF variant of the alloys is produced by tightly
controlling the compositions of carbon, silicon, and nitrogen to very low levels
employing the VIM/ESR double melting practice and controlling the grain size to
ASTM #5 or smaller during thermomechanical processing. The LCF variant has an
enhanced resistance to fatigue at temperatures up to about 650 °C. The Custom Age
625 Plus alloy is an age-hardenable variant of Alloy 625 in which the titanium content
is increased to about 1.3% to accelerate the precipitation of the γ phase particles.
Alloy 625 is very close to Alloy 718 in terms of the phase transformations and
the associated microstructures. Both these alloys can be precipitation strengthened
primarily by the metastable γ phase particles. The corresponding hardening phase
in both the alloys is the ordered orthorhombic δ phase based on Ni3 Nb [15]. This
behavior of the two alloys is different from most precipitation-hardenable nickel-
base alloys, which are strengthened by γ phase precipitates. The Alloy 718 is a
high-strength alloy intended for applications up to 700 °C with good fatigue strength
and excellent stress-rupture properties. Like Alloy 625, Alloy 718 has good corrosion
resistance in various aggressive environments and is resistant to oxidation up to about
1000 °C and can be used at cryogenic temperatures, down to about –250 °C. The
sluggish age-hardening response of Alloy 718 enables it to be welded and annealed
with no spontaneous hardening unless cooled slowly [3]. Alloy 718 contains about
17–21% chromium, 2.8–3.3% molybdenum and 4.75–5.5% niobium and much lower
amounts of aluminum (0.2–0.8%) and titanium (0.65–1.15%).
1.9 Why a Book on Alloy 625?
Ever since the introduction of Alloy 625 for ultra-critical steam piping applica-
tions, it continues to find new applications in the aerospace, automobile, chemical
processing, oil refining & production, marine, waste treatment, pulp & paper, power
and nuclear industries. The alloy undergoes significant microstructural modifica-
tions during long term thermal exposure at intermediate temperatures. It develops
complex microstructures by precipitating various intermetallic and carbide phases in
the disordered nickel matrix that embrittle the alloy. However, a good understanding
of their formation can help reverse the properties of the alloy to the codal values.
1.9 Why a Book on Alloy 625? 25
Table 1.6 Major applications of Alloy 625 in various industries

Industry Properties Applications
Fuel refining High resistance at elevated distillation tower; seamless
temperatures against pipes; overhead condensers;
naphthenic acid corrosion, transfer lines; nozzles; return
oxidation and sulfidation, bends
and chloride stress-corrosion
cracking
Seawater applications Excellent resistance against Mooring cables; propeller
localized attack, high blades for boats; submarine
corrosion-fatigue strength, propulsion motors; exhaust
high tensile strength, and ducts of naval boats; sheathing
resistance to chloride for undersea communication
stress-corrosion cracking cables; submarine transducer
controls; steam-line bellows;
electrical cable connectors,
fasteners and flexure devices;
oceanographic instrument
components
Aerospace industry High tensile, creep and Aircraft ducting systems,
rupture strength, outstanding exhaust systems, thrust-reverser
fatigue strength and excellent systems; fuel and hydraulic line
weldability tubing; heat exchanger tubing;
honeycomb structures for
housing engine controls; spray
bars, bellows, turbine shroud
rings; combustion system
transition liners; turbine seals;
compressor vanes; and
thrust-chamber tubing for rocket
Chemical processing Good combination of Bubble caps; tubing; reaction
strength and corrosion vessels; distillation columns;
resistance against oxidizing heat exchangers; transfer
as well as reducing corrosive piping; valves, etc.
media at elevated
temperatures
Core and control rod Strength and resistance Valves; stems; tubing; springs
components of nuclear water against localized corrosion in
reactors high temperature
(260–316 °C) waters
Hydrocracking and catalytic Good combination strength Pressure containing cracking
cracking units and resistance against units; reaction vessels; tubing
hydrogen sulfide
(high-temperature
corrosion), and ammonia and
ammonium sulfide
(lower-temperature corrosion
and erosion-corrosion)
26 1 Introduction
The book provides content to those who desire to develop a complete under-
standing of Alloy 625. The book’s emphasis is on the relationships between the
microstructure and its mechanical properties, and their variation during prolonged
service exposures. It also provides an overview of its corrosion behavior in various
environments. The book would be helpful as a guide to practicing engineers in the
industry interested in using Alloy 625 and in academia for students pursuing advanced
courses in Materials Science.
The book is divided into eight chapters, including the “Introduction” chapter,
to introduce the high-performance alloys “Superalloys”. The chapter gives the
reader an overview of different aspects of the superalloys in general, including their
contribution to the global economy. Other chapters exclusively deal with “Phases”,
“Microstructure”, “Mechanical Behavior”, “Corrosion Behavior”, “Fabrication”, and
“Life Management” of Alloy 625 components. A separate chapter has been included
on “Alloy 625 PLUS” to give readers a brief account of the age-hardenable variant
of Alloy 625. These properties of the alloy are compared with those of many other
alloys. All the alloys are referred to mostly through their generic names throughout
the book.
References
1. Sims CT (1987) In: Sims CT, Stoloff NS, Hagel WC (eds) Superalloys II: high temperature
materials for aerospace and industrial power, Chapter 1. Wiley, New York. ISBN: 0-471-01147-
9
2. Donachie MJ (2002) Superalloys: a technical guide, 2nd edn, Chapter 14. ASM International.
ISBN: 0-87170-749-7
3. Inconel alloy 718, 2007. https://www.specialmetals.com/documents/technical-bulletins/inc
onel/inconel-alloy-718.pdf
4. CarTech ® Custom Age 625 PLUS® Alloy identification type analysis, n.d. https://www.car
pentertechnology.com/hubfs/7407324/Material%20Saftey%20Data%20Sheets/725.pdf
5. HAYNES ® 242 alloy data sheet, 2020, http://haynesintl.com/docs/default-source/pdfs/new-
alloy-brochures/high-temperature-alloys/brochures/242-brochure.pdf?sfvrsn=a17229d4_28
6. Donachie MJ (2002) Superalloys: a technical guide, 2nd edn., Chapter 1. ASM International.
ISBN: 0-87170-749-7.
7. Geddes B, Leon H, Huang X (2010) Superalloys: alloying and performance. ASM International.
ISBN-10: 0-61503-040-9
8. Energy Conversion, Encyclopedia Britannica, 15th edn., 18 (2002) 332–413
9. Holt RT, Wallace W (1976) Impurities and trace elements in nickel-base superalloys. Int Met
Rev 21:1–24. https://doi.org/10.1179/imtr.1976.21.1.1
10. Zhang D, Cheng Y, Jiang R, Wan N (2018) Introduction. In: Turbine blade investment casting
die technology. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-662-54188-3_1
11. Poole JM, Fischer JJ, Hack GAJ, McColvin GM (1994), advances in high temperature structural
materials and protective coatings. National Research Council of Canada http://www.ewp.rpi.
edu/hartford/~ernesto/F2011/EP/MaterialsforStudents/Opsahl/Hetmanczyk2007.PDF
12. HAYNES® 244® alloy data sheet, 2020. http://haynesintl.com/docs/default-source/pdfs/new-
alloy-brochures/high-temperature-alloys/brochures/244-brochure.pdf
13. Cao WD (2004) Nickel-base alloy, U.S. Patent 6730264 B2
14. Verma A, Singh JB (2021) Stabilization of a D022 phase in Ni–Cr–Mo–W–Ti Alloys. Metall
Mater Trans A 52:4317–4323. https://doi.org/10.1007/s11661-021-06404-4
References 27
15. Ross EW, Sims CT (1987) In: Sims CT, Stoloff NS, Hagel WC (eds) Superalloys II: high
temperature materials for aerospace and industrial power, Chapter 4. Wiley, New York. ISBN:
0-471-01147-9
16. Vanadium supply and demand outlook. The National Academies Press, Washington 1978.
https://doi.org/10.17226/19907
17. Murray SP, Pusch KM, Polonsky AT, Torbet CJ, Seward GGE, Zhou N, Forsik SAJ, Nandwana
P, Kirka MM, Dehoff RR, Slye WE, Pollock TM (2020) A defect-resistant Co–Ni superalloy
for 3D printing. Nat Commun 11:4975. https://doi.org/10.1038/s41467-020-18775-0
18. Press Release, MarketWatch.com, 28 June 2021
19. Report Nickel Superalloy Market 2020, Global Market Insights, Delaware, USA, (n.d.)
20. Eiselstein HL, Tillack DJ (1991) The invention and definition of alloy 625, in: 1991, pp 1–14.
https://doi.org/10.7449/1991/superalloys_1991_1_14
21. NACE MR0175/ISO 15156-3, petroleum and natural gas industries—materials for use in H2S-
containing environments in oil and gas production—part 3: cracking-resistant CRAs (corrosion-
resistant alloys) and other alloys. Am Natl Stand Inst/NACE Int (2009)
22. Curà F, Mura A, Sesana R (2012) Aging characterization of metals for exhaust systems. Int J
Automot Technol 13:629–636. https://doi.org/10.1007/s12239-012-0061-0
Chapter 2
Phases in Alloy 625
Alloy 625, originally designed as a single-phase solid-solution alloy, contains high

concentrations of various alloying elements added primarily to impart desired
mechanical and corrosion properties. The high concentrations of elements like
chromium, molybdenum and niobium induce the precipitation of multiple phases
during solidification, processing and thermal exposure. The precipitation of various
phases in the austenite nickel matrix makes the microstructure of the alloy very
complex and alters its properties significantly. Precipitation of many phases is asso-
ciated with cubic to non-cubic transformations, which decide the distribution and
morphology of particles in the matrix. Such cubic to non-cubic phase transformations
give rise to several physically distinct crystallographic orientations of the precipi-
tating phase called “variants”, whose number depends upon the lattice symmetry
reduction due to the transformation. The Chapter briefly introduces crystallographic
aspects of various phases in Alloy 625 and lays a foundation for their indentification
and understanding of phase transformations associated with their evolution.
2.1 Definitions of Phase, Crystal Structure

and Solid-solution
A phase is defined as a chemically homogeneous and physically uniform state of

matter. A crystalline phase has characteristic chemistry and crystal structure. In
a crystalline phase, atoms take positions over geometrically arranged points in a
symmetrical pattern termed “lattice”. This arrangement of atoms is called “crystal
structure”. The smallest group of atoms, having the crystal symmetry, is called a
“unit cell”. A unit cell repeat itself in a three-dimensional space. A crystalline solid
containing a uniform mixture of two or more chemical species that share a crystal
lattice is called a “solid solution”. The word “solution” signifies the intimate mixing
of the species at the atomic level. The species or element present in the highest
amount is termed “solvent”, while elements in the lesser concentrations are termed
https://doi.org/10.1007/978-981-19-1562-8_2
30 2 Phases in Alloy 625
Fig. 2.1 Unit cells of a FCC crystal and b γ phase (L12 structure)
“solutes”. The solubility limit of a solute in a solid solution is governed by its atomic
size and crystal structure compared to the solvent. Some elements readily form solid
solutions over a wide range of concentrations, while others may not.
When the solute concentration exceeds the solubility limit, a second phase precip-
itates at temperatures high enough for diffusion to occur. When atoms of different
species are distributed randomly over lattice points, the crystalline structure is called
a (chemically) disordered phase. When atoms of various types are distributed in an
orderly manner, defined by specific equivalent positions of the lattice, the phase is
called an “ordered” phase. The ordered arrangement of two or more atoms gives a
covalent character to the metallic bonding of the phase, and such phases are often
referred to as intermetallic compounds. The lattice structure of an ordered phase is
termed “superlattice”. A superlattice may be regarded as a superimposition of lattices
of individual atomic species. For instance, nickel and aluminum atoms in a nickel-13
wt% aluminum alloy are distributed randomly at the corners and face centers of its
face-centered cubic (FCC) unit cell with the same probability. This phase is termed
the γ phase (Fig. 2.1a). The γ phase orders below 1395 °C to form an ordered FCC
structure [1], L12 structure, where aluminum atoms occupy all the corners of the unit
cell and the face-centered sites are occupied by nickel atoms (Fig. 2.1b). The phase
with the L12 structure is often termed as the γ phase because of its similarity with
the disordered FCC γ phase.
2.2 Crystal Structures of Phases in Alloy 625
Alloy 625 primarily comprises a nickel-base solid solution as a matrix phase that may
contain a variety of intermetallic and carbide phases. Table 2.1 lists crystallographic
features of various phases that usually form in Alloy 625 [2–9]. The intermetallic
Table 2.1 Crystallographic details of various phases that may form in Alloy 625
Phase Common Pearson’s Space Prototype Formula Crystal Atoms Lattice parametersb (nm) Angle References
structure symbol group structure per a b c (°)
typea unit
cell
Gamma (γ ) A1 cF4 Fm-3 m Cu Ni Face-centered 4 0.3609 0.3609 0.3609 90° [2, 4]
cubic
Gamma double D022 tI8 I4/mmm Al3 Ti Ni3 (Nb,Ti,Al) Ordered 8 0.362 0.362 0.741 90° [2, 5]
prime (γ ) body-centered
tetragonal
Ni2 (Cr, Mo) 25
D2h oP6 Pmmm Pt2 Mo Ni2 (Cr,Mo) Ordered 6 0.2513 0.7553 0.3580 90° [2, 8c]
body-centered
orthorhombic
2.2 Crystal Structures of Phases in Alloy 625
Delta (δ) D0a oP8 Pmmn β-Cu3 Ti Ni3 Nb Ordered 8 0.5116 0.426 0.4565 90° [2]
body-centered
orthorhombic
M23 C6 Carbide D84 cF116 Fm-3 m Cr23 C6 Cr23 C6 Complex 116 1.050–1.070 1.050–1.070 1.050–1.070 90° [2, 6]
cubic
M6 C Carbide E93 cF112 Fd-3 m Fe3 W3 C (Cr,Mo,Ni)6 C Complex 112 1.091–1.13 1.091–1.13 1.091–1.13 90° [2–8]
cubic
MC Carbide B1 cF8 Fm-3 m NaCl (Nb,Ti)C Cubic 8 0.430–0.444 0.430–0.444 0.430–0.444 90° [2–8]
Mu (μ) Phase D85 hR13 R-3 m W6 Fe7 Mo6 Ni7 Hexagonal 39 0.48 0.48 2.56 γ = [2, 10, 3]
120°
Laves Phase C14 hP12 P63 /mmc Zn2 Mg (Cr,Ni)2 (Si,Nb,Mo) Hexagonal 12 0.47–0.48 0.47–0.48 0.77–0.78 γ = [2, 5, 10, 3]
Ni3 Mo2 Si 120°
a The “common structure type” is based on the Strukturbericht designation commonly used to describe frequently encountered similar types of crystal structures
b The range signifies that the lattice parameter values vary with composition
c The reported lattice parameter of the Ni (Cr, Mo) phase in a model Ni–Cr–Mo alloy containing Cr and Mo solutes equivalent to the amount present in Alloy 625
2
31
phases that may form are Ni2 (Cr, Mo), gamma double prime (γ ) and the delta
(δ) phases, while the carbides phases may be MC, M23 C6 and M6 C. Detrimental
phases, like sigma (σ ), mu (μ), and Laves phases, may also form in the alloy, partic-
ularly during solidification or processing of the alloy. The following describes crystal
structures of these phases.
2.2.1 Gamma (γ) Phase
The γ phase is a disordered solid solution of nickel-containing other alloying

elements and has an FCC structure (Fig. 1a). An FCC unit cell has four atoms at
the following coordinate positions:
N i : 0, 0, 0; 1/2, 1/2, 0; 1/2, 0, 1/2; 0, 1/2, 1/2
Each atom at the corner of the cell contributes one-eighth to the unit cell, and
each atom at the centers of the faces contributes one-half resulting in four numbers
of effective atoms per unit cell (Table 2.1).
2.2.2 Gamma Double Prime (γ ) Phase
The γ phase is an intermetallic compound of N3 M stoichiometry with an ordered

body-centered tetragonal structure. This structure is termed the D022 structure
(Fig. 2.2). A unit cell of the D022 structure contains eight atoms, two of which
are M atoms and six are N atoms, arranged at the following coordinates of the unit
cell:
M : 0, 0, 0; 1/2, 1/2, 1/2

N : 0, 0, 1/2; 1/2, 1/2, 0; 0, 1/2, 1/4; 1/2, 0, 1/4; 0, 1/2, 3/4; 1/2, 0, 3/4
This arrangement of atoms in the D022 structure is related to the arrangement

of atoms in the L12 structure. The former can be visualized as a stacking of two
L12 unit cells, stacked one above the other, along a <001> 1 direction with a relative
displacement of 1/2 <110> perpendicular to the <001> . Because of this closeness to
the L12 structure, the D022 phase is termed as γ phase. The c parameter of the D022
1 Directions and planes are denoted by the standard Miller indices used to describe crystallographic
planes and directions of crystal lattices11 . This system expresses planes by integers h, k, and l, and
directions by integers, usually expressed by u, v and w. Planes and directions expressed as (hkl) and
[uvw] notations, respectively, represent specific planes or directions in the crystal basis. In contrast,
planes and directions expressed, respectively by {hkl} and < uvw > notations denote the set of all
planes and directions that are symmetrically equivalent to (hkl) and [uvw]. All Miller indices are
expressed in the cubic crystal system unless otherwise subscripted.
2.2 Crystal Structures of Phases in Alloy 625 33
Fig. 2.2 The unit cell of the

D022 structure of the γ
phase
structure is roughly double the a-parameter. Figure 2.2 shows a unit cell of the D022
structure of the γ phase with Ni3 Nb stoichiometry, which has its lattice parameters
as a = 0.362 nm and c = 0.740 nm [2, 3]. The precipitation of the γ phase from the
parent γ phase matrix follows a distinct orientation relationship with it, given by
(001)γ " //{001}

[100]γ " //100
This orientation relationship implies a matching between (001)γ " of the γ phase
with any one of the {001} plane of the γ phase. Since the [001]γ " direction of the
tetragonal cell may align with any one of the three 001 axes of the cubic cell, the
ordered D022 phase possesses three mutually orthogonal orientational variants.2
2All the indices for the for non-cubic phases/structures throughout the book are subscripted by the
corresponding phase or structure. Indices without subscripts indicate the cubic basis of the γ phase.
2.2.3 Ni2 (Cr, Mo) Phase
The Ni2 (Cr, Mo) phase is an intermetallic compound of N2 M stoichiometry with

an ordered body-centered orthorhombic structure. The unit cell of the Ni2 (Cr, Mo)
phase has a Pt2 Mo type structure that contains six atoms, of which two are M, and
four are N atoms, arranged at the following coordinates of the orthorhombic cell.
M : 0, 0, 0; 1/2, 1/2, 1/2

N : 0, 1/3, 0; 0, 2/3, 0; 1/2, 1/6, 1/2; 1/2, 5/6, 1/2
The unit cell of the ordered orthorhombic Ni2 (Cr, Mo) phase vis-à-vis the disor-
dered FCC cell is shown in Fig. 2.3. It has lattice parameters a = 0.2513 nm, b =
0.7553 nm, c = 0.3580 nm [11]. When the orthorhombic Ni2 (Cr, Mo) phase precip-
itates out from the parent γ matrix, it follows an orientation relationship with the
matrix, given by:
[001]o // 001
[010]o // 110
The C-axis ([001]o ) of the orthorhombic cell (the subscript “o” denotes the
orthorhombic structure) may align itself with any of the three axes of the cube and
the other two orthogonal axes, A ([100]o ) and B ([010]o ), may direct themselves
along appropriate 110 directions. The two structures follow the following vector
relationships.
1 3
A= (a1 + a2 ); B = (−a1 + a2 ); C = a3
2 2
Where a1 , a2 and a3 refer to the three axes of the cubic cell. This relationship results
in six independent orientation variants of the Ni2 (Cr, Mo) phase with respect to the
γ matrix, defined as per Table 2.2.

Ni2 Cr phase with N2 M
stoichiometry
Table 2.2 Lattice

Variant (1 0 0)o (0 1 0)o (0 0 1)o
correspondence and variant
nomenclature of the ordered 1 1/2(1 1 0) 3/2(1 1 0) (0 0 1)
Ni2 (Cr, Mo) phase in relation 2 1/2(1 1 0) 3/2(1 1 0) (0 0 1)
to the parent FCC lattice
3 1/2(1 0 1) 3/2(1 0 1) (0 1 0)
4 1/2(1 0 1) 3/2(1 0 1) (0 1 0)
5 1/2(0 1 1) 3/2(0 1 1) (1 0 0)
6 1/2(0 1 1) 3/2(0 1 1) (1 0 0)
2.2.4 Delta (δ) Phase
The δ phase has an ordered orthorhombic D0a (β-Cu3 Ti type) structure with Ni3 Nb
stoichiometry. It is the equilibrium phase of the γ phase in the binary nickel-
niobium system. The δ phase forms during extended thermal exposures above 650
°C. Figure 2.4 shows a unit cell of the D0a structure of the δ phase. For the N3 M
stoichiometry, there are eight atoms in the unit cell of the δ phase, of which two are
M atoms, and the remaining six are N atoms. The coordinates of these atoms are:
M : 0, 0, 2/3; 1/2, 1/2, 1/3

N : 0, 1/2, 1/3; 1/2, 0, 2/3; 1/4, 0, 1/6; 3/4, 0, 1/6; 1/4, 1/2, 5/6; 3/4; 1/2; 5/6
When the δ phase precipitates out in the γ matrix, it follows the following
precipitate-matrix orientation relationship.
(001)δ //{111}
[010]δ //110

D0a structure of the δ phase
Table 2.3 Lattice

Variant (1 0 0)δ (0 1 0)δ (0 0 1)δ
correspondence and variant
nomenclature of the δ phase δ1 1/2(1 1 2) (1 1 0) 2/3(1 1 1)
in relation to the FCC lattice δ2 1/2(1 1 2) (1 1 0) 2/3(1 1 1)
δ3 1/2(1 1 2) (1 1 0) 2/3(1 1 1)
δ4 1/2(1 1 2) (1 1 0) 2/3(1 1 1)
δ5 1/2(1 2 1) (1 0 1) 2/3(1 1 1)
δ6 1/2(2 1 1) (0 1 1) 2/3(1 1 1)
δ7 1/2(1 2 1) (1 0 1) 2/3(1 1 1)
δ8 1/2(2 1 1) (0 1 1) 2/3(1 1 1)
δ9 1/2(2 1 1) (0 1 1) 2/3(1 1 1)
δ10 1/2(1 2 1) (1 0 1) 2/3(1 1 1)
δ11 1/2(2 1 1) (0 1 1) 2/3(1 1 1)
δ12 1/2(1 2 1) (1 0 1) 2/3(1 1 1)
This orientation relationship implies matching close-packed planes of the precip-

itate and matrix phases. This orientation relationship gives 12 orientation variants of
the δ phase, defined according to Table 2.3.
2.2.5 Carbide Phases
Three types of carbide phases, namely, MC, M23 C6 and M6 C, may form in Alloy 625.
The MC carbide has an ordered cubic crystal structure of NaCl type (Fig. 2.5). The
unit cell of the MC carbide contains four atoms each of M and C type at following
coordinates:
M : 0, 0, 0; 1/2, 1/2, 0; 1/2, 0, 1/2; 0, 1/2, 1/2

C : 1/2, 0, 0; 0, 1/2, 0; 0, 0, 1/2; 1/2, 1/2, 1/2
A unit cell of the MC phase may have a lattice parameter in the range of 0.43–
0.444 nm [3, 4], depending upon its composition. The M23 C6 and M6 C phases have
complex FCC and diamond cubic structures, respectively. Figures 2.6 and 2.7 show
unit cells of the M23 C6 and M6 C carbides in relation to the unit cell of the parent
matrix phase. The M23 C6 phase contains 92 M atoms and 24 C atoms in its unit cell,
while the M6 C phase contains 96 M atoms and 16 C atoms. Like the MC phase, the
unit cells of the M23 C6 and M6 C phases may have lattice parameters in the range
1.050–1.070 and 1.091–1.13 nm [5, 8, 6], respectively, which are approximately
three times that of the disordered nickel solid-solution matrix. When these carbides
(designated by subscript C) precipitate out from a supersaturated matrix, they follow
cube to cube orientation relationships with the matrix as

MC carbide (ordered FCC
cubic)

M23 C6 carbide (a complex
cubic structure) in relation to
an FCC unit cell (smaller
cell)
{100}C // {100}
001C // 001
or

M6 C carbide (a complex
diamond cubic structure) in
relation to an FCC unit cell
(smaller cell)
{111}C //{111}

11̄0 C // 11̄0
2.2.6 Topologically Close-Packed Phases
The topologically close-packed (TCP) phases are made of layers of close-packed

atomic {111} planes, separated by relatively large distances, unlike the geometrically
close-packed phases. The geometrically close-packed phases, like γ and γ , are
closely packed in all directions. The crystal structures of the TCP phases are quite
complex, and their unit cells may contain many atoms. As a consequence, TCP
phases display a wide range of compositions. Several TCP phases, like σ, μ, R, χ,
G and Laves, are reported in nickel-base alloys containing high concentrations of
refractory elements like molybdenum, chromium, tungsten, tantalum, niobium, etc.
These phases generally form through electron bonding of the terminal elements that
form the phase. Among the elements present in these phases, one or more usually
exhibit an electropositive character (e.g., chromium, molybdenum and tungsten).
The TCP phases that may form in Alloy 625 are σ, μ and Laves phases. The μ
phase usually forms in alloys with high levels of molybdenum or tungsten and σ
forms in alloys containing a high amount of chromium. The Laves usually forms
in alloys containing high levels of molybdenum, titanium and tantalum. Unlike the

tetragonal structure of the
Fe2 Crσ TCP phase
electron bonding nature of σ and μ phases, the terminal atoms in the Laves phases
are bonded by their size factors. Figures 2.8, 2.9 and 2.10 show the unit cells of σ, μ
and Laves phases, respectively. The body-centered tetragonal unit cell of the σ phase
contains 30 atoms, while the rhombohedral unit cell of the μ phase contains 13 atoms
(equivalent hexagonal cell contains 39 atoms). The hexagonal unit cell of the Laves
phase contains 12 atoms. Both σ and μ phases are represented by a typical formula
Ax By , where x and y may vary from 1 to 7. However, the difference in the two phases
comes from the atoms involved in their formation. The σ phase usually forms with
nearly equal atomic size elements, while the μ phase forms when their atomic size
differs significantly [6]. The Laves phases tend to have an A2 B stoichiometry with
general formula (Fe, Mn, Cr, Si)2 (Mo, Ti, Nb). The close-packed layers of all the
TCP phases maintain a high degree of coherency with {111} planes of the γ , γ and
δ phases.
2.3 Basic Concepts of Diffraction and Phase Identification
Various phases can be identified through their diffraction behavior. A summary of

principles and concepts of diffraction important for understanding the diffraction
behavior of phases in the present context is given below.
2.3.1 Diffraction Behavior of Crystalline Solids

and the Bragg’s Law
Different phases can be identified from the interaction behavior of x-rays or other
electromagnetic radiations with electrons of the atoms. A brief description of this
behavior and how it helps identify a phase is discussed considering x-ray radiations,
though the same principles apply to all radiations.

rhombohedral structure of
the W6 Fe7 μ phase
When x-rays interact with atoms in a crystalline lattice, electrons emit x-rays of the
same frequency in all directions. However, the emitted waves are not in phase in all
directions and cause destructive interference (cancel intensity of one another). Only
in certain specific directions the emitted waves are in phase and reinforce the intensity
of one another. This specific direction depends upon the angle of the incident x-rays,
its wavelength (λ), and the spacing between the reflecting atomic planes (d) that
satisfy Bragg’s condition λ = 2dSinθ, where θ is the angle of incidence (Fig. 2.11).
Such a co-operative scattering (diffraction) of x-rays by all the atoms of the unit cell
is analogous to the reflection of x-rays by the atomic plane.
2.3 The Basic Concepts of Diffraction and Phase Identification 41
Fig. 2.10 The unit cell of the Zn2 Mg Laves phase in relation to an FCC unit cell (green colored
atoms)
Fig. 2.11 The basic principles of x-ray diffraction and Bragg law
The intensity of a diffracted wave is proportional to the square of its structure

factor. The structure factor depends upon the constituent atoms and their arrange-
ments in the unit cell and the Miller indices of the reflecting plane. Each structure
factor, F, can be considered a vector (commonly known as a k-vector) in the 3-
dimensional space having an amplitude and a phase, and represents the total of
waves scattered by all the atoms of the unit cell in the direction of reflection. The
structure factor for a given diffracting plane, {hkl}, is given by [10]

N
Fhkl = f n exp 2πi[hu n + kvn + lwn ] (2.1)
1
where f n is the atomic scattering factor/amplitude associated with the nth atom in
the unit cell, un , vn , wn are the fractional coordinates of that atom, and N are the total
number of atoms in the unit cell. For example, substituting the positions (0,0,0), (1/2,
1/2, 0), (1/2, 0, 1/2), and (0, 1/2, 1/2) of four atoms of an FCC unit cell in Eq. 2.1
would give its structure factor as

F = f 1 + expi(hk) + expi(hl) + expi(kl) (2.2)
In this equation, expnπi = 1 when n = even, and = −1 when n is odd. Therefore,

F = 4f when h, k and l indices are all odd or all even, and F = 0 when mixed.
Relationship 2.2 implies that only atomic planes with unmixed Miller indices cause
constructive reflections from their planes.
This analysis can be further extended to understand the effect of ordering on the
structure factor by introducing chemical order in the lattice. Considering the L12
ordered phase formed after ordering of the nickel-13% aluminum solid solution. The
L12 lattice contains nickel and aluminum atoms at specific positions of the FCC unit
cell as
Al : (0, 0, 0)
N i : (1/2, 1/2, 0), (1/2, 0, 1/2), (0, 1/2, 1/2)
Substituting these positions in Eq. 2.1 would

give the structure factor relationship

for the L12 structure as FL12 = f Al + f Ni expi(hk) + expi(hl) + expi(kl) , and

f Al + 3 f Ni (for unmixed h, k, l)
FL12 = (2.3)
f Al − f Ni (for mixed h, k, l)
where f Ni and f Al are atomic scattering factors of Ni and Al atoms, respectively. The
structure factor equals f Al + 3f Ni when h, k, l are all odd or even, similar to the FCC
structure. But it becomes non-zero (= f Al – f Ni ) for the mixed reflections, unlike
the forbidden reflections in a face-centered cubic structure. This analysis implies
that even for the unmixed reflections, the diffraction peaks will appear for an L12
structure, though their intensities would be much less than those with unmixed h,
k, l reflections. The intense reflections that arise due to the addition of the phase
factors of the two types of atoms are termed “fundamental reflections”. In contrast,
the chemically sensitive weaker reflections that appear due to the difference in the
phase factors are termed “superlattice reflections”.
2.3.2 The Reciprocal Lattice
When striking a photographic plate or a detector, the diffracted waves from a crystal
with non-zero structure factors leave their imprints in the form of well-defined spots
that form a diffraction pattern. If diffraction occurs from a polycrystalline mate-
rial containing randomly oriented crystals, these spots appear as rings. Allowed
wave vectors that yield diffracted waves constitute the k-space, also known as the
“momentum” or “reciprocal” space. The transfer of momentum due to construc-
tive interference of the diffracted waves also forms a lattice termed the “reciprocal
lattice”.
A reciprocal lattice, represented by a1∗ , a2∗ and a3∗ axes, is defined by vectors
orthogonal to the “real” lattice given by Massalski and Barrett [11]
(a2 ∧ a3 )
a∗1 =
V
∗ (a3 ∧ a1 )
a2 =
V
(a ∧ a2 )
a∗3 =
1
(2.4)
V
where a1 , a2 and a3 represent the “real” (original) lattice basis vectors, V (= a1 .a2 ∧
a3 ) represents the volume of the direct unit cell, and the symbol ∧ represents the
cross product between two vectors. Since each reciprocal lattice axis is the vector
product of two (real) lattice axes, a reciprocal lattice axis is perpendicular to the
plane defined by the two lattice axes in the real space. The axes of the two lattices
are related as follows:
a1 .a∗1 = a2 .a∗2 = a3 .a∗3 = 1 (2.5)
and
a1 .a∗2 = a1 .a∗3 = a2 .a∗1 = a2 .a∗3 = a3 .a∗1 = a1 .a∗2 = 0 (2.6)
Figure 2.12 shows the relationship between the real and reciprocal lattices. The
unit cell of the real lattice is indicated by solid black lines, while broken red lines
draw the unit cell of the corresponding reciprocal lattice. The origin of the reciprocal
lattice axes is designated by O. The repeat translation of the reciprocal lattice unit cell
in three dimensions forms the complete reciprocal lattice. Each lattice point in the
Fig. 2.12 Relationship

between the unit cells of real
and reciprocal lattices. Solid
black lines show the unit cell
of the real lattice, while
broken red lines draw the
unit cell of the reciprocal
lattice
reciprocal space can be represented by a vector, H hkl , corresponding to a particular

set of planes (hkl) of the real lattice according to the relation,
H hkl = h.a∗1 + k.a∗2 + l.a∗3 (2.7)
which is normal to the lattice planes (hkl) in the real space. The magnitude of
the vector H hkl is the inverse of the d-spacings of (hkl) planes, 1/d hkl , from the
lattice origin. Therefore, the location of the point in the reciprocal space defines the
orientation and d-spacing of lattice planes in the corresponding real space lattice.
The farther away a reciprocal lattice point is from the origin, the smaller is the d-
spacing of the corresponding lattice planes. Therefore, the reciprocal lattice contains
a uniquely defined array of points with the periodicity of the corresponding real
lattice. The reciprocal lattice is similar to a “real” lattice but is termed so because all
its dimensions are reciprocal length units. Vectors in the reciprocal lattice are usually
suffixed by * to distinguish them from the real lattice. The intensity of reciprocal
points (in diffraction patterns) is characteristic of a given phase, which can be utilized
along with their position (1/d hkl ) as fingerprints to identify the phase uniquely.
2.3.3 The Ewald Sphere
How the intensity of reciprocal points (reflection spots) depends upon the orienta-
tion of the crystal with respect to the incident x-ray beam can be understood from
the Ewald sphere concept, which relates wave vectors of the incident x-rays, the
diffracted x-rays and the diffraction angle (θ ) for a given reflection in the reciprocal
space. An Ewald sphere is a geometrical construction of a radius defined by the
reciprocal of the wavelength of the incident wave, 1/λ, with the diffracting crystal
located at its center, C (Fig. 2.13). Figure 2.13 shows two Ewald spheres of radii
1/λ1 and 1/λ2 with corresponding centers as C 1 and C 2 to illustrate the effect of the
radiation wavelength, discussed later. However, for the time being, the subscripts
can be ignored. The incident beam can be visualized as a vector from I to C. The
diffracted beam is the vector from C to P. Both the incident beam and the diffracted
beam are at an angle θ from a set of crystal planes, say (hkl), separated by the d-
spacing d hkl . Both incident beam vector, CO, and the diffracted beam vector CP
Fig. 2.13 A schematic representation of the Ewald sphere construction, superimposed by a recip-
rocal lattice. The radius of the sphere is given by 1/λ. The figure shows two Ewald spheres of radii
1/λ1 and 1/λ2 to highlight the difference in the number of reciprocal lattice points in contact with
the Ewald surface for the two wavelengths. Vector OP represents the diffraction vector, g, due to
constructive interference of the incident beam from the (hkl) plane
start at point C and end at points O and P, respectively, on the surface of the Ewald
sphere. The vector from O to P is the reciprocal lattice vector Hhkl and is defined as
the diffraction vector g associated with Bragg’s reflection of the (hkl) plane. All the
reciprocal lattice points that lie on the surface of the Ewald sphere satisfy the Bragg
condition. Therefore, the reciprocal lattice point, P*, on the sphere’s surface repre-
sents the constructive interference of the incident beam with the (hkl). The incident
beam passes through the origin of the reciprocal lattice, O, on the Ewald sphere and
coincides with the lattice position of the real lattice. By changing the orientation of
the reciprocal lattice, all reciprocal lattice points can be mapped and measured. The
Ewald sphere construction, combined with the reciprocal lattice, gives a simple way
of visualizing the diffraction phenomenon for a single crystal.
A similar diffraction principle is applicable for other radiations like electrons
and neutrons. However, the difference in the radiation wavelength would affect the
number of reciprocal lattice points on the surface of the Ewald sphere. This is illus-
trated by Ewald spheres of two different radii 1/λ2 and 1/λ2 , in Fig. 2.13. This implies
that when the wavelength of the radiation is large, e.g., say, of x-rays, the radius of
the Ewald sphere would be of the order of the spacing between the reciprocal points
and only one reciprocal lattice point would intersect with the surface of the Ewald
sphere at a given crystal orientation. But when λ is much small, say, of the order of
picometer as in the case of electrons accelerated at about 200 keV, a large number
of reciprocal points would intersect with the sphere because the radius of the Ewald
sphere would be about two orders larger than that of the lattice spacing.
An Ewald sphere with a large radius has important implications for interpreting
the diffraction patterns of a crystal in different zones. A zone represents certain sets of
crystal planes that intersect along a common line, and the line of their intersection is
termed the “zone axis”. In principle, any two non-parallel planes can cross, but a zone
contains many different sets of crystal planes. A zone axis, [uvw], thus represents all
the planes whose normals are perpendicular to the [uvw] direction. Therefore, for an
electron diffraction pattern in a [uvw] zone axis, i.e., when the incident beam is along
the [uvw] direction, all the {hkl} planes for which hu + kv + lw = 0 and which lie
on the surface of the Ewald sphere would appear as diffraction spots. For instance,
the [001] zone axis of an FCC phase would show reflections from (200), (020), (220)
and their combinations that satisfy the hu + kv + lw = 0 condition.
2.4 Lattice Correspondence Between Cubic and Non-cubic

Phases
Consider a transformation from a cubic to non-cubic phase. If Miller indices of

directions and planes of a cubic phase are respectively written as column and row
matrices as [u]C and (h)C, the corresponding indices in the non-cubic crystal structure,
[u]N and (h)N , can be obtained by the following matrix relationships.
2.4 Lattice Correspondence Between Cubic and Non-cubic Phases 47
[u] N = N
[u]C
C
(2.8)
(h) N = (h)C [ N
C ]−1 (2.9)
−1
where N
C and N
C are 3 × 3 matrices expressing the correspondence relation-
−1
ship between the two bases, so that the columns of the N
C matrix are the cube
components of the base vectors of the ordered structure (superlattice cell). Using
these matrices, it is possible to find the correspondence relationship of any direction
or plane between the parent cubic structure and the non-cubic superlattice structure.
2.5 Identification of Phases in Alloy 625
All the phases that form in Alloy 625 are ordered derivatives of the disordered FCC
γ phase. However, the slight difference between the atomic structure factors of the
ordering elements, e.g., between Ni and Nb of the δ phase and their low volume
fractions, does not give a reasonable number of diffraction peaks with sufficient
intensity when examined by x-ray diffraction. X-ray diffraction can identify these
particles if they are extracted out of the matrix, but such an analysis is associated
with its limitations. Electron diffraction by transmission electron microscopy is the
best technique for unambiguous identification of such phases. Further, the phase
transformations relevant to the precipitating phases in the present context arise due
to chemical ordering of the lattice below a specific temperature. Chemical ordering
of the disordered lattice breaks cubic symmetry of the disordered matrix as different
size of the ordering atoms distorts the lattice slightly in the direction of ordering.
Therefore, certain planes and directions of the matrix and the precipitating phase
remain parallel or nearly parallel during the ordering transformation, based on orien-
tation relationships between the two. Consequently, the fundamental reflections of the
precipitating phase coincide with those of the matrix phase. However, the chemical
order in the ordered phase manifests itself as superlattice reflections at character-
istic positions, which are otherwise forbidden for the disordered FCC phase. These
superlattice reflections help in identifying the nature of the precipitating phase. The
superlattice reflections appear at unique positions in a diffraction pattern depending
upon the direction of order, i.e., the ordered variant involved. Positions of these
superlattice reflections can be identified based on the structure factor and lattice
correspondence analysis of the ordered phase. This analysis can be used to simulate
electron diffraction patterns for a given zone axis.
2.5.1 Identification of the γ Phase
The structure factor for the D022 structure of the N3 M γ phase is given by [12]

h k l l h k
F D022 = f M + f M exp 2πi + + + f N exp 2πi + f N exp 2πi +
2 2 2 2 2 2

k l h l
+ f N exp 2πi + + f N exp 2πi +
2 4 2 4

k 3l h 3l
+ f N exp 2πi + + f N exp 2πi +
2 4 2 4
where f N and f M are the atomic scattering factors for N and M atoms, respectively.
On rearranging the terms, one gets

F D022 = 1 + exp πi(h + k + l)

l l
f M + f N exp πi exp πi h + exp πik + exp πi (2.10)
2 2
All reflections for which h + k + l is odd, the structure factor is zero and the reflec-
tions are forbidden. The forbidden reflections arise because of the body-centered
nature of the D022 unit cell. For h + k + l = even, the structure factor for fundamental
and superlattice reflections, respectively can be thus be expressed as

for h, k, l all even, l = 4n
F fD022 = 2(3 f N + f M ) n = 0, 1, 2 . . .
for l even, hand k odd, l = 4n + 2
(2.11)
⎧ ⎫
⎨ for h, k, l all even, l = 4n + 2 ⎪
⎪ ⎬
FsD022 = 2( f M − f N ) for l even, h andk odd, l = 4n n = 0, 1, 2 . . . (2.12)
⎪
⎩ ⎪
⎭
for l odd, h and k mixed
The subscripts f and s denote the fundamental and superlattice reflections, respec-
tively. The values of the F for different values of h, k and l, are listed in Table
2.4.
Table 2.5 gives lattice correspondence matrices expressing the relationship
between the parent FCC structure and three variants of the tetragonal structure of the
γ phase. Table 2.6 provides the correspondence between planes of the FCC and the
D022 structures, calculated using Eq. 2.9. The plane correspondences between the
two structures assume an axial ratio of 2 for the D022 structure. Table 2.4 indicates
that reflections like (002)γ *, and (110)γ * and (011)γ * would appear as superlattice
reflections for the D022 variant having the c-axis parallel to [001] of the FCC structure.
These reflections are equivalent to (001)*, (110)* and (0 1 ½)* reciprocal vectors
of the cubic lattice. Similarly, identical superlattice reflections corresponding to the
other two variants of the γ the phase would also appear when all the three variants
are present. Therefore, the fundamental reciprocal vectors {200}* and {220}* would
be halved by {001}* and {110}* superlattice reflections, and the {240}* reciprocal
vectors would be divided into four parts by the {1/2 1 0}* superlattice reflection when
2.5 Identification of Phases in Alloy 625 49
Table 2.4 Structure factor (F) for different h, k and l values of planes of the D022 structure with
N3 M stoichiometry
h+k+l h k l F Typical reflections
Miller indices in Miller indices in
D022 basis cubic basis
Odd Odd Even Even 0 (100)γ , (102)γ , (100), (101),
(300)γ (300)
Even Odd Even (010)γ , (012)γ , (010), (011),
(212)γ (211)
Even Even Odd (001)γ , (201)γ , (0 0 21 ), (2 0 21 ),
(003)γ
(0 0 23 )
Odd Odd Odd (111)γ , (311)γ , (1 1 21 ), (3 1 21 ),
(331)γ
(3 3 21 )
Even Even Even l/2 Even 2(3f N + f M ) (220)γ , (004)γ , (220), (002),
(024)γ , (404)γ (022), (402)
Odd Odd l/2 Odd (112)γ , (116)γ , (111), (113),
Even Even l/2 Odd (312)γ , (136)γ (311), (133)
2(f N − f M ) (002)γ , (202)γ , (001), (201),
(042)γ (041)
Odd Odd l/2 Even (110)γ , (114)γ , (110), (112),
(130)γ , (310)γ (130), (310)
Odd Even Odd (101)γ , (301)γ , (1 0 21 ), (3 0 21 ),
(303)γ , (321)γ
(3 0 23 ), (3 2 21 )
Even Odd Odd (011)γ ,(031)γ , (0 1 21 ), (0 3 21 ),
(013)γ , (211)γ
(0 3 23 ), (2 1 21 )
Some illustrative examples of allowed (F = non-zero) and forbidden(F = 0) reflections are listed
along with their equivalent indices in cubic basis. The orientation of the D022 structure is assumed
to be of Variant 1 of the ordered phase (Table 2.5)
all the three variants of the γ phase are present. Therefore, all the diffraction patterns
containing {200}*, {220}* and {240}* reflections would show superlattice reflec-
tions, as illustrated by the simulated [001] zone axis diffraction pattern (Fig. 2.14).
Thus, a <001> zone axis would contain superlattice reflections corresponding to all
the three variants of the D022 phase, which can be imaged individually by dark-field3
imaging in a transmission electron microscope.
3 Bright-field (BF) and dark field (DF) are two diffraction contrast imaging modes in transmission
electron microscopy, depending upon whether the transmitted or a diffracted electron beam is chosen
for forming the image [14]. In the BF mode, imaged features appear dark in a bright background,
while they appear bright in a dark background in the DF mode.
Table 2.5 Lattice

C −1
T
C
= T
Variant C T
correspondence matrices
relating the FCC phase to ⎡ ⎤ ⎡ ⎤
different variants of the D022 100 200
⎢ ⎥ ⎢ ⎥
phase 1 ⎢0 1 0⎥ 1⎢
2 0⎥
⎣ ⎦ 2⎣0 ⎦
002 001
⎡ ⎤ ⎡ ⎤
010 002
⎢ ⎥ ⎢ ⎥
2 ⎢0 0 2⎥ 1⎢
0 0⎥
⎣ ⎦ 2⎣2 ⎦
100 010
⎡ ⎤ ⎡ ⎤
002 020
⎢ ⎥ ⎢ ⎥
3 ⎢1 0 0⎥ 1⎢
0 2⎥
⎣ ⎦ 2⎣0 ⎦
010 100
Notation T
C represents correspondence from tetragonal basis,
T, to cubic basis, C
2.5.2 Identification of the Ni2 (Cr, Mo) Phase
For the Pt2 Mo-type phase of N2 M stoichiometry, the structure factor relationship is
given by Singh [14]

h k l k 2k
F = f M + f M exp 2πi
N2 M
+ + + f N exp 2πi + f N exp 2πi
2 2 2 3 3

h k l h 5k l
+ f N exp 2πi + + + f N exp 2πi + +
2 6 2 2 6 2

2k 4k
F N2 M
= 1 + exp πi(h + k + l) f M + f N exp πi + exp πi
3 3
This relationship simplifies to the form

πk
F N2 M
= 1 + exp πi(h + k + l) f M + 2 f N cos exp πik (2.13)
3
Again, all the reflections for which h + k + l is odd are forbidden because of the
body-centered nature of the unit cell. When h + k + l is even, the reflections would
be fundamental or superlattice depending upon the value of k, and their structure
factors will be
F fN2 M = 2(2 f N + f M ) for k = 3, 6 . . . (2.14)

Table 2.6 Plane

Cubic D022 phase
correspondence of different
variants of the D022 phase (100) Variant (010) Variant (001) Variant
with respect to the FCC lattice 111 112 112 112
111 112 112 112
111 112 112 112
111 112 112 112
200 200 020 004
020 020 004 200
002 004 200 020
220 220 024 204
220 220 024 204
202 204 220 024
202 024 220 024
022 024 204 220
022 024 204 220
024 028 404 240
024 028 404 240
042 044 208 420
042 044 208 420
204 208 420 044
204 208 420 044
402 404 240 028
402 404 240 028
240 240 028 404
240 240 028 404
420 420 044 208
420 420 044 208
The γ phase planes which would show superlattice reflections
along their reciprocal vectors are shown in Bold
FsN2 M = 2( f N − f M ) for k = 3, 6 . . . (2.15)
F for different values of h, k and l are listed in Table 2.7.

Lattice correspondence matrices relating the parent cubic structure to different
variants of the ordered orthorhombic structure (designated as o) of the Ni2 (Cr, Mo)
phase are listed in Table 2.8. Some relevant plane correspondences between the
FCC phase and different variants of the Ni2 (Cr, Mo) phase are given in Table 2.9. To
simulate the position of superlattice reflections of the orthorhombic phase in electron
diffraction patterns, an analysis of its structure factor (Table 2.7) and correspondence
of planes with the cubic phase (Table 2.9) can be performed like the one done in
Fig. 2.14 Simulated [001]

zone axis pattern of the γ
phase illustrating the
appearance of superlattice
reflections due to different
variants of the ordered phase.
1, 2 and 3 refers to the [001],
[010] and [100] variants of
the γ phase
Sect. 2.5.1. The reciprocal vectors {220}*, {113}* and {024}* of the orthorhombic
phase would each be divided into three parts because of superlattice reflections of
one or more variants of the ordered phase. Specific variants would show superlat-
tice reflections in particular directions in the reciprocal lattice. These superlattice
reflections can identify different variants of the Ni2 (Cr, Mo) phase unambiguously.
Figure 2.15 shows a set of such simulated electron diffraction patterns.
2.5.3 Identification of the δ Phase
For the δ phase with N3 M stoichiometry, the structure factor is given by Sundararaman
[13]

l h+k l
F D0a = f M exp 4πi + exp 2πi +
3 2 3
⎡
k l h 2l h l 3h l ⎤
exp 2πi + + exp 2πi + + exp 2πi + + exp 2πi +
⎢ 2 3 2 3 4 6 4 6 ⎥
+ fN ⎢
⎣ ⎥
⎦
h k 5l 3h k 5l
+ exp 2πi + + + exp 2πi + +
4 2 6 4 2 6
(2.16)
Table 2.7 Structure factor (F) for different h, k and l values of planes of the Ni2 (Cr,Mo) phase
h+k+l h k l F Typical reflections
Orthorhombic FCC basis
basis
Odd Odd Even Even 0 (100)o , (102)o , (110), (112),
(300)o (330)
Even Odd Even (010)o , (012)o , ( 13 1
3 0), ( 13 1
3 2),
(212)o
( 53 37 2)
Even Even Odd (001)o , (201)o , (001), (221),
(003)o (003)
Odd Odd Odd (111)o , (311)o , ( 23 43 1), (2 43 1),
(331)o (241)
Even Even K/3 Even Even 2(2f N + f M ) (002)o , (200)o , (002), (220),
(202)o , (060)o (222), (220)
Odd K/3 Odd Even (130)o , (132)o , (020), (022),
(330)o , (332)o (240), (242)
Odd K/3 Even Odd (101)o , (103)o , (111), (113),
(161)o , (361)o (131), (151)
Even K/3 Odd Odd (031)o , (231)o , (111), (131),
(033)o , (233)o (113), (133)
Even K/3 Even 2(f M − f N ) (020)o , (022)o , ( 23 23 0), ( 23 23 2),
(220)o , (042)o
( 43 38 0), ( 43 43 2)
Odd Even (110)o , (112)o , ( 23 43 0), ( 23 43 2),
(150)o
( 23 38 0)
Odd Non-integral Odd (121)o , (123)o , ( 13 35 1), ( 13 35 3),
(321)o , (141)o
( 73 11
3 1), ( 1 7
3 3 1)
Even Odd (011)o , (013)o , ( 13 31 1), ( 13 31 3),

(211)o , (051)o
( 53 37 1), ( 56 65 1)
Some illustrative examples of allowed (F = non-zero) and forbidden (F = 0) reflections are listed
along with their equivalent indices in cubic basis. The orientation of the Ni2 (Cr,Mo) phase is
assumed to be of Variant 2 of the ordered phase (Table 2.8)
The values of F for various combinations of h, k and l are listed in Table 2.10.
The structure factor is non-zero for all reflections except for which h + k is odd and
l = 3n, where n is an integer.
The lattice correspondence matrices relating the FCC structure to the
orthorhombic structure of the δ phase (designated as δ) are listed in Table 2.11.
The plane correspondence between the two phases can be identified using the corre-
spondence matrices. Some relevant plane correspondence relationships between the
Table 2.8 Lattice

O −1

C −1
O
= C
C
= O
Variant C O
relating the FCC phase to ⎡ ⎤ ⎡ ⎤
different Ni2 (Cr,Mo) phase 1 30 3 −3 0
⎢
1⎢
⎥ ⎢ ⎥
3 0⎥
1⎢
variants 1 2 ⎣ −1 ⎦ 3⎣ 1 1 0⎥
⎦
0 02 0 0 3
⎡ ⎤ ⎡ ⎤
1 −3 0 3 30
⎢
1⎢
⎥ ⎢ ⎥
1 3 0⎥
1⎢
2 2⎣ ⎦ 3⎣−1 1 0⎥
⎦
0 0 2 0 03
⎡ ⎤ ⎡ ⎤
1 3 0 30 3
⎢
1⎢
⎥ ⎢ ⎥
0 0 2⎥
1⎢
3 2⎣ ⎦ 3⎣ 1 0 −1 ⎥
⎦
1 −3 0 03 0
⎡ ⎤ ⎡ ⎤
1 −3 0 3 0 −3
⎢
1⎢
⎥ ⎢ ⎥
0 2⎥
1⎢
4 2⎣ 0 ⎦ 3 ⎣ −1 0 −1 ⎥
⎦
−1 −3 0 0 3 0
⎡ ⎤ ⎡ ⎤
0 0 2 0 −3 −3
⎢
1⎢
⎥ ⎢ ⎥
3 0⎥
1⎢
5 2 ⎣ −1 ⎦ 3⎣ 0 1 −1 ⎥
⎦
−1 −3 0 3 0 0
⎡ ⎤ ⎡ ⎤
0 0 2 0 3 −3
⎢
1⎢
⎥ ⎢ ⎥
1 3 0⎥
1⎢
6 2⎣ ⎦ 3⎣ 01 1 ⎥
⎦
−1 3 0 30 0
Notation O
C represents correspondence from orthogonal basis,
O, of the Ni2 (Cr,Mo) phase to the cubic basis, C, of the γ matrix
FCC phase and 12 variants of the δ phase are given in Table 2.12. From Table 2.10,
specific planes that exhibit superlattice reflections of the δ phase can be identified
based on their structure factor values. However, the superlattice reflections would
appear only for a specific variant of the δ phase. For example, the allowed (200)δ *
and (001)δ * superlattice reflections of the δ phase appear only along (400)δ * and
(006)δ * reciprocal vectors of the δ phase (Table 2.10). As a result, the (400)δ * and
(006)δ * reciprocal vectors would be divided into 2 and 6 parts, respectively of the
δ phase. The (400)δ and (006)δ planes are parallel to only some specific planes of
the {220} and {224} families of the cubic structure depending upon the ordering
direction (i.e., variant) of the δ phase. For instance, the (400)δ is parallel to the (2 2
0) FCC plane for δ 1 and δ 4 variants only, while the (006)δ planes are parallel to (2
2 4) for the δ 7 variant only (Table 2.12). Therefore, zone axes containing (2 2 0)*
and (2 2 4)* reciprocal vectors would exhibit superlattice reflections corresponding
Table 2.9 Plane correspondence of different variants of the Ni2 (Cr,Mo) superlattice with respect
to FCC lattice
Cubic Ni2 (Cr,Mo) Phase
Variant 1 Variant 2 Variant 3 Variant 4 Variant 5 Variant 6
111 031 101 101 031 101 031
111 101 031 031 101 101 031
111 101 031 101 031 031 101
111 031 101 031 101 031 101
200 130 130 130 130 002 002
020 130 130 002 002 130 130
002 002 002 130 130 130 130
220 060 200 132 132 132 132
220 200 060 132 132 132 132
202 132 132 200 060 132 132
202 132 132 060 200 132 132
022 132 132 132 132 200 060
022 132 132 132 132 060 200
311 161 231 231 161 103 033
311 231 161 161 231 103 033
311 231 161 231 161 033 103
311 161 231 161 231 033 103
131 161 231 103 033 231 161
131 231 161 033 103 231 161
131 231 161 103 033 161 231
131 161 231 033 103 161 231
113 033 103 231 161 231 161
113 103 033 161 231 231 161
113 103 033 231 161 161 231
113 0 33 103 161 231 161 231
The Ni2 (Cr,Mo) phase planes which would show superlattice reflections along their reciprocal
vectors are shown in Bold
to the δ 1 /δ 4 and δ 7 variants. Reciprocal vectors corresponding to other planes would

show superlattice reflections for other variants. This is illustrated by the simulated
[001] and [110] zone axes electron diffraction patterns of the δ phase (Fig. 2.16).
It is important to note here that the {111}* and {311}* reciprocal vectors in the
Fig. 2.15 Simulated electron diffraction patterns corresponding to the <103> and <112> zone axes
in the vicinity of the [001] zone, which can be utilized to identify different variants of the Ni2 (Cr,Mo)
phase. The numbers 1–6 mark the positions of the superlattice reflections corresponding to different
variants of the phase. Different zones have been underlined
Table 2.10 Structure factor (F) for different h, k and l values of planes of the δ (D0a ) along with
some illustrative examples of allowed (F = non-zero) and forbidden (F = 0) reflections
h k l F Examples
Odd Odd l = 3n 2(f M – f N ) (110)δ , (133)δ , (313)δ , (113)δ , (330)δ
l = 3n (f M – f N ) (111)δ , (112)δ , (331)δ , (132)δ
Even l = 3n 0 (100)δ , (120)δ , (123)δ , (323)δ
l = 3n 3(f M – f N ) (101)δ , (121)δ , (102)δ , (122)δ , (321)δ
Even Odd l = 3n 0 (210)δ , (213)δ
h/2 = odd l = 3n, l = odd 3(f M – f N ) (211)δ , 231)δ
l =3n, l = even 3(f M – f N ) (212)δ
Even Odd l = 3n 0 (010)δ , (013)δ , (016)δ , (036)δ , (410)δ
h/2 = Even l = 3n, l = odd 3(f M – f N ) (011)δ
l =3n, l = even 3(3f N + f M ) (012)δ
Even Even l = 3n, l = odd 2(3f N + f M ) (203)δ , (223)δ , (243)δ , (263)δ
h/2 = odd l = 3n, l = even 2(f M – f N ) (200)δ , (220)δ , (206)δ
l = 3n, l = odd (3f N + f M ) (221)δ , (201)δ
l = 3n, l = even (f M – f N ) (222)δ , (202)δ
Even Even l = 3n, l = odd 2(f M – f N ) (003)δ , (023)δ , (423)δ , (403)δ , (043)δ
h/2 = Even l = 3n, l = even 2(3f N + f M ) (020)δ , (026)δ , (426)δ , (400)δ , (006)δ
l = 3n, l = odd (f M – f N ) (001)δ , (005)δ , (012)δ
l = 3n, l = even (3f N + f M ) (002)δ , (022)δ , (004)δ , (422)δ
Table 2.11 Lattice

δ −1 δ

C −1
δ
= C
C
= δ
Variant C
relating the disordered γ ⎡ ⎤ ⎡ ⎤
phase to different variants of 3 −6 4 2 2 −4
⎢
1⎢
⎥ ⎢ ⎥
6 4⎥
1⎢
the δ phase δ1 6⎣ 3 ⎦ 6 ⎣ −3 3 0 ⎥
⎦
−6 0 4 3 3 3
⎡ ⎤ ⎡ ⎤
3 6 4 2 −2 −4
⎢
1⎢
⎥ ⎢ ⎥
6 −4 ⎥
1⎢
δ2 6 ⎣ −3 ⎦ 6⎣3 3 0 ⎥
⎦
−6 0 4 3 −3 3
⎡ ⎤ ⎡ ⎤
−3 6 −4 −2 −2 −4
⎢
1⎢
⎥ ⎢ ⎥
−6 −4 ⎥
1⎢
δ3 6 ⎣ −3 ⎦ 6⎣ 3 −3 0 ⎥⎦
−6 0 4 −3 −3 3
⎡ ⎤ ⎡ ⎤
−3 −6 −4 −2 2 −4
⎢
1⎢
⎥ ⎢ ⎥
3 −6 4 ⎥
1⎢
δ4 6⎣ ⎦ 6 ⎣ −3 −3 0 ⎥
⎦
−6 0 4 −3 3 3
⎡ ⎤ ⎡ ⎤
3 6 4 2 −4 2
⎢
1⎢
⎥ ⎢ ⎥
0 4⎥
1⎢
δ5 6 ⎣ −6 ⎦ 6⎣3 0 −3 ⎥
⎦
3 −6 4 3 3 3
⎡ ⎤ ⎡ ⎤
−6 0 4 −4 −2 2
⎢
1⎢
⎥ ⎢ ⎥
−6 −4 ⎥
1⎢
δ6 6 ⎣ −3 ⎦ 6⎣ 0 −3 −3 ⎥
⎦
3 −6 4 3 −3 3
⎡ ⎤ ⎡ ⎤
−3 −6 −4 −2 4 2
⎢
1⎢
⎥ ⎢ ⎥
0 −4 ⎥
1⎢
δ7 6⎣ 6 ⎦ 6 ⎣ −3 0 −3 ⎥
⎦
3 −6 4 −3 −3 3
⎡ ⎤ ⎡ ⎤
6 0 −4 4 2 2
⎢
1⎢
⎥ ⎢ ⎥
4 ⎥
1⎢
δ8 6⎣3 6 ⎦ 6⎣ 0 3 −3 ⎥
⎦
3 −6 4 −3 3 3
⎡ ⎤ ⎡ ⎤
−6 0 4 −4 2 2
1⎢
⎢ ⎥ ⎢ ⎥
δ9 ⎥ 1⎢ ⎥
6 ⎣ 3 −6 4 ⎦ 6 ⎣ 0 −3 3 ⎦
3 6 4 3 3 3
(continued)

δ −1 δ

C −1
δ
= C
C
= δ
Variant C
⎡ ⎤ ⎡ ⎤
3 −6 4 2 4 2
⎢
1⎢
⎥ ⎢ ⎥
0 −4 ⎥
1⎢
δ 10 6⎣6 ⎦ 6 ⎣ −3 0 3⎥
⎦
3 6 4 3 −3 3
⎡ ⎤ ⎡ ⎤
6 0 −4 4 −2 2
⎢
1⎢
⎥ ⎢ ⎥
6 −4 ⎥
1⎢
δ 11 6 ⎣ −3 ⎦ 6⎣ 0 3 3⎥
⎦
3 6 4 −3 −3 3
⎡ ⎤ ⎡ ⎤
−3 6 −4 −2 −2 2
⎢
1⎢
⎥ ⎢ ⎥
0 4 ⎥
1⎢
δ 12 6 ⎣ −6 ⎦ 6⎣ 3 0 3⎥
⎦
3 6 4 −3 3 3
Notation δ
C represents the correspondence matrix for the trans-
formation from the orthorhombic δ phase to the cubic (C)
structure
[110] zone axis are shown to be halved by (010)δ and (210)δ reflections, respec-
tively, despite their forbidden nature (Table 2.11). The appearance of such forbidden
reflections may occur due to the double diffraction4 of the diffracted beam.
No single zone axis would show superlattice reflections of all variants of the δ
phase. Often the superlattice reflections of more than one variant may be super-
imposed in a given zone axis. For example, the superlattice reflections of δ 2 and
δ 4 variants that divide the (2 2 0) reflection in half (Fig. 2.16a) are superimposed.
Therefore, a judicious combination of different zone axes is required to delineate all
the variants unambiguously. A [001] zone axis diffraction would show superlattice
reflections corresponding to six variants that are superimposed by those of the other
six (Fig. 2.16a). Similar limitations would be there for other zone axis diffraction
patterns. For instance, (001)δ superlattice reflections of δ 4 , δ 6 and δ 11 variants super-
impose in the [110] zone axis (Fig. 2.16b). Therefore, imaging of particles using
this superlattice reflection would bring particles of all these three variants in bright
contrast. In such cases, different variants can be unambiguously identified using a
combination of electron diffraction images with specific superlattice reflections and
the habit plane analysis of the microstructural features.
4 Double diffraction occurs when a diffracted beam travelling through a crystal is diffracted again
either within the same crystal or while passing into another crystal [14]. Double diffraction may
cause the appearance of otherwise forbidden reflections.
Table 2.12 Plane correspondence between FCC and different variants of the δ phase
FCC phase δ Phase
δ1 δ2 δ3 δ4 δ5 δ6 δ7 δ8 δ9 δ10 δ11 δ12
111 002 362 602 362 002 362 362 602 002 602 362 362
111 362 602 362 002 362 362 602 002 602 362 36 2 002
111 362 002 362 602 602 002 362 362 362 002 602 362
111 602 362 002 362 362 602 002 362 362 362 002 602
200 364 364 364 364 364 604 364 604 604 364 604 364
020 364 36 4 364 364 604 364 604 364 364 604 364 604
002 604 604 604 604 364 364 364 364 364 364 364 364
220 608 040 608 040 368 320 368 320 368 320 368 320
220 040 608 040 608 320 368 320 368 320 368 320 368
202 368 368 320 320 608 368 040 320 36 8 608 320 040
202 320 320 368 368 040 320 608 368 320 040 368 608
022 368 320 320 368 368 040 320 608 608 320 040 368
022 320 368 368 320 320 608 368 040 040 368 608 320
422 3 6 16 3 18 8 15 6 8 360 3 6 16 12 12 8 3 18 8 600 6 0 16 15 6 8 12 12 8 360
(continued)
59
60
FCC phase δ Phase

δ1 δ2 δ3 δ4 δ5 δ6 δ7 δ8 δ9 δ10 δ11 δ12
422 360 15 6 8 3 18 8 3 6 16 360 12 12 8 15 6 8 6 0 16 600 3 18 8 12 12 8 3 6 16
422 3 18 8 3 6 16 360 15 6 8 15 6 8 6 0 16 360 12 12 8 12 12 8 3 6 16 600 3 18 8
422 15 6 8 360 3 6 16 3 18 8 3 18 8 600 3 6 16 12 12 8 12 12 8 360 6 0 16 15 6 8
242 3 6 16 360 15 6 8 3 18 8 6 0 16 360 12 12 8 15 6 8 3 6 16 600 3 18 8 12 12 8
242 3 18 8 15 6 8 360 3 6 16 12 12 8 3 18 8 600 3 6 16 15 6 8 12 12 8 360 6 0 16
242 360 3 6 16 3 18 8 15 6 8 600 3 6 16 12 12 8 3 18 8 360 6 0 16 15 6 8 12 12 8
242 15 6 8 3 18 8 3 6 16 360 12 12 8 15 6 8 6 0 16 360 3 18 8 12 12 8 3 6 16 600
224 6 0 16 12 12 8 600 12 12 8 3 6 16 3 18 8 360 15 6 8 3 6 16 15 6 8 360 3 18 8
224 12 12 8 600 12 12 8 6 0 16 3 18 8 360 15 6 8 3 6 16 15 6 8 360 3 18 8 3 6 16
224 12 12 8 6 0 16 12 12 8 600 15 6 8 3 6 16 3 18 8 360 318 8 3 6 16 15 6 8 360
224 600 12 12 8 6 0 16 12 12 8 360 15 6 8 3 616 3 18 8 360 3 18 8 3 6 16 15 6 8
(continued)
2 Phases in Alloy 625
FCC phase δ Phase
δ1 δ2 δ3 δ4 δ5 δ6 δ7 δ8 δ9 δ10 δ11 δ12
420 324 3 18 4 324 3 18 4 044 15 6 4 044 15 6 4 324 12 12 4 324 12 12 4
420 3 18 4 324 3 18 4 324 12 12 4 324 12 12 4 324 15 6 4 044 15 6 4 044
240 324 3 18 4 324 3 18 4 324 12 12 4 324 12 12 4 044 15 6 4 0 44 15 6 4
240 3 18 4 324 3 18 4 324 15 6 4 044 15 6 4 044 12 12 4 324 12 12 4 324
204 324 324 15 6 4 15 6 4 324 044 3 18 4 12 12 4 044 324 12 12 4 3 18 4
204 15 6 4 15 6 4 324 324 3 18 4 12 12 4 324 044 12 12 4 3 18 4 044 324
402 044 044 12 12 4 12 12 4 324 324 3 18 4 15 6 4 324 324 15 64 3 18 4
402 12 12 4 12 12 4 044 044 3 18 4 15 6 4 324 324 15 6 4 318 4 324 324

042 044 12 12 4 12 12 4 044 324 3 18 4 15 6 4 324 324 15 6 4 3 18 4 324
042 12 12 4 044 044 12 12 4 15 6 4 324 324 3 18 4 3 18 4 324 324 15 6 4
024 324 15 6 4 15 6 4 324 044 3 18 4 12 12 4 324 324 12 12 4 3 18 4 044
024 15 6 4 324 324 15 6 4 12 12 4 324 044 3 18 4 3 18 4 044 324 12 12 4
The δ phase planes which would show superlattice reflections along their reciprocal vectors are shown in Bold
61
Fig. 2.16 Simulated electron diffraction patterns of the δ phase: a [001] zone axis; b [110] zone
axis
2.5.4 Identification of Carbide Phases
Substituting the coordinates of M and C atoms into the Eq. 2.1 gives the structure
factor relationship for the MC phase as

FMC = f M exp 2πi(0) + exp πi(h + k) + exp πi(h + l) + exp πi(k + l)

+ f C exp πi(h) + exp πi(k) + exp πi(l) + exp πi(h + k + l)

FMC = f M 1 + exp πi(h + k) + exp πi(h + l) + exp πi(k + l)

+ f C exp πi(h) + exp πi(k) + exp πi(l) + exp πi(h + k + l)
Where f M and f C are atomic scattering factors of M and C atoms, respectively. For
the MC phase, the structure factor is again zero for all the reflections for mixed
types of indices, and corresponding reflections are forbidden as in a face-centered
structure. However, for unmixed reflections, F MC = 4(f M ± f C ) and the positive or
negative sign would again be dependent upon the index of the plane. The fundamental
reflections with F MC = 4(f M + f C ) would appear only for planes for which h, k, l
are all even, while planes with all odd indices would exhibit superlattice reflections
with F hkl = 4(f M − f C ). Figure 2.17 shows simulated [100] and [111] zone axes
diffraction patterns for the MC carbide phase.
The depiction of the structure factor calculations for the M6 C and M23 C6 phases
are beyond this Chapter’s scope due to the complexities and the large number of
Fig. 2.17 a [001] and b [111] zone axes simulated diffraction pattern of the MC carbide in relation
to the austenite matrix phase. Solid circles represent reflections due to the austenite matrix and
hollow hexagonal symbols represent reflections due to the MC carbide phase
atoms per unit cell associated with these phases. However, the similar Bravais lattice
and crystal structures of the M6 C/M23 C6 phases and the γ phase (Table 2.1) imply
that their structure factors would allow reflections identical to the FCC γ phase, see
Fig. 2.18 for the case of M23 C6 .
The electron diffraction pattern mainly identifies the carbide phases. As the lattice
parameters of carbide phases are different from the matrix phase (Table 2.1), their
interplanar spacings differ. The interplanar spacing of a specific plane in the MC
phase is significantly different compared to the corresponding plane of the γ phase.
On the other hand, the interplanar spacing in the M6 C and M23 C6 phases is about
three times of the corresponding plane in the γ phase because of the nearly thrice the
lattice parameters of the M6 C/M23 C6 phases (Table 2.1). Therefore, the formation
of the M6 C and M23 C6 phases would subdivide the spacing between the austenite
reflections into three equal parts as illustrated by simulated [001] and [111] zone
axis electron diffraction patterns of the M23 C6 phase (Fig. 2.18). However, it would
be rather difficult to distinguish between the M6 C and M23 C6 phases because of the
commonality between their Bravais lattices and crystal structures and the closeness
of their lattice parameter parameters. The lattice parameters of the two differ only by
about 4%. The M6 C and M23 C6 phases have the same FCC Bravais lattice and differ
only in their space groups (Fd3m and Fm3m, respectively) owing to the presence of
a diamond glide in the former. However, the two phases can be readily distinguished
based on x-ray microanalysis (chemical composition analysis) in conjunction with
electron or x-ray diffraction analysis.
Fig. 2.18 a [001] and b [111] zone axes simulated diffraction pattern of the M23 C6 carbide in
relation to the austenite matrix phase. Solid circles represent reflections due to the austenite matrix
and hollow hexagonal symbols represent reflections due to the M23 C6 carbide phase
2.6 Summary 65
2.6 Summary
Alloy 625 comprises a matrix phase, a nickel-rich disordered solid-solution phase

of FCC structure, and may contain precipitates of other phases depending upon
processing conditions. The precipitating phases may be ordered intermetallic phases,
such as γ , δ, Ni2 (Cr, Mo), μ, Laves, etc. or carbides of MC, M6 C and M23 C6 type,
where M represent a metal atom. The size, volume fraction and morphology of these
phases determine the final properties of the alloy. These phases can be identified by
any diffraction technique that uses x-ray, electrons or neutrons. However, the low
volume fractions and closeness in the atomic scattering factors of elements in their
compounds make electron diffraction an ideal technique. Further, the formation of
most of these phases is associated with cubic to non-cubic phase transformations.
Their precipitation gives rise to different orientational variants in the parent cubic
matrix.
References
1. Singleton MF, Murray JL, Nash P, Al-Ni phase diagram. (1991) In: Massalski TB (ed in chief)
Binary alloy phase diagrams. ASM International Materials Park, p183
2. Villars P, Calvert LD (1986) Pearson’s handbook of crystallography data for intermetallic
phases, vol 3. ASM, Metals Park
3. Floreen S, Fuchs GE, Yang WJ (1994) The metallurgy of Alloy 625. Superallovs 718, 625, 706
and various derivatives. TMS, Pittsburgh, pp 13–38
4. Radavich JF, Fort A (1994) The metallurgy of alloy 625. Superallovs 718, 625, 706 and various
derivatives. TMS Pittsburgh, pp 632–645
5. Tawancy HM (1996) Precipitation characteristics of mu-phase in wrought nickel-base alloys
and its effect on their properties. J Mater Sci 31:3929–3936
6. Rai SK, Kumar A, Shankar V, Jayakumar T, Bhanu Sankara Rao K, Raj B (2004) Character-
ization of microstructures in Inconel 625 using X-ray diffraction peak broadening and lattice
parameter measurements. Scripta Mater 51:59–63
7. Ross EW, Sims CT (1987) In: Sims CT et al (eds) Superalloys II, Chapter.4, New York, Wiley,
pp 97–133
8. Verma A, Singh JB, Kaushik SD, Siruguri V (2020) Lattice parameter variation and its effect
on precipitation behaviour of ordered Ni2(Cr,Mo) phase in Ni-Cr-Mo alloys. J Alloys Comp
813:152–195
9. Tawancy HM (2017) On the precipitation of intermetallic compounds in selected solid-solution-
strengthened Ni-base alloys and their effects on mechanical properties. Metallogr Microstruct
Anal 6:200–215
10. Cullity BD (1959) Elements of X-Ray diffraction. Addison Wesley
11. Massalski TB, Barrett CS (1966) Structure of metals. McGraw-Hill, New York, p 266
12. Singh JB (2002) Ph.D. dissertation. IIT Bombay
13. Sundararaman M (1986) Microstructural studies on the high temperature materials Inconel 718
and Inconel 625 alloys. Ph.D. dissertation, University of Bombay
14. Williams DB, Carter CB (2009) Transmission electron microscopy, 2nd edn. Springer Science,
Boston, vol 3
Chapter 3
Physical Metallurgy of Alloy 625
Alloy 625 is designed as a solid-solution alloy with good combinations of mechanical

and corrosion properties over a temperature range from room temperature to about
800 °C. It derives its strength from the stiffening of the nickel–chromium matrix due
to the addition of molybdenum and niobium. These elements also impart superior
resistance to a wide range of corrosive environments as well as oxidation and carbur-
ization resistance. However, the alloy develops a highly complex microstructure
when different intermetallic phases and various carbides precipitate in the austenite
matrix during processing, heat treatments or both. The precipitation of these phases
modifies alloy’s behavior depending upon their nature, morphology and location of
formation. This chapter gives an overview of the alloy’s chemistry and its phase
transformation behavior. The chapter also briefly describes how the microstructure
is modified when various phases evolve.
3.1 Alloying Additions in Alloy 625
In general, alloying additions in superalloys can be categorized into three broad

groups [1]. The first group includes elements like nickel, cobalt, iron, chromium,
molybdenum, tungsten, and vanadium, which prefer to partition in the nickel lattice
and stabilize the face-centered cubic (FCC) phase. The second group of elements, like
aluminum, titanium, niobium and tantalum, promotes the formation of intermetallic
phases such as Ni3 (Al, Ta, Ti) (γ phase) and Ni3 (Nb, Ta, Ti) (γ phase). The third
group includes boron, carbon, magnesium and zirconium, which tend to segregate to
grain boundaries. Elements like chromium, molybdenum, niobium and tantalum may
also form carbide phases and detrimental topologically closed packed (TCP) phases
if their overall composition is not controlled adequately or improper fabrication
practices are employed [1]. The alloying elements in Alloy 625 may comprise about
55–62% nickel, about 20–24% chromium, about 7–11% molybdenum, about 3–4.5%
niobium plus tantalum, up to about 0.4% of aluminum and titanium, a maximum of
https://doi.org/10.1007/978-981-19-1562-8_3
68 3 Physical Metallurgy of Alloy 625
Table 3.1 Nominal composition range of the Alloy 625

Alloy Ni Cr Mo Nb + Ta Al Ti Fe C Si P S
Min. Bal. 20 8 3.15 0.2 0.2 – – – – –
Max. 23 10 4.15 0.4 0.4 5 0.01 0.5 0.015 0.015
0.1% carbon, up to about 0.5% silicon, up to about 0.5% manganese, up to about

0.015% boron, and the balance iron [2]. The patented design also envisaged up to
about 8% tungsten though rarely used in commercial alloys. Over the years, the
alloy composition has undergone a small change in the range of various elements.
Table 3.1 gives the nominal composition range of Alloy 625. Most commercial alloys
contain about 60% nickel, about 22% chromium, about 9% molybdenum, about 4%
niobium, about 0.2% aluminum, about 0.15% titanium, about 0.03% carbon and the
balance iron. This section presents the role of each element in the design of Alloy
625.
3.1.1 Nickel
The nearly filled 3d electron shell of the nickel allows Alloy 625 to accommodate
many alloying elements without phase instability [1]. This provides the nickel-base
alloys good solubility for various elements to strengthen its austenite (γ ) matrix
directly through solid-solution hardening and impart resistance against different envi-
ronments. Nearly filled third electron shell of the nickel also reduces its propensity
to form topologically close-packed phases. Alloy 625 must contain a minimum of
about 55% nickel for good high-temperature properties as annealed alloys containing
approximately 57% nickel show a peak in stress-rupture strength at about 650 °C
(Fig. 3.1) [3].
Fig. 3.1 Effect of the nickel

concentration on the rupture
strength of alloys annealed
for 1 h at 1038 °C and tested
at 649 °C for 1000 h. The
alloys contained nickel and
other elements as 13–21%
Cr, 4.25% Nb, 2–3% Mo,
0.1–0.25% Al, 0.1–0.25% Ti,
0.2% Si, 0.2% Mn,
0.02–0.04% C and balance
Fe [3]
3.1 Alloying Additions in Alloy 625 69
Fig. 3.2 Nickel–chromium

binary phase diagram [4].
The nominal range of
chromium in Alloy 625 is
marked in ‘cyan blue’
3.1.2 Chromium
Chromium plays an essential role in imparting corrosion resistance and solid-solution

strengthening to the nickel matrix. It forms an adherent chromium oxide (Cr2 O3 )
surface layer that protects the surface against environmental attack at elevated temper-
atures [1]. The crystal structure of chromium is body-centered-cubic (BCC), while
nickel is face-centered-cubic (FCC). Such a difference in crystal structures ther-
modynamically results in the eutectic type of phase diagrams with limited solid
solubility. However, the nearly filled 3d electron shell of the nickel accommodates
a large amount of chromium to accommodate the necessary chromium for Alloy
625 in its solid solution. In Alloy 625, about 20–22% chromium is recommended
with a maximum level of 24% chromium as it may cause the formation of undesired
deleterious TCP phases beyond 24%. The nominal range of chromium is marked
in ‘cyan blue’ on the Ni–Cr phase diagram (Fig. 3.2) [4]. Increasing chromium
content from 16 to 22% increases the strength of the nickel matrix without any
age-hardening [3]. Higher concentrations may stabilizes the Ni2 Cr phase at low
temperatures, as depicted in Fig. 3.2. In many alloys, chromium also improves the
mechanical strength by precipitation hardening the matrix by forming secondary
M23 C6 and M6 C carbides.
3.1.3 Molybdenum
Like chromium, the crystal structure of molybdenum is also BCC and forms a eutectic
type Ni-Mo binary phase diagram with a large austenite nickel solid-solution field
(Fig. 3.3 [5]). The nominal range of molybdenum in nickel for Alloy 625 is marked
in ‘cyan blue’ in Fig. 3.3. Similar crystal structures of molybdenum and chromium
Fig. 3.3 Nickel rich side of

the nickel-molybdenum
binary phase diagram [5].
The nominal range of
molybdenum in Alloy 625 is
marked in ‘cyan blue’
make them completely miscible in each other, which is reflected in the precipi-
tation behavior of the Ni2 (Cr, Mo) phase. The combined effect of chromium and
molybdenum on the phase stability of the austenitic nickel phase can be understood
considering their ternary phase diagram. A ternary phase diagram comprises three
elements and maps their phase fields in a triangular base as a function of temperature
along a vertical axis. The concentration of each element is represented along the
three sides of an equilateral triangle, and an isothermal section of the 3-dimensional
ternary phase diagram gives the phase fields at a given temperature. Figure 3.4 shows
an isothermal section of the Ni–Cr–Mo system taken at 1250 °C temperature. This
section was generated using the Thermo-Calc software and the nickel database. The
Fig. 3.4 An isothermal

section of the nickel–
chromium–molybdenum
ternary phase diagram
simulated at 1250 °C
temperature using the
ThermoCalc software and
the nickel database. The
nominal range of chromium
and molybdenum in Alloy
625 is marked in ‘cyan blue’
ternary phase diagram also shows a nickel-rich austenitic phase-field bound by about
45% chromium and about 35% molybdenum of respective binary axes. Beyond these
concentrations, the alloy tends to form σ and P topologically close-packed phases.
The addition of molybdenum in nickel increases the strength of the γ matrix through
solid-solution hardening due to the former’s larger atomic size [6]. In addition, molyb-
denum improves the creep resistance of the alloy because of its low diffusivity. It also
imparts good strength when combined with elements like chromium and niobium
and increases the alloy’s age-hardening response. In combination with chromium,
it also provides resistance against corrosion in extremely versatile environments of
both oxidizing and reducing chemicals by improving the stability of the Cr2 O3 film
and giving resistance to localized corrosion in aqueous chloride containing media.
3.1.4 Tungsten
Tungsten addition in nickel superalloys plays a similar role as that of molybdenum

but provides better solid-solution strengthening than molybdenum due to the larger
atomic radius of the former [7]. Tungsten also contributes to room temperature yield
strength and creep-rupture strengths of the alloy. However, commercial Alloy 625
rarely contain tungsten, possibly because of niobium that plays a similar role in
contributing to the alloy’s room temperature yield strength and rupture strength [8].
3.1.5 Niobium and Tantalum
The commercial grades of niobium invariably contain a small proportion of tantalum

since the two cannot be separated entirely because of their very similar properties [8].
The nominal composition of Alloy 625 and most other superalloys, therefore, report a
combined concentration of niobium plus tantalum. However, niobium is preferred to
tantalum because of its lower cost and density. In Alloy 625, the solubility of niobium
is about 2.5% and increases with decreasing molybdenum plus chromium content.
An increase in niobium content increases the stiffness of the alloy in the annealed
condition and exhibits a significant increase in the yield strength in the annealed
and aged conditions when present more than 3% (Fig. 3.5) [3]. This increase in
strength is due to the formation of the γ Ni3 Nb phase in the austenite matrix [8,
9]. In combination with molybdenum and chromium, niobium imparts better creep
properties to the alloy (Figs. 3.6 and 3.7) [3]. However, niobium higher than 4% may
increase segregation during solidification, leading to poor malleability and lower
product yield. This restricts the concentration of niobium plus tantalum in Alloy 625
to 4.5% with a maximum of 4% pure niobium.
Fig. 3.5 Variation in the

0.2% yield strength of Alloy
625 as a function of niobium
content [3]. The figure
compares the yield strength
of the alloy in annealed and
annealed and aged conditions
Fig. 3.6 Creep strain as a

function of time in
Ni–Cr–Mo–Nb alloys tested
at 816 °C at 52 MPa [3]
Fig. 3.7 Effect of

chromium, molybdenum and
niobium concentration on the
total creep of forged and
annealed alloy, annealed at
1149 °C for 1 h. The alloys
were tested at 816 °C at 66
MPa stress [3]
3.1.6 Iron
Iron does not play any significant role in Alloy 625. Its presence in most nickel-based
superalloys, except in iron-nickel–chromium alloys, is a consequence of the use of
ferroalloys for the addition of other elements. On the contrary, iron promotes the
formation of TCP phases and the metastable γ phase. The maximum limit of iron
in Alloy 625 is restricted to about 5%.
3.1.7 Aluminum and Titanium
The addition of aluminum in most superalloys increases their strength and environ-
mental resistance at elevated temperatures. It strengthens the alloy by the precipi-
tation of the well-known γ phase particles that primarily contains aluminum along
with other elements like titanium, niobium, etc. [3]. Aluminum also forms a tena-
cious and protective Al2 O3 scale, which restricts the inward diffusion of oxygen and
protects the alloy from oxidation. Titanium is generally added to aid the formation
of γ precipitates, which is more effective in raising the solvus temperature of the
γ phase [10]. Titanium further increases the effectiveness of the γ hardening by
increasing the lattice parameter and the antiphase-boundary energy of the γ phase
[7]. Therefore, a large titanium/aluminum ratio imparts higher strength to the alloy
even with a relatively low amount of aluminum. In nickel–iron–base superalloys
like Alloy 718, titanium promotes the co-precipitation of γ and γ phases, which
gives higher strength to alloys over a broader range of temperatures [11]. Titanium
also forms MC-type carbide and controls nitrogen levels during solidification as it
quickly bonds with nitrogen to form TiN phase particles [12].
Aluminum and titanium in Alloy 625 are primarily used as deoxidizers [2]. Even
though the maximum amount of aluminum in the alloy is 0.4%, it can dissolve a
much higher amount of titanium. The concentrations of aluminum and titanium are
intentionally kept low to avoid age-hardening of the alloy by γ phase particles. Low
levels of aluminum and titanium also improve the weldability and brazeability of the
alloy [3]. However, retaining about 0.2% each of aluminum and titanium in the alloy
improves creep properties of the alloy considerably compared to an alloy without
aluminum and titanium [3]. A small amount of titanium also has a marked effect on
age-hardening behavior of the alloy induced by γ precipitates. Figure 3.8 shows
the influence of titanium on the age-hardening of an Alloy 625 containing about
3.85% Nb [13]. Reducing titanium from 0.4 to 0.05% retards the precipitation of the
γ phase. An alloy with 0.05% titanium has a hardness value close to 0% titanium.
Retaining about 0.2% each of aluminum and titanium also improves the malleability
of the alloy [2], which helps in its hot workability. However, the total content of
aluminum plus titanium in the alloy must be restricted to a maximum of about 0.4%
to avoid age-hardening.
Fig. 3.8 Effect of titanium

concentration on γ
precipitate induced
hardening of Alloy 625 at
650 °C. The alloys contained
about 3.85% niobium [13]
3.1.8 Carbon
Carbon plays an important role in superalloys. During liquid-phase processing, it

acts as a deoxidizer. After deoxidation, the carbon left in the melt combines immedi-
ately with refractory elements like titanium, niobium, molybdenum, etc. to form MC
carbides that segregate at inter-dendritic regions during solidification. During heat
treatment and service exposure, the primary carbides degenerate to form secondary
carbides of M23 C6 and M6 C phases at grain boundaries over prolonged exposure [3].
If some carbon is retained in the austenite solid solution due to improper melting prac-
tice, the retained carbon may readily form the secondary carbides [14, 15]. Carbon
in Alloy 625 must be kept low and not exceed 0.1%.
3.1.9 Nitrogen
Nitrogen is considered harmful for malleability and ductility of the alloy. For a given
carbon content, increasing nitrogen contamination reduces the two properties of the
alloy. It forms brittle particles of titanium nitride that embrittle grain boundaries
and assist the precipitation of MC carbides [12]. Nitrogen can also dissolve in MC
and M6 C to form carbonitrides during solidification. However, the formation of
carbonitrides may leave excess carbon in the austenite matrix, which can cause
premature failure due to the accelerated formation of grain boundary carbides [15]
that embrittle the alloy. The Alloy 625 must not contain nitrogen more than about
0.03%.
3.1.10 Sulfur
Sulfur is a detrimental element in iron and nickel alloys [12, 16–18]. Its low solubility
in nickel solid solutions causes the formation of a low-melting-point eutectic of 643
°C at grain boundaries. This eutectic compound melts during hot-working of the
alloy reducing its workability. Sulfur also reduces fatigue life, creep resistance and
adhesion of the protective oxide scales. The addition of small amounts of manganese
or magnesium reduces the embrittling effect of sulfur by forming particles of their
respective sulfides dispersed in the matrix. In Alloy 625, the amount of sulfur is
restricted to a maximum of 0.015%.
3.1.11 Phosphorus
Like sulfur, phosphorus is also considered harmful due to its low solubility in nickel
and the formation of a low-melting-point eutectic of 875 °C at grain boundaries [12].
However, it has been reported to strengthen grain boundaries in some alloys when
present in small amounts, up to 0.02%, [19, 20]. Segregation of a small amount of
phosphorous at grain boundaries impedes the self-diffusion of nickel across grain
boundaries, thereby enhancing the creep life [19]. For example, adding 0.008%
phosphorous increases the stress-rupture life of Alloy 718 up to 704 °C [21, 22]
and improves ductility at 840 °C as compared to the undoped alloy. Like sulfur,
phosphorous in Alloy 625 is also restricted up to a maximum of 0.015%.
3.1.12 Grain Boundary Strengthening Elements
Minor additions of elements like boron and zirconium improve creep-rupture resis-
tance of nickel-base superalloys. A small amount of hafnium improves the ductility of
grain boundary regions. A synergistic effect of phosphorous and boron in enhancing
the creep resistance and stress-rupture life has also been reported in a boron-
containing Alloy 718. Addition of 0.011% boron in an Alloy 718 containing 0.005%
carbon and 0.022% phosphorous increases its stress-rupture life over 200% at 650 °C
[22]. This improvement in creep-rupture properties of the alloy with boron and phos-
phorus is attributed to their segregation at grain boundaries that improves their cohe-
sion and vacancy pinning capability, which slow down diffusion and reduce particle
growth [23]. A maximum of 0015% of boron may be added for better creep-rupture
properties of Alloy 625, although a higher content may reduce hot malleability of
the alloy [2].
Table 3.2 Compositions of the Alloy 625 and its LCF variant whose fatigue properties are
compared in Fig. 3.9 [3]
Alloy Ni Cr Mo Nb Al Ti C Si Fe N
625 61.0 21.5 9.0 3.6 0.20 0.20 0.06 0.25 2.5 –
625 LCF 61.0 21.5 9.0 3.6 0.20 0.20 0.03a 0.15a 2.5 0.02a
a Refers to the maximum concentration
3.1.13 Trace Elements
Commercial superalloys always contain many elements, in minor concentrations,

that are not intentionally added but are mostly detrimental to properties. At the same
time, some elements are added to control the effects of other elements. For example,
silicon, manganese and magnesium are added as refining agents during melting and
processing. Silicon is added as a deoxidizer, while manganese and magnesium miti-
gate the sulfur effect by removing the detrimental low-temperature eutectic phase
from grain boundaries [12]. These additions help in getting better mechanical prop-
erties of the finished product. In Alloy 625, the concentrations of silicon, manganese
and magnesium are restricted to a maximum of 0.5% each to avoid their detri-
mental effects on high-temperature strength. Likewise, the presence of copper may
be limited such that the total of sulfur, copper and phosphorus together does not
exceed 0.1% to avoid the loss in mechanical properties or malleability. The pres-
ence of such trace elements, intentional or unintentional, may significantly affect the
alloy’s specific properties, like ductility, fatigue life or environmental resistance. For
example, tight control of carbon, silicon, and nitrogen during the manufacturing of
Alloy 625 (termed LCF variant), designed for the fatigue limited sheet applications
like bellows and expansion joints, significantly increases its fatigue life compared to
a standard Alloy 625. Table 3.2 compares the composition, and Fig. 3.9 compares
the low-cycle fatigue properties of the Alloy 625 LCF with those of a standard Alloy
625 [3].
3.2 Characteristic Features of Phases in Alloy 625
The major phases that may be present in Alloy 625 are:
3.2.1 Gamma (γ) Phase
The gamma (γ ) phase refers to the continuous FCC nickel matrix of the alloy that
contains all the alloying elements dissolved in its disordered solid-solution without
3.2 Major Phases in Alloy 625 77
Fig. 3.9 A comparison of

the range of low-cycle
fatigue strength of 625 and
625 LCF alloys at
temperatures over 480–650
°C [3]
causing phase instability. The dissolution of chromium, molybdenum and niobium

strengthens the alloy by straining the matrix. These elements have atomic diame-
ters 1–13% and electron vacancy numbers 1–7% different from nickel [1]. The high
melting point and slow diffusivity of refractory elements also improve creep resis-
tance of the alloy. Most of these elements also significantly reduce stacking fault
energy of the alloy (Fig. 3.10) [24–27], which makes the cross slip of dislocations
difficult and, consequently, increases creep resistance of the alloy.

stacking fault energy of
binary nickel alloys
containing various alloying
additions [27]
3.2.2 Gamma Double Prime (γ ) Phase
The Ni3 Nb based γ phase with a D022 structure is the main hardening phase of
niobium bearing nickel–chromium-iron alloys [1] like Alloy 706, Alloy 718, Rene
62 and Udimet 63. However, binary nickel-niobium alloys form a D0a phase with
Ni3 Nb composition rather than the D022 phase. Formation of the γ phase has been
attributed to the presence of a small amount of iron, which promotes its forma-
tion in alloys containing 2–6% niobium [28]. Further, niobium bearing superalloys
invariably contain some amounts of aluminum and titanium also, which promote
the co-precipitation of γ phase with γ phase depending upon relative concentra-
tions of the two elements. The γ phase is the main strengthening phase in most
precipitation-hardened nickel-based superalloys [1]. The two phases may precipi-
tate out as separate particles with distinct morphologies, respectively as disk-shaped
and cuboidal particles (e.g., Alloy 718 [29, 30]), or form a compact morphology
comprising a cuboidal γ phase particle coated by the γ phase (as in Alloy 706
[30]) or as γ particle sandwich between γ phase particles as in Alloy 625 Plus [31]
(Fig. 3.11). The difference in the precipitation behavior of the two phases is governed
by the concentration of aluminum and titanium with respect to that of niobium. The
ratio of niobium to aluminum plus titanium governs the relative rates of nucleation
and growth and volume fractions of the two phases. A higher value of Nb/(Al + Ti)
ratio for Alloy 718 (about 5% Nb, 0.5% Al, 0.9% Ti) compared to that for Alloy 706
(about 3% Nb, 0.2% Al, 1.7% Ti) favors the precipitation of discrete γ particles in
the former, while a lower ratio in Alloy 706 favors the precipitation of the γ phase
particles first followed by the nucleation of the γ phase on all sides of the γ phase
[30].
In Alloy 625, the γ particles form as a metastable phase during thermal exposure
over a temperature range 595–760 °C. Floreen et al. [13] have given a formula
Ni3 (Nb>0.05 Ti<0.5 Al<0.5 ) for the γ phase in Alloy 625. Figure 3.12 shows a pair
of bright- and dark-field images of ellipsoidal γ particles taken by transmission
electron microscopy. The particles appear as elongated ellipses due to the projection
of the three-dimensional ellipsoid onto a two-dimensional image plane. Inset shows
a selected area electron diffraction pattern from the imaged region, which shows
streaking of superlattice reflections perpendicular to the thinner direction. Streaking
in diffraction is a manifestation of the relaxation in Bragg condition when the crystal
Fig. 3.11 Schematic

depicting compact
precipitate morphology
comprising a γ phase
particle sandwiched between
γ phase particles
Fig. 3.12 Bright-field and dark-field transmission electron microscopy images of γ phase precip-
itates in an age-hardened Alloy 625. Inset shows a <001> zone-axis electron diffraction pattern
showing fine superlattice reflections of the of γ phase. Note elongation in the superlattice reflections
perpendicular to thickness of the ellipsoidal
is very thin and arises in a direction perpendicular to the thickness [32]. These
particles are coherent with the austenite matrix. The misfit strain associated with
ellipsoidal γ particles embedded in the γ -matrix is about 2.9% [33], which is much
larger than the maximum γ -γ misfit strain (~1.2%) in γ strengthened nickel-base
superalloys [1]. Therefore, precipitation of the γ phase particles imparts very high
strength to the γ phase bearing alloys. However, the γ phase transforms to its
stable δ structure at temperatures above 650 °C. Therefore, careful heat treatment is
required to ensure the precipitation of the γ phase instead of the δ phase.
3.2.3 Delta (δ) Phase
The δ phase is the equilibrium phase of the γ phase. High niobium and silicon
and low aluminum contents promote the formation of δ phase while substitution
of tantalum for niobium inhibits its formation [34]. The formation of δ precipitates
occurs in the temperature range over 750–950 °C [35]. The δ phase particles assume
a plate morphology with {111} habit plane (Fig. 3.13), though randomly oriented
globular δ particles have also been reported in some cases at the grain boundaries
[36]. The globular morphology of δ particles is better than the plate morphology as the
latter embrittles the alloy. The δ phase forms by heterogeneous nucleation on grain
boundaries and twin boundaries at relatively low temperatures or by intragranular
nucleation at relatively high temperatures [37]. The nucleation of the δ phase may
occur directly from the supersaturated γ matrix. In addition, the δ phase may form
Fig. 3.13 A scanning

electron micrograph of an
aged Alloy 625 showing the
predominant formation of
needle-shaped δ phase
particles
from the existing γ phase particles in which stacking faults act as nuclei of the δ
phase [35]. As shown later in Sect. 4.2, both γ and δ phases have the rectangular
ordering of niobium atoms in their close-packed planes (Figs. 4.6 and 4.8) and the two
phases differ only in the stacking sequences of close-packed planes. The γ phase
follows a … A1 B1 C1 A2 B2 C2 A1 B1 C1 … while the δ phase follows a …ABAB…
type stacking sequence of their close-packed planes [35, 37]. The A1 and the A2
layers in the γ phase, and similarly the B1 and the B2 layers and the C1 and the
C2 layers, represent the same stacking sequence with atom positions (Fig. 4.6),
vertically above/below one another, but contain niobium atoms in such a manner that
the superimposition of minority atoms occur only after six layers. A missing plane,
say B1 , in the stacking of close-packed planes in the γ phase brings stacking of the
four layers (say …C1 A2 C2 A1 …) similar to that in the δ phase. Stacking faults in the
γ phase, therefore, acts as nuclei of the δ phase for the γ -δ transformation [35,
37]. All γ precipitate strengthened nickel-base alloys are consequently susceptible
to the formation of δ phase during processing or service at temperatures above about
650 °C [35]. Although the δ phase particles are known to embrittle the alloy, their
controlled precipitation at grain boundaries inhibits grain boundary sliding and may
be beneficial for creep-rupture ductility [38].
3.2.4 Ni2 (Cr, Mo) Phase
The Ni2 (Cr, Mo) phase is an equilibrium phase commonly observed in nickel–
chromium-molybdenum alloys during thermal exposure at temperatures ~600 °C.
The nickel, chromium, and molybdenum constitute major constituent elements of
the phase in which the ratio of the nickel to the sum of molybdenum plus chromium
content (in atomic per cent) approximately corresponds to Ni2 (Cr, Mo) stoichiom-
etry. In many nickel–chromium–molybdenum alloys, such as Hastelloy C, Hastelloy
C276, Hastelloy C4, etc. molybdenum is partially replaced by tungsten to further
enhance the strength at elevated temperatures as well as to improve corrosion resis-

tance in certain media. The thermal stability of the Ni2 (Cr, Mo) phase depends upon
relative concentrations of chromium and molybdenum in the alloy [39]. The addition
of molybdenum increases the thermodynamic stability and the solvus temperature of
the Ni2 (Cr, Mo) phase [39–41]. The Ni2 (Cr, Mo) phase is stable at temperatures up to
about 630 °C in Alloy 625 (containing about 26 at% Cr and 6 at% Mo) [42], while it
is stable up to about ~775 °C in Haynes 242 (containing about 10 at% Cr and 16 at%
Mo) [43]. Besides, an increase in the molybdenum concentration increase kinetics of
the precipitation of the Ni2 (Cr, Mo) phase [39, 44]. For example, it takes a prolonged
thermal exposure of more than 1000 h at 600 °C to form the Ni2 (Cr, Mo) phase parti-
cles in Alloy 625 [45], while it forms within a few hours at temperatures from 650 to
750 °C in Haynes 242 [43]. The increase in the precipitation kinetics in Haynes 242
is due to a higher diffusivity of the molybdenum than chromium in the nickel matrix
[39, 46]. The addition of tungsten enhances the thermal stability of the Ni2 (Cr, Mo)
phase [47]. This has been exploited by partially replacing molybdenum with tungsten
in Haynes 242 alloy to produce Haynes 244 alloy [48]. Recent independent studies
have also confirmed the similar effect of W on the thermal stability of the Ni2 (Cr, Mo)
phase in model Ni–Cr–Mo–X (X = W or/and Ti) [49]. Like γ particles, the Ni2 (Cr,
Mo) phase also form homogeneously with an ellipsoidal morphology (Fig. 3.14a, b)
though they are thicker than γ particles. Besides, Sundararaman et al. [50] have also
reported a snowflake morphology of Ni2 (Cr, Mo) precipitates (Fig. 3.14c). Precipi-
tation of the Ni2 (Cr, Mo) phase increases the alloy’s susceptibility to hydrogen and
stress corrosion cracking [51].
Fig. 3.14 a and b Bright-field and dark-field transmission electron microscopy images of Ni2 (Cr,
Mo) precipitates with ellipsoidal morphology in a Ni–Cr–Mo alloy (Courtesy Dr. Amit Verma). c
Snow-flake morphology of Ni2 (Cr, Mo) precipitates in a service aged Alloy 625. Reprinted from
Ref. [49].
3.2.5 Carbide Phases
Carbide particles of several phases may form in nickel-base alloys containing refrac-
tory elements. These alloys may contain carbon in the range of about 0.02–0.2 wt%.
The most common carbide phases are MC, M23 C6 , M6 C and M7 C3 , where M denotes
metal atoms [1]. In general, alloys containing high chromium, titanium and aluminum
favor the M23 C6 phase, high molybdenum and tungsten favor the M6 C phase and
high niobium, tantalum and titanium favor the MC phase [1]. M7 C3 forms in alloys
with low concentrations of chromium and refractive elements but usually transforms
to M23 C6 on aging. In Alloy 625, the formation of carbides of MC, M23 C6 and M6 C
phases have been reported during solidification of the melt and during fabrication
and service. The carbides that form during solidification are termed “Primary” while
those forming during fabrication and service are termed “Secondary”. The MC phase
is the most common primary carbide, though the primary carbides of M6 C and M23 C6
type have also been reported (e.g., [52, 53]).
The MC phase forms with refractory elements like niobium, tantalum, hafnium,
and titanium. The high stability of the MC with these elements is because of their
high (negative) free energy of formation [1]. However, the thermodynamic stability
of their MC carbides differs. In decreasing order of stability, it is HfC, TiC, TaC
and NbC [2], though they prefer to form in the order as HfC, TaC, NbC and TiC
[1]. When multiple refractory elements are present, atoms of different species may
substitute for each other, as in (Ti, Nb)C. Partial replacement of titanium, tantalum
or niobium by molybdenum or tungsten reduces the stability of the MC phase [1].
The reduced stability makes the MC phase prone to decomposition, which is the
primary carbon source for the formation of secondary M23 C6 and M6 C carbides over
the temperature range of 700–980 °C [1]. Besides, the secondary carbides may also
precipitate directly from the carbon supersaturated austenite matrix.
The M23 C6 phase is a chromium-rich carbide. It precipitates abundantly in the
temperature range 650–900 °C, mostly as a result of the decomposition of the primary
MC carbides in nickel-base superalloys containing moderate to large amounts of
chromium [1]. The M23 C6 carbide particles are enriched with chromium and prefer
to nucleate at grain boundaries and other defects, like twin boundaries, dislocations
and stacking faults [52]. In Alloy 625 the approximate composition of M23 C6 is
(Cr0.85 Fe0.01 Ni0.07 Mo0.07 )23 C6 [13].
The MC carbide may also decompose to form M6 C carbide at about 800–980 °C
when molybdenum and tungsten in the alloy is more than 6–8%. Further, M6 C and
M23 C6 may interact to form one from the another. For example, pronged thermal
exposure of Rene 41 and M-252 alloys converts M6 C to M23 C6 , while that of Mar—
M 200 converts the M23 C6 to M6 C [1]. Unlike the more rigid M23 C6 phase, the
M6 C exhibits a wider composition range. Raghavan et al. [54] have observed that
in Ni–Cr–Mo alloys, chromium can substitute for molybdenum up to 30% in the
M6 C phase, while in M23 C6, the solubility of molybdenum is only 10%. More-
over, when the ratio of Cr/Mo atoms in the alloy exceeds 3, particles of the M23 C6
carbide nucleate predominantly, while the particles of the M6 C type carbide precip-
itate when it is less than 3. The approximate composition of the M6 C in Alloy 625
is (Cr0.21 Fe0.02 Ni0.37 Nb0.08 Mo0.24 Si0.08 )6 C [13]. In alloys containing molybdenum
or tungsten, M6 C may form as grain boundary precipitates along with M23 C6 [1].
The relative abundance of the two types of carbides is determined by the amounts of
molybdenum, tungsten and chromium in the alloy.
In Alloy 625, the MC phase forms as discrete particles with coarse cuboidal or
“script” morphologies distributed heterogeneously at transgranular and intergran-
ular locations (Fig. 3.15). It is primarily (Nb, Ti)C, with minor amounts of nickel
and chromium [13]. The formation of carbide particles may enhance or degrade
the mechanical properties of the alloy depending on their morphology and distri-
bution. The secondary carbides may precipitate as continuous grain boundary films
or discrete particles at grain boundaries. While continuous films of carbides along
grain boundaries severely degrade the impact and rupture properties of the alloy,
the formation of discrete carbide particles is beneficial in inhibiting grain boundary
sliding during creep.
Fig. 3.15 Formation of

primary carbide in Chinese
script morphology in cast
Alloy 625
3.2.6 Topologically Close-Packed Phases
Nickel–iron base superalloys containing high amounts of transition metals, like

tantalum, niobium, chromium, tungsten, and molybdenum, are prone to the forma-
tion of topologically close-packed (TCP) phases. Elements like aluminum and silicon
promote their formation, while boron and zirconium inhibit their occurrence [1].
The TCP phases are hard and brittle, whose presence may significantly degrade
the overall mechanical properties of the alloy [1]. These phases form through non-
metallic directional electron bonding of terminal elements. They nucleate at austenite
grain boundaries and usually grow as Widmanstätten plates parallel to {111} planes
of the γ matrix. The plate morphology promotes crack initiation and easy propa-
gation, which reduces the alloy’s ductility and creep-rupture strength, although the
yield strength remains unaffected. Further, the TCP phases weaken the matrix as
their formation scavenge refractory elements, causing a loss of matrix strength. The
precipitation of TCP phases can be minimized and even eliminated by carefully
controlling the composition of various refractory elements in the alloy. The TCP
phases that may form in Alloy 625 are σ, μ, and Laves, though their occurrence,
particularly of the σ phase, has been rarely reported. The σ phase is structurally
close to the M23 C6 phase because of the similar number of chromium and molyb-
denum atoms required to form the σ phase. If all the carbon atoms are removed
from the M23 C6 carbide lattice, the remaining lattice can be converted into the σ
phase by a slight shift in atom positions [1]. That is why the σ phase often nucleates
on M23 C6 particles [1]. Once nucleated, it grows principally in the austenite matrix
into the plate morphology. Likewise, the μ phase is structurally similar to the M6 C
phase and may form in M6 C bearing alloys, particularly when the concentrations
of molybdenum and tungsten are high. The Laves phase in Alloy 625 forms during
solidification. It is considerably rich in niobium, molybdenum and silicon compared
to the nominal composition of the alloy. However, the composition of each element
in the Laves phase may vary significantly depending upon the processing history of
the alloy [13, 55].
3.3 Solidification Behavior of Alloy 625
The high concentration of refractory elements in superalloys makes their solidifi-

cation quite complex compared to materials like aluminum and copper. In general,
the phase diagram and heat and mass transport principles govern the solidification
behavior, while the solidification kinetics determines the development of the cast
microstructure. During solidification of an alloy, first, the solute-lean alloy solidi-
fies, followed by dendritic solidification of the solute-rich liquid. The solidification
front grows in the directions of heat and composition gradients. The distribution of
solutes in the solidified front is governed by their partitioning coefficient, k. The
partitioning coefficient of an element is defined as the ratio of its composition in the
3.3 Solidification Behavior of the Alloy 625 85
solid to that in the liquid within the solidification temperature range. The k value
of an element characterizes its relative thermodynamic tendency to remain in liquid
or solid and gives an idea of the extent of micro-segregation expected during solid-
ification of the alloy. A value of k less than unity indicates that dendrite cores will
be depleted of the solute relative to the inter-dendritic regions, while a value greater
than unity implies enrichment of the dendritic cores. A k value of unity indicates no
dendritic micro-segregation will occur. Elements like niobium, molybdenum, tita-
nium, and silicon in nickel solution have k < l and segregate to inter-dendritic regions,
while elements, like iron, have k > l and tend to partition to dendrite cores. Little
chromium enrichment occurs in either of the two regions because of its k value close
to zero. This behavior of solutes causes enrichment of nickel and iron in dendrite
cores in Alloy 625 and the segregation of niobium, molybdenum and silicon to inter-
dendritic regions. This segregation behavior of solutes results in a local variation in
the composition at the subgrain level, which may cause the formation of a second
phase at the end of the solidification.
The high concentrations of heavier solutes in superalloys cause their segregation in
inter-dendritic regions, which promote the precipitation of TCP phases and carbides
during the final stages of solidification. Therefore, the solidification of superalloys
requires controlled cooling of the melt. Controlled cooling avoids the formation of
continuous channels of heavy solutes rejected during dendrite formation. When such
channels solidify, they form continuous TCP phases and carbides, which are highly
detrimental to the strength and ductility of the alloy.
The concentration of carbon in Alloy 625 is usually sufficiently high to promote
the formation of both carbides and Laves phases at the end of solidification. Like
niobium and molybdenum, carbon segregates aggressively to the liquid inducing the
formation of eutectic type reactions involving MC-type carbide, Laves phases, or both
toward the terminal stages of solidification. The presence of chromium, molybdenum,
niobium, iron and silicon promotes the formation of Laves phase in Alloy 625 rather
than the Ni3 Nb. Cieslak [55] has studied the effect of niobium, silicon and carbon
on the solidification behavior of Alloy 625, containing the three elements in the
range ~0–3.6 wt%, ~0.03–0.40 wt%, and ~0.009–0.036 wt%, respectively. Table
3.3 summarizes the phase transformation sequence and terminal reactions in these
alloys. He has shown that the terminal liquid that solidifies in the alloy containing
high niobium but low carbon and silicon content is enriched with niobium solutes
and form the NbC and Laves phases within the γ matrix at inter-dendritic regions.
Both NbC and Laves phases are high in niobium, though the two phases may contain
other elements in small quantities. The formation of the γ phase in the terminal liquid
progresses with a eutectic type L → γ + NbC solidification reaction. Figure 3.16
depicts this eutectic reaction in a pseudo-binary phase diagram. Floreen et al. [13]
have reported a temperature range of 1190 to 1205 °C for the eutectic reaction in
Alloy 625. As the eutectic reaction continues to form the γ /NbC phase, the remaining
liquid gets depleted with niobium and carbon. The local liquid composition again
shifts back toward the composition where the liquid solidifies to form the γ phase.
The eutectic reaction continues until the interfacial composition satisfy the three-
phase L → γ + NbC non-invariant reaction. This behavior of niobium enrichment
Table 3.3 A summary of the phase transformation sequences and terminal reactions in Alloy 625
containing different amounts of Si and C elements [55, 56]
Si and C concentration Phase transformation Terminal solidification
sequence Reaction Temperature (°C)
0.03Si, 0.009 C L→L+γ →L+γ + L → L + γ + Laves 1150
NbC → L + γ + NbC +
Laves → γ + NbC +
Laves
0.03Si, 0.038 C L→L+γ →L+γ+ L → L + γ + NbC 1246
NbC → γ + NbC
M6 C → L + γ + NbC +
M6 C + Laves → γ +
NbC + M6 C + Laves
Laves → γ + NbC +
Laves
Fig. 3.16 A hypothetical

pseudo binary phase diagram
showing a lower temperature
eutectic (T e ) in equilibrium
with MC Phase [13]. M. P.
represents melting point of
the alloy
and depletion in the remaining liquid continues till the last stages of solidification
when the last liquid solidifies by a eutectic reaction L → γ + Laves at ~1150 °C. The
addition of carbon in niobium bearing alloys promotes the formation of the γ and NbC
constituent at the expense of the γ and Laves constituent. This solidification behavior
of Alloy 625 is schematically represented as a function of the C/Nb ratio (Fig. 3.17).
When C/Nb is high, the alloy forms γ and NbC without Laves phase. At intermediate
values of C/Nb, it first forms γ and NbC followed by the formation of Laves phase.
When C/Nb is low, it forms γ and Laves phase with no NbC. However, the formation
of Laves phases without NbC is not uncommon in Alloy 625 when carbon is less than
3.3 Solidification Behavior of the Alloy 625 87
Fig. 3.17 Schematic

depicting the effect of carbon
and niobium on the
solidification path in Alloy
625 [13]. When C/Nb is
high, the alloy solidifies to
form γ and NbC without
Laves phase (Path 1). At
intermediate values of C/Nb,
it first forms γ and NbC
followed by the formation of
Laves phase (Path 2). When
C/Nb is low, it directly forms
γ and Laves phase with no
NbC (Path 3)
0.01% [56]. On the other hand, silicon promotes the eutectic formation of the Mo-
rich M6 C carbide and enhances the formation of γ /Laves constituents even in Alloy
625 with low levels of carbon. This behavior of silicon is similar to that observed in
other superalloys [57]. Independent studies by Bardos et al. [57] supports this role of
silicon in promoting the formation of Laves phase. Bardos et al. [57] have reported
the formation of Ni3 SiNb2 phase in a ternary alloy even though a Ni2 Nb Laves phase
does not exist. Alloy 625 containing high silicon may therefore have a significantly
different solidified microstructure with higher volume fractions of M6 C carbide and
Laves phases.
The carbon content also influences the solidification range (i.e., the difference
between the liquidus and the solidus temperatures). Figure 3.18 shows a plot of the
solidification range during cooling as a function of carbon in a nickel alloy containing
22.1% Cr, 8.9% Mo, 3.6% Nb, 4.3% Fe, 0.27% Al, 0.16% Ti, 0.0015% B, and varying
Fig. 3.18 Plot shows

solidification range as a
function of carbon in a nickel
alloy containing 22.1% Cr,
8.9% Mo, 3.6% Nb, 4.3%
Fe, 0.27% Al, 0.16% Ti,
0.0015% B. The figure also
shows the individual effects
on the solidification range
when the amounts of
molybdenum, niobium, iron
and titanium are reduced
close to their lower limits
and boron and nitrogen are
increased to their highest
limits [13]
amounts of carbon [55, 56]. An increase in the carbon content significantly increases
the solidification range of Alloy 625. Likewise, silicon and niobium contents signif-
icantly increase the solidification range of the alloy. However, the increase in the
solidification range due to niobium is much more than carbon or silicon. The solidi-
fication range directly influences the formation of the inter-dendritic NbC and Laves
phases, as a decrease in the solidification range reduces the amount of segrega-
tion. Other elements also individually affect the solidification range of the alloy. For
example, reducing the amounts of molybdenum, niobium, iron and titanium close
to their lower limits (Table 3.1) tend to reduce the solidification range (Fig. 3.18).
Increasing the boron to 0.018% increases the solidification range significantly while
increasing the nitrogen content to 0.10% has little effect.
Reducing the solidification range is essential as it reduces the amount of segre-
gation during solidification and, therefore, improves hot workability. Thus, reducing
the carbon and niobium contents is beneficial in reducing their quantity available
for the formation of NbC or Laves phases and reducing their segregation during
solidification. Therefore, the formation of NbC and Laves phase can be reduced by
controlling the solute concentration and reducing the solidification range. Likewise,
reducing elements like iron, molybdenum and silicon close to their lower limits is
beneficial in minimizing the precipitation of the Laves phase [13].
The formation of Laves and NbC phases plays a significant role in the mechan-
ical properties of cast and wrought Alloy 625. Their particles can have detrimental
effects on ductility and rupture life if present in excessive or highly localized distri-
butions. Laves phase particle can be eliminated by suitable homogenization treat-
ment, typically annealing for a period of about 15 h at about 1180 °C [58], or by
thermo-mechanical treatments. However, the NbC particles are very stable and cannot
be eliminated by conventional processing. NbC particles are distributed randomly
during subsequent thermo-mechanical processing. Therefore, the Laves phase is
usually absent while NbC particles are observed as dispersed particles in wrought
products. Improper thermo-mechanical processing may cause the formation of a
banded microstructure locally containing a high density of NbC and Laves phase
particles in wrought products [13]. The formation of such bands of hard particles
degrades the ductility in a direction transverse to the bands. Figure 3.19 shows an
example of a banded microstructure with a high local density of Laves phase particles
in an Alloy 625 [13]. Alloys with such microstructures display poor ductility when
strained perpendicular to the bands.
3.4 Phase Transformations in Alloy 625
Alloy 625 undergo a variety of transformations when exposed to elevated temper-

atures. These transformations are governed by nucleation and growth of the trans-
forming phase, which are functions of temperature and time. Such transformations
are conveniently represented by “C” shape time–temperature-transformation (TTT)
curves for a given volume fraction of the transformed phase, where the curve’s nose
3.4 Phase Transformations in Alloy 625 89
Fig. 3.19 Photograph of the banded microstructure formed by the accumulation of NbC and Laves
phase particles in a wrought Alloy 625 plate. Reprinted from Ref. [13]. Copyright 1994 by The
Minerals, Metals & Materials Society. Used with permission
(or knee) corresponds to the fastest transformation temperature. At temperatures

above the nose, the rate of transformation is slow because of the low nucleation rate
even though the atomic mobility of solutes is high. On the other hand, at temper-
atures below the nose where the nucleation rate is high, the transformation rate is
slow because the atomic mobility is slow. Further, in alloys like Alloy 625, where
multiple phases may form with overlapping fields of time, temperature or both, curves
corresponding to different phases may overlap.
Alloy 625 forms various carbides and intermetallic phases during thermal expo-
sures for periods ranging from a few minutes to thousands of hours. Figure 3.20 give
the TTT diagram for the beginning of the precipitation of various phases in Alloy
625 in solution annealed condition, drawn based on the diagram proposed by Floreen
et al. [13], where all the phases are in the austenite solid solution. The original figure
does not contain the precipitation curve for the Ni2 (Cr, Mo) phase, which has been
included in Fig. 3.20 based on the literature data. The TTT curves in Fig. 3.20 are
for an alloy with nominal composition. A variation in the composition, even within
the composition range, may vary their position with respect to time and temperature.
The precipitation of the carbides begins at grain boundaries in the temperature
range of about 700–1040 °C. Both MC and M6 C type carbides form at temperatures
ranging from about 870–1040 °C, while the M23 C6 phase forms at temperatures
in the range of about 700–915 °C. In the overlapping temperature range, all three
carbides may form. Figure 3.21 show the formation of all three types of carbides
after an exposure of 8 h at about 870 °C [13].
Prolonged exposure in the temperature range of about 700–980 °C may begin
the precipitation of both Laves and δ phase. The simultaneous precipitation of the
two phases has been attributed to the similar kinetics of their precipitation, which is
controlled by the diffusion of niobium solutes. However, the co-precipitation of Laves
and δ phase may not always coincide and depends upon the relative concentrations
of carbon and niobium solutes, as illustrated by the co-precipitation of carbide and δ
Fig. 3.20 Time–temperature-transformation (TTT) diagram of the beginning of the precipitation

of various phases in Alloy 625. The diagram is modified from the TTT diagram proposed by Floreen
et al. [13] to include the precipitation of the Ni2 (Cr, Mo) phase. Broken lines show the TTT curves
proposed by Floreen et al., while solid lines show the new curves for γ and Ni2 (Cr, Mo) phases
drawn based on the new data [45, 59]. The upper and lower bound of the two curves were decided
by their temperature stability regimes in the literature
Fig. 3.21 A transmission

electron microscopy
micrograph of various
carbides precipitated at grain
boundaries in Alloy 625 after
annealing of 8 h at 870 °C.
Reprinted from Ref. [13].
Copyright 1994 by The
Minerals, Metals &
Materials Society. Used with
permission
phases during prolonged service exposure of an alloy at around 800 °C (Fig. 3.22).
The δ phase typically have an acicular or plate shape morphology, while the Laves
phase particles are irregular or blocky shaped, similar in morphology to those of
M6 C and M23 C6 carbides [13].
In the temperature range of about 595–760 °C, the γ phase forms with its nose at
around 650 °C, corresponding to the fastest kinetics. The precipitation of the Ni2 (Cr,
Mo) phase in Alloy 625 has been reported at a temperature as low as 540 °C after
3.4 Phase Transformations in Alloy 625 91
Fig. 3.22 a Optical micrograph of a service aged Alloy 625 showing the precipitation of carbide
(thin line in light contrast) and needle-shaped δ phase particles at grain boundaries. b A transmission
electron microscopy image of δ precipitates at a grain boundary
100 h of aging [59]. However, the phase is thermally stable up to about 628 °C and
dissolve above it [42].
Plastic deformation may affect the precipitation behavior of all the phases by
shifting their curves toward less incubation time and toward lower temperatures
[60–62]. This behavior is attributed to three main factors, namely, (i) an increase
in the density of nucleation sites due to an increase in the defect density; (ii) an
increase in the diffusion coefficient due to the elastic distortions of the lattice; (iii) an
increase in diffusion due to dislocation pipe diffusion. Radavich and Fort [61] have
reported faster precipitation of the δ phase particles after pre-straining of Alloy 625.
Similarly, Suave et al. [62] have reported the precipitation of the δ phase particles at
temperatures as low as 650 °C, while that of the γ phase at temperature 550 °C in
a deformed alloy.
All the phases dissolve at temperatures above their upper-temperature bounds.
For example, carbides, δ and Laves phases dissolve into the solution at temperatures
above 1100 °C. Carbides dissolve within an hour at 1100 °C, while δ and Laves
phases may take much longer time to dissolve completely.
3.5 Microstructural Evolution During Aging of Alloy 625
Solution annealing the alloy in the temperature range 1050–1150 °C does not bring
about any appreciable difference in the microstructure [63]. A typical microstruc-
ture of wrought alloys subjected to solution annealing at 1150 °C shows equiaxed
grains with grain boundaries free of precipitates (Fig. 3.23a) except for the occa-
sional occurrence of randomly distributed blocky precipitates of primary carbides.
Fig. 3.23 a Optical micrograph of a solution annealed Alloy 625. b Typical transmission electron
microscopy image showing planar arrays of dislocations and stacking faults (SF) in the solution
annealed Alloy 625. Broken lines mark the trace of {111} glide plane of the dislocation arrays
The alloy exhibit frequent {111} annealing twins or stacking faults along with the
planar arrangement of dislocations on {111} planes (Fig. 3.23b). The frequent obser-
vations of the planar arrangement of dislocations and stacking faults is indicative
of the low to an intermediate value of the matrix’s stacking fault energy (SFE).
Alloys, like aluminum alloys, associated with a high SFE (~250–300 mJ/mm2 )
exhibit microstructures with lattice dislocations only without stacking faults or twins
(e.g., [64]), while alloys with a low value of SFE (~25–50 mJ/mm2 ) are associated
with high incidences of dislocation dissociation and stacking fault formation (e.g.,
[65]).
3.5.1 Precipitation of the γ Phase
As mentioned in Sect. 3.2,2., the γ phase precipitates in the temperature range of

about 600–760 °C as a metastable phase in Alloy 625. Short time aging of Alloy 625
at temperatures up to 700 °C does not produce any noticeable precipitation of the
γ phase and the microstructures essentially remain similar to the solution annealed
alloy [63]. Aging for 10 h at 650 °C results in the formation of fine γ phase particles
that are difficult to resolve by transmission electron microscopy but show distinct
superlattice reflections in the electron diffraction patterns [63, 66]. Samples aged for
24 h at 650 °C forms distinguishable and homogeneously distributed thin lens shape
γ particles in the matrix (Fig. 3.24a) [66]. After prolonged annealing, the precipitates
assume their characteristic ellipsoidal morphology (Fig. 3.24b). Figure 3.25 shows a
three-dimensional drawing of an ellipsoidal particle of thickness t having radii of h
and R along the minor and major axes of the ellipse. The habit planes of ellipsoidal
3.5 Evolution of the Microstructure of Alloy 625 93
Fig. 3.24 Transmission electron microscopy images (in dark-field) of γ phase particles in Alloy
625 after a ageing for 24 h at 650 °C, and b after a prolonged ageing period
Fig. 3.25 A
three-dimensional schematic
drawing of an ellipsoidal
particle of thickness (height)
t and minor and major
semi-axes h and R,
respectively
particles are parallel to their flat surfaces, which are parallel to {100} planes of matrix
and are always perpendicular to c-axis of their unit cell.
Samples aged for prolonged periods also tend to nucleate γ particles hetero-
geneously at structural singularities, like dislocations and twin boundaries. Aging
of the alloy at 700 °C for a period of 168 h exhibit homogeneous precipitation of
the γ particles and their frequent precipitation on matrix dislocations [63, 66]. At
still higher aging temperatures, heterogeneous nucleation of γ particles preferably
occurs at dislocations. Figure 3.26 shows the precipitation of γ particles on a planar
array of dislocations and twin boundaries in a sample aged at 750 °C for 24 h. The
heterogeneous precipitation of the γ particles on dislocations resemble “leaves on
a stem” morphology with the dislocation line parallel to the “stem” and the ellip-
soidal γ phase particles appearing “leaves” attached to the “stem” (Fig. 3.27 [63]).
The heterogeneous nucleation on dislocations does not entail any change in the
habit plane of the γ phase particles, but may affect the number density of particles
corresponding to a given variant depending upon the strain field of dislocations that
provide the nucleation sites for the nucleating variant.
The precipitation of the γ particles constrains the matrix due to its non-integral
unit cell axial ratio (c/a = 2.036), and the constraint strain increases with an increase
in the particle size. The ellipsoidal morphology of the γ particles is a consequence
Fig. 3.26 a Transmission electron microscopy images of heterogeneous precipitation of γ phase

precipitates on dislocations and coherent twin boundaries in Alloy 625 aged at 750 °C for 100 h. b
A magnified image of γ precipitates on matrix and twin side of a boundary. c and d Bright- and
dark-field pairs of a few precipitates that nucleated on a twin-boundary and grew into the matrix.
Inset in b shows a <110> electron diffraction pattern from the twin region. Reprinted from Ref.
[63] by permission from Dr. M. Sundararaman
of the minimization of the strain energy arising due to this constraint strain. The
constrained strain, εC, of an ellipsoidal particle having a tetragonal distortion perpen-
dicular to its habit plane, is related to the stress-free transformation strain εT, by the
following relationship [67]

(1 − 2ν) t T
εC = 1 − ε (3.1)
2(1 − ν) R
Fig. 3.27 a Bright-field transmission electron microscopy image of the “leaves on a stem”
morphology of γ precipitates nucleated on dislocations during ageing of Alloy 625 at 750 °C.
b and c Dark-field images showing the γ precipitates that formed “leaves” and “stem” of the
configuration. Reprinted from Ref. [63] by permission from Dr. M. Sundararaman
where t = 4 h/3 is the thickness of the ellipsoidal precipitate with major axis R and
minor axis h and ν is Poisson’s ratio. As per Eq. 3.1, as the γ particles grow (i.e.,
the aspect ratio R/t increases) with the progress of transformation, the constrained
strain εC increases and gradually approaches the stress-free transformation strain εT .
3.5.2 Precipitation of the δ Phase
The metastable γ phase transforms to equilibrium δ phase at temperatures above

650 °C in Alloy 625. Cozar et al. [58] have shown the formation of a few δ phase
needles along with profuse γ precipitation after aging for 2048 h at 700 °C. At
750 °C, it nucleates on grain boundaries and twin boundaries as well as within
grains after the aging of 100 h (Fig. 3.28a) [63], though the number density of δ
precipitates remains rather small. At temperatures 800 °C and above, the kinetics
of δ precipitation is considerably enhanced. However, at these temperatures, the
density of γ precipitates reduces significantly (Fig. 3.28b) [63]. Figure 3.28c, d show
intragranular and intergranular precipitation of δ precipitates in an Alloy 625 aged
at 800 °C for 240 h. Plastic deformation reduces the temperature and the incubation
period for the δ phase. Suave et al. [62] have reported the beginning of the nucleation
of the δ phase within 10 h at 750 °C in deformed Alloy 625 against its nucleation
after 100 h at the same temperature.
The morphological evolution of the δ phase particles in Alloy 625 is similar to that
in Alloy 718. Sundararaman et al. [29, 63] have shown that the δ phase particles first
nucleate predominantly at austenite grain boundaries and incoherent ledges of twin
boundaries and later at coherent twin boundaries. At high temperatures, intragranular
Fig. 3.28 Transmission electron microscopy images of δ phase precipitates in Alloy 625. a Intra-
granular precipitates after ageing of 100 h at 750 °C. b Intragranular δ precipitates coexisting with
a sparsely distribution of γ precipitates after ageing at 800 °C for 240 h. c and d A bright- and
dark-field pair of images showing δ precipitates nucleated at a grain boundary. Reprinted from Ref.
[63] by permission from Dr. M. Sundararaman
δ particles may nucleate homogeneously in the supersaturated γ matrix. Alterna-

tively, stacking faults of existing γ particles may act as their nuclei, as mentioned
in Sect. 3.2.3. The δ precipitates maintain (010)δ ||{111}γ and [100]δ || 011γ (or
(001)δ || {111}γ and [010]δ || 110γ depending upon whether the (010)δ or the (001)δ
is considered as the close-packed plane) orientation relationship with the austenite
matrix and grow parallel to {111} planes of the matrix. During growth, the growing
δ precipitates often pass through pre-existing γ particles belonging to appropriate
variants, while γ precipitates belonging to other variants hinders the advancement
of the growing δ particles. When sufficiently large, the needle shape δ precipitates
assume plate shape morphology and lose its coherency with the austenitic matrix
and the γ -δ interface becomes semi-coherent. An array of interfacial dislocations is
generated to accommodate the γ -δ misfit (Fig. 3.29). These dislocations have been
identified to be 1/2 <110> type. On the other hand, the precipitate is fully incoherent
in a direction normal to the habit plane, as the stacking sequence along this direction
of the γ and δ structures are different.
Fig. 3.29 Transmission

electron microscopy image
of dislocations at γ -δ
interfaces of a δ precipitation
in an Alloy 625 aged for 240
h at 800 °C. (Courtesy Dr.
M. Sundararaman)
3.5.3 Precipitation of the Ni2 (Cr, Mo) Phase
The Ni2 (Cr, Mo) phase forms with Ni2 X (X = Cr, Mo) stoichiometry in alloys that
contain nickel, chromium and molybdenum in the ratio that may or may not satisfy
the Ni2 X stoichiometry. The thermal stability of the Ni2 (Cr, Mo) phase is a function
of the relative concentrations of chromium and molybdenum in the phase, where the
chromium and molybdenum atoms both take positions of the X atoms in the Ni2 X
stoichiometry of the Pt2 Mo type lattice (Sect. 2.2.3). The addition of molybdenum
increases the thermodynamic stability and the solvus temperature of the Ni2 (Cr, Mo)
phase [39 – 41]. For example, the Ni2 (Cr, Mo) phase is stable at temperatures up to
about 628 °C in Alloy 625 (containing about 26 at% Cr and 6 at% Mo) [42], while
it is stable up to about ~775 °C in Haynes 242 (containing about 10 at% Cr and 16
at%) [43]. The increased stability of the Ni2 (Cr, Mo) phase in alloys is attributed
to its reduced formation energy with higher molybdenum. In binary alloy systems,
the Ni2 Cr is stable as its formation energy is −7.095 kJ/ mol [51]. In comparison,
the Ni2 Mo and Ni2 W phases are respectively barely stable and unstable as their
formation energies are nearly zero and +10 kJ/ mol, respectively [51]. The forma-
tion energies of binary compounds suggest that a gradual substitution of chromium
and molybdenum in Ni–Cr alloys makes the Ni2 (Cr, Mo) phase unstable. On the
contrary, studies have shown that the substitution of chromium and molybdenum
atoms increases its stability by lowering the formation energy of the Ni2 (Cr, Mo)
phase compared to the Ni2 Cr phase [68, 69]. Another independent study on the
stability of the Ni2 (Cr1−x Mox ) phase has shown that its formation energy decreases
up to x = 0.25 and starts increasing for x > 0.25 indicating the highest stability for the
Ni2 (Cr0.75 Mo0.25 ) composition of the Ni2 (Cr, Mo) phase [40]. On the other hand, the
addition of tungsten in Ni–Cr alloys destabilizes the Pt2 Mo type phase as shown by
its suppression in Ni–Cr–W alloys [70]. However, in the presence of molybdenum,
tungsten addition appears to increase the thermal stability of the Pt2 Mo type phase
[47], as witnessed by their higher thermal stability in Haynes 244 than Haynes 242.
An independent study on model Ni–Cr–Mo alloys has also confirmed an increase in
the thermal stability of the Pt2 Mo type phase with partial substitution of molybdenum
and tungsten [49]. These studies indicate that both Mo and W together increases the
thermal stability of the Pt2 Mo type phase in Ni–Cr–Mo–W alloys.
The Ni2 (Cr, Mo) phase forms via a disorder to order transformation reaction
wherein the chemical ordering of the disordered FCC lattice gives rise to ordered
body-centered orthorhombic structure, which may happen via continuous ordering at
relatively lower temperatures or by nucleation and growth mechanisms at somewhat
higher temperatures. An increase in the molybdenum concentration in Ni–Cr–Mo
alloys raises the solvus temperature of the Ni2 (Cr, Mo) phase due to higher thermal
stability to the phase. An increase in molybdenum concentration also increases the
kinetics of the Ni2 (Cr, Mo) phase. This effect of molybdenum is reflected in different
precipitation kinetics of the Ni2 (Cr, Mo) phase in Alloy 625 and Haynes 242. While
a significant amount of the Ni2 (Cr, Mo) phase forms within 10 h at temperatures
ranging from 650 to 750 °C in Haynes 242 [43], it takes about 1000 h at 600 °C
for its precipitation in Alloy 625 [45]. This difference in the kinetics is attributed
to solute species governing the formation of the Ni2 (Cr, Mo) phase. The kinetics is
slow when chromium controls the formation of the phase and is fast when molyb-
denum controls the precipitation as the diffusivity of molybdenum in the nickel
lattice is higher than chromium. This is deduced based on activation energy anal-
ysis of transformation peaks associated with the formation of the Ni2 (Cr, Mo) phase
in different model Ni2 (Cr1−x Mox ) alloys with varying chromium and molybdenum
solute concentrations [39, 71]. Further, higher misfit strain energy in alloys containing
higher molybdenum concentration due to comparatively bigger atomic size of Mo
would also assist in enhancing kinetics of the precipitation of the Ni2 (Cr, Mo) phase
and the morphology of the phase.
The difference in the kinetics also manifests itself in the morphology of the Ni2 (Cr,
Mo) phase. The formation of the Ni2 (Cr, Mo) phase is mainly reported with an ellip-
soidal morphology [45, 72–76]. However, particles with snowflake morphology in
service exposed wrought ammonia cracker tubes have also been reported [50]. Inter-
estingly, different morphologies of the Ni2 (Cr, Mo) phase in Alloy 625 are reported
by the same research group working on ammonia cracker tubes service exposed to
similar conditions but procured separately at different periods from different vendors.
Ammonia cracker tubes are about 9 mm thick, about 90 mm in outer diameter and
12 m long designed for service exposure of 100,000 h at temperatures in the range of
about 650–700 °C. However, local variations in the temperature during service expo-
sure were reported along the tube’s length [75]. Chakravartty et al. [75] have reported
particles of Ni2 (Cr, Mo) phase resembling ellipsoidal morphology in sections of
wrought tubes service exposed for 100,000 h at temperatures in between 600 and
650 °C. In contrast, Sundararaman et al. [50] have reported the snowflake morphology
in the sections of wrought tubes service exposed for about 70,000 h at temperatures
close to but below 600 °C. From these details, it can be safely deduced that temper-
atures of the tube sections reported by Chakravartty et al. [75] and Sundararaman
et al. [50] are likely to differ by about 20–40 °C. This difference in the temperature
is not less considering the narrow temperature window (~60 °C) for the precipi-
tation of the Ni2 (Cr, Mo) phase (Fig. 3.20). Ignoring the likely difference in the
relative concentrations of chromium and molybdenum, this temperature between the
two tubes may bring a significant variation in the kinetics of the Ni2 (Cr, Mo) phase
in the two cases. Interestingly, Singh et al. [42] have observed cuboidal/rhombus
morphology of Ni2 (Cr, Mo) phase particles in service exposed cast Alloy 625 and
found their size much bigger compared to particles of the same phase in the wrought
alloys [50, 75]. Such cuboidal/rhombus morphology is the crystallographic mani-
festation of the coherent faces when two perpendicular axes of the ordered cell do
not lie in the foil [76]. The large particle size of the Ni2 (Cr, Mo) phase in cast Alloy
625 could be attributed to local enrichment of molybdenum solutes in the vicinity of
inter-dendritic that may have aided the precipitation kinetics.
3.5.4 Precipitation of the Carbide Phases
The austenite phase has low solubility of carbon. Lower levels of carbon in
nickel-base alloys are maintained by reducing its content by adding strong carbide
forming elements like niobium, tantalum, and titanium [2], which combine with
carbon to form MC-type carbides during solidification. The MC carbide particles
are commonly observed in most nickel-based superalloys, including Alloy 625
(Fig. 3.30). Carbide particles that form during solidification are termed “primary
carbides”. Besides MC carbides, the formation of M23 C6 and M6 C types of primary
carbides have also been reported in Alloy 625 [42]. Figure 3.30b shows a micrograph
of the M23 C6 primary carbide. All the primary carbides appear as coarse particles,
often irregular in shape, distributed randomly within the austenite grains and at grain
boundaries and incoherent segments of twin boundaries [52]. The degeneration of the
(Nb, Ti)C carbides is the primary source of carbon for the formation of “secondary
carbides” that form during alloy processing or thermal exposure.
The precipitation of MC, M6 C and M23 C6 secondary carbides during thermal
annealing are reported by various researchers at temperatures ranging from 600 to
1050 °C [13, 52, 54, 77–81]. The M23 C6 carbide primarily precipitates at grain bound-
aries above 650 °C and usually occurs as irregular, discontinuous, blocky particles
or as continuous grain boundary film. The M6 C carbides precipitate at temperatures
above 800–850 °C when the M23 C6 becomes unstable. The M6 C carbides also precip-
itate at grain boundaries along with M23 C6 [1] as a thin film at grain boundaries or
in Widmanstätten morphology at intragranular locations [78].
Vernot-Loier and Cortial [78] have reported the formation of the MC carbide
particles at 1050 °C, which dissolves at temperatures above 1100 °C. Precipitation
of all the carbides follows a cube to cube orientation relationship with the austenite
phase.
Chakravartty et al. [75] have reported the precipitation of the M23 C6 type carbide
film at a temperature below 600 °C in Alloy 625 service exposed for a prolonged
time. Sundararaman et al. [52] have shown the formation of a nearly continuous film
Fig. 3.30 Transmission electron microscopy micrographs of primary a MC and b M23 C6 carbides
in cast Alloy 625 alloy. c and d Electron diffraction patterns from corresponding MC and M23 C6
particles. Reprinted from Ref. [42], Copyright (2015), with permission from Elsevier
of the M23 C6 phase at many grain boundaries after aging of 90 h at 650 °C and
even much thicker film within 24 h at 750 °C. The coalescence of carbide particles
formed these films. Figure 3.31a shows the precipitation of M23 C6 carbide particles
along grain boundaries after a prolonged aging at 650 °C. The extent of carbide
precipitation at grain boundaries varies from boundary to boundary depending upon
the energy and misorientation of the boundary [80]. When carbide particles form
at grain boundaries, particles orient with respect to one of the two austenite grains
(Fig. 3.31b). Apart from nucleation at grain boundaries, heterogeneous nucleation
of the M23 C6 carbides may also occur at dislocations and incoherent segments of
annealing twin boundaries (Fig. 3.31c, d). At temperatures of 800 °C and above,
co-precipitation of the carbide and the δ phases occur pretty frequently at the grain
boundaries (Fig. 3.22) [52]. The secondary carbides first precipitate at intergranular
sites, but they precipitate progressively within grains when grain boundaries are
saturated. The precipitation of the M6 C carbides at grain boundaries is sensitive to
the amount of silicon as it promotes the nucleation of M6 C. The presence of silicon
Fig. 3.31 Transmission electron microscopy images depicting the precipitation of M23 C6 carbide
in Alloy 625 at: a grain boundaries during prolonged ageing at about 650 °C; b a dark-field image
showing the growth of carbide particles into grain B after 24 h of ageing at 750 °C; c and d respec-
tively show the precipitation of M23 C6 carbide particles at dislocations and incoherent segments of
twin boundaries. c and d Reprinted from Ref. [63] by permission from Dr. M. Sundararaman
as low as less than about 0.15% may significantly retard the precipitation of M6 C
carbides, mainly when the carbon is below about 0.035% [13].
The morphology of grain boundary carbides has an important bearing on the
overall properties of the alloy. For example, small discrete particles of secondary
carbides at grain boundaries increase the creep-rupture life of the alloy. In contrast,
precipitation of continuous grain boundary films can severely degrade the impact
and rupture properties of the alloy by providing an easy fracture path [15].
3.5.5 Precipitation of the TCP Phases
Alloy 625 is susceptible to the formation of undesirable σ, μ and Laves TCP phases
due to the presence of high amounts of metals like niobium, chromium, tungsten,
and molybdenum. These phases may form during solidification, processing or service
and their precipitation deplete refractory elements in the γ matrix, causing a loss of
strength. Proper control of alloy’s chemistry and processing conditions can avoid the
precipitation of the TCP phases in Alloy 625.
The hexagonal Laves phase is the most frequently observed of the three TCP
phases that may form in Alloy 625 [13, 82]. It usually forms as blocky and irregular
particles at grain boundaries, similar to the formation of grain boundary M6 C and
M23 C6 carbide particles. Figure 3.20 shows a single curve for the beginning of the
precipitation of the δ and Laves phases. Prolonged thermal exposures at temperatures
over the 700–980 °C range may precipitate Laves and δ phases at grain boundary
regions that may already contain carbide particles. Identifying the Laves phase in
such a configuration may need the support of complete electron diffraction and
chemical analysis to delineate it from grain boundary carbides because of their similar
morphologies. While the grain boundary carbides may be dissolved by an annealing
treatment of about an hour at temperatures about 1100 °C or higher, the dissolution
of the δ and Laves particles may require a significantly longer time. For example,
Floreen et al. [13] have shown minimum annealing of 24 h at 1100 °C to dissolve
even small quantities of Laves and δ phases completely.
Figure 3.32 shows an example of the particles of Laves phase of Ni3 Mo2 Si type
precipitated at grain boundaries during aging of 24 h at 760 °C [82]. Silicon appears
to stabilize this phase, as evidenced by the EDS spectrum.
The formation of the μ phase in Alloy 625 is reported less frequently than the Laves
phase. Evans et al. [83] have reported the μ phase at grain boundaries during creep
deformation of thin foils of Alloy 625. Tawancy [84] has reported the precipitation of
the μ phase with blocky morphology in Alloy 625 and many other nickel–chromium-
molybdenum alloys containing more than 3% iron during prolonged thermal expo-
sures of up to 16,000 h at temperatures over 540–870 °C. The precipitation kinetics
increases with increasing temperature in this temperature range and is fastest at 870
°C. The μ-phase particles are characterized by defect structure comprising twins
and stacking faults parallel and normal to the basal plane [85] and exhibit a pref-
erential tendency to nucleate at pre-existing molybdenum-rich carbides both within
grains and grain boundaries [83]. Tawancy [84] has shown that all nickel–chromium–
molybdenum alloys, like Hastelloy C, C-276, C-22, which contain iron more than
3% alloys, exhibit the precipitation of a Mo6 Ni7 type μ-phase at temperatures over
the 540–870 °C range (Fig. 3.33) [82]. In contrast, alloys like Hastelloy C-4, 230,
B2 and S, which contain iron less than or equal to 3%, do not show the precipitation
of the μ-phase. Alloy 625 also exhibits the precipitation of the μ-phase only when
it contains iron more than 3%. The presence of iron stabilizes the otherwise ther-
modynamically unstable Mo6 Ni7 type μ-phase [84]. Tawancy [84] has correlated
this behavior of the μ-phase precipitation to the concentrations of major solutes and
iron and concluded that, for a given combined concentration of molybdenum and
tungsten, the tendency to form the μ-phase reduces with an increase in the nickel to
iron plus cobalt ratio.
The σ phase is known to form in alloys containing high concentrations of iron
and chromium. It may precipitate at grain boundaries, incoherent twin boundaries,
or both. Its kinetics is very slow and may take hundreds and sometimes thousands of
hours. Very limited cases of the precipitation of the σ phase are reported in Alloy 625.
Evans et al. [83] have reported the formation of σ phase precipitates of approximately
Cr5 Ni3 Mo2 composition during creep rupture of a thin Alloy 625 foil.
Fig. 3.32 Precipitation of silicon-stabilized Laves phase in Alloy 625 after ageing of 24 h at 760
°C. a Bright-field TEM image showing an array of Laves phase particles at grain boundaries. b
[120] zone axis microdiffraction pattern from the encircled Laves phase particle in a consistent
with its hexagonal structure. c Corresponding EDS spectrum shows the predominant presence of
silicon, molybdenum and nickel and minor iron and chromium elements. Reprinted by permission
from Springer Ref. [82]. Copyright (2017)
Several studies on ammonia cracker tubes of Alloy 625, service exposed for
prolonged periods at temperatures up to about 850 °C, are reported [15, 42, 75,
79, 86]. However, none of these studies reported the formation of any TCP phase.
The ammonia cracker tubes operate at temperatures ranging from about 600 °C to
700 °C. Higher temperatures reported in certain portions of tubes were due to local
temperature excursions during operation. The no observation of the TCP phases may
likely be because of shorter periods of the temperature excursion to the temperature
Fig. 3.33 Precipitation of μ phase in Alloy C-276 after ageing of 1 h at 870 °C. a Bright-field TEM
image showing a blocky particle of μ phase particle with characteristic internally faulted structure.
b–e Microdiffraction patterns corresponding to different zone axes b [001], c [0 1 0], d [1 7 1] and
e [1 8 1] of the μ phase. f EDS spectrum showing the elemental composition of the μ phase in the
alloy. Reprinted by permission from Springer Ref. [82]. Copyright (2017)
at which the TCP phases form or the low concentrations of elements like Fe and Si
that promote their formation.
Fig. 3.34 Precipitation free zone around a M23 C6 carbides precipitated at grain boundaries after
ageing at 700 °C for 200 h, and b δ precipitates after prolonged ageing at around 750 °C. Reprinted
a from Ref. [63] by permission from Dr. M. Sundararaman. Image b Courtesy Dr. M. Sundararaman
3.5.6 Precipitation-Free Zones
Two distinct γ precipitate free zones have been observed in Alloy 625. One around
the extensively precipitated grain boundary M23 C6 /M6 C carbides and the other
around large δ precipitates (Fig. 3.34). The formation of the γ free zones may
be attributed to their dissolution close to carbide and δ precipitates. Conversely,
the depletion of solutes impedes further nucleation of γ precipitates. Kirman and
Warrington [87] have suggested forming precipitate free zones around NbC precipi-
tates in niobium bearing nickel-base alloys due to either vacancy or solute depletion.
Vacancy depletion plays a vital role in creating the precipitate free zone around NbC
particles in Alloy 718 [52]. A significant difference in the volume misfit between the
NbC and the austenite phase generates internal stresses, which are reduced by the
migration of vacancies to the growing carbide precipitates. The size/width of such
precipitate free zones increases with increasing aging time and the precipitate size
[50]. Processing history may affect the extent of precipitation-free zones [13].
The precipitation-free zones in Alloy 625 form due to the depletion of niobium,
chromium or molybdenum solutes. Raghavan et al. [54] have shown that the
growth of the M23 C6 precipitates depletes chromium and molybdenum from the
adjacent austenite matrix, while that of the M6 C particles depletes molybdenum.
Sundararaman et al. [50] have argued that the γ free zones in the vicinity of grain
boundary carbides are mainly due to solute depletion. The vacancy depletion plays
a minor role because the misfit between the austenite and the M23 C6 or M6 C carbide
in Alloy 625 is not very large (Sect. 2.2). Therefore, precipitation of the two carbides
would not create much internal stress. On the other hand, the precipitation of either of
the carbide phases would deplete the adjacent region of chromium or molybdenum.
The depletion of chromium or molybdenum would enhance the solubility of γ
precipitates in the vicinity of carbides, resulting in precipitate free zones. Similarly,
the precipitation of δ precipitates forms precipitates free zones around them.
The precipitate free zones are more ductile than the matrix. Small size
precipitation-free zones may be beneficial in improving the creep life of precipitation-
hardened alloys containing a high-volume fraction of precipitates. A thin precipitate
free zone helps relieve the stress concentrations due to the accumulation of dislo-
cations during creep. However, when the precipitate free zone is too broad, it may
cause easy failure due to the weakening of the matrix there.
3.6 Summary
Alloy 625 is designed to be a solid solution strengthened alloy. However, processing

and heat treatment of Alloy 625 at temperatures above 550 °C precipitate out ordered
intermetallic phases γ , δ and Ni2 (Cr, Mo) and various carbides in the disordered
nickel matrix. These phases form due to the interaction of multiple solutes present
in high concentrations. Each phase has unique characteristics and morphology and
evolves depending on the exposure time and temperature. Deformation accelerates
the kinetics of precipitation. The precipitation of these phases would modify the
alloy’s mechanical, corrosion, and welding behavior. The broad composition range
of the alloy allows a variation in its composition range. Such a variation may affect
some properties strongly. Tighter control of a few elements may improve some alloy
properties significantly. However, this improvement in properties by a composition
adjustment may be a trade-off with other properties.
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Metall Trans 1:2667–2675
Chapter 4
Mechanical Behavior of Alloy 625
Alloy 625 contains substantial alloying elements that impart excellent strength and
creep resistance in solid-solution conditions. As noted in Chap. 3, these elements
may cause the precipitation of different intermetallic and carbide phase parti-
cles during thermo-mechanical processing. Precipitation of these phases affects
mechanical behavior of the alloy. The ordered intermetallic phases form as small
and coherent particles distributed homogenously throughout the matrix. Twinning
plays an essential role in the continuity of deformation across intermetallic phase
particles during the alloy’s deformation. This chapter discusses various factors that
govern the mechanical behavior of Alloy 625.
4.1 Fundamentals of Plastic Deformation of Crystalline

Solids
Plastic deformation occurs by the movement of dislocations when the shear stress
exceeds a critical value, known as “critical resolved shear stress”. It occurs primarily
by two modes, namely, slip and twinning.
4.1.1 Deformation by Slip
Slip is the most commonly observed deformation mode. Slip deforms metals by
sliding a part of the crystal, over the remaining, along definite crystallographic planes
called “slip planes”. Slip is generally confined to the low-index planes as they contain
a high density of atoms per unit area, thereby providing the least lattice friction
(Peierls stress) to the motion of dislocations. The translational symmetry of the crystal
lattice perfectly restores the crystal structure after the slip. A slip plane containing
a slip direction defines a “slip system”. For example, in the face-centered cubic
https://doi.org/10.1007/978-981-19-1562-8_4
112 4 Mechanical Behavior of Alloy 625
Fig. 4.1 a Schematic arrangement of atoms depicting an edge dislocation; b Conservative motion of
an edge dislocation within the glide plane in the direction of slip (arrow mark); c Non-conservative
motion of dislocation by a climb in a direction perpendicular to the slip plane. Square symbol
represents the row of atoms that moved from one location to another as a result of climb.
structure, four independent {111} octahedral planes, each having three independent
<110> close-packed directions, together give 12 independent slip systems.
Slip occurs most readily in specific directions on certain close-packed crystal-
lographic planes, and the displacement that defines the magnitude and direction of
the movement of atoms is called Burgers vector (b) of the dislocation. Dislocations
are linear crystallographic defects or singularities in a crystalline lattice where extra
atoms are arranged linearly within the body of the crystal. Dislocations are basically
of two types, edge and screw dislocations, though a combination of the two, called
“mixed dislocations”, is most commonly observed. In an “edge dislocation”, the extra
atoms are arranged in a row of mismatched atoms along a straight line as an extra
half-plane (Fig. 4.1a) within the crystal, while extra atoms in a “screw dislocation”
trace a spiral path around the dislocation line with a pitch of one interplanar distance
within the crystal.
Dislocation motion is generally of two types, conservative and non-conservative,
depending on whether the number of atoms in the neighborhood of a dislocation core
changes due to the motion [1, 2]. When a dislocation moves in the glide plane in the
direction of slip, its movement is termed “conservative”. When a dislocation moves
by climbing in a direction normal to the slip plane, it is termed “non-conservative”.
Figure 4.1b, c, respectively show the conservative and non-conservative movements
of the edge dislocation shown in Fig. 4.1a. The climb usually occurs when deforma-
tion is assisted by thermal activation of atoms at elevated temperatures or when the
crystal possesses a density of interstitials and vacancies, which are attracted toward
dislocation cores by their interacting stress fields [1, 2]
When the slip associated with dislocations displaces atoms into their coincidence
positions, dislocations are termed “perfect dislocations”. Perfect dislocations move
atoms by integral multiple of atomic distances in a specific direction along the slip
plane (Fig. 4.1). Dislocations with Burgers vector 1/2<110> in a face-centered cubic
crystal move atoms by one atom distance are called “unit dislocations”. Dislocations
with Burgers vectors having magnitudes larger than unity are also possible. But,
4.1 Fundamentals of Plastic Deformation in Crystalline Materials 113
they are unstable and tend to dissociate into two or more dislocations of smaller
Burgers vector as per the dislocation dissociation reaction b1 → b2 + b3 provided
the reaction satisfies the condition, b21 > b22 + b23 , where b1 is the Burgers vector
of the un-dissociated dislocations, and b2 and b3 are Burgers vectors of dissociated
dislocations. The driving force for such dissociation reactions comes from a reduction
in strain energy of the dislocation, which is proportional to the square of its Burgers
vector.
If the magnitude of the Burgers vector is not equal to a crystal’s translation vector,
the dislocation is called a “partial dislocation”. The movement of partial dislocations
causes a local error (fault) in the stacking sequence on the dislocation slip plane.
Such stacking faults (SFs) are common in face-centered cubic (FCC) materials like
nickel and copper alloys due to their low stacking fault energies. In these alloys,
a perfect dislocation, say 1/2[11̄0], may dissociate into two partial dislocations of
1/6<112> type as per the dissociation reaction:
1/2[11̄0] → 1/6[21̄1] + SF + 1/6[12̄1̄] (4.1)
In FCC structures, dislocations of 1/6<112> type are commonly called “Shockley

partials”.
4.1.2 Deformation by Twinning
Twinning generally occurs when the slip is restricted due to fewer operable slip
systems or when the slip’s critical resolved shear stress is more than the twinning
stress. It is commonly observed at low temperatures or high strain rates (e.g., shock
loading) in metals with body-centered cubic (BCC) and hexagonal close-packed
(HCP) crystal structures. Twinning is also common in many FCC metals and alloys
with low stacking fault energy (SFE). Twinning occurs when atoms in a portion are
homogeneously sheared to orientations that are mirror related to atoms in the un-
twinned lattice across a plane called the ‘twinning plane’ (Fig. 4.2a). Twinning occurs
in a definite direction, called the ‘twinning direction’, on a specific crystallographic
plane. Twinning is characterized by four essential elements, namely, the twinning
plane, K 1 , the twinning direction, η1 , an undistorted plane (other than the K 1 ), K 2 ,
and a second twinning direction, η2 ; the last two elements essentially arise from the
condition of homogeneous shear (Fig. 4.2b).
Twinning differs from slip mainly in the following respects: (1) The orientation
of the crystal above and below the slip plane remains the same after the slip, while in
twinning, the orientation of the twinned crystal is different across the twin plane; (2)
In slip, the deformation usually occurs in discrete multiples of the atomic spacing,
while in twinning the atom’s movement is much less than a translation vector of the
lattice; (3) In slip, the deformation occurs on relatively widely spread planes, while
in twinning every atomic plane in the twinned region is involved in the deformation;
(4) A large amount of the bulk plastic deformation can be produced by slip, while
Fig. 4.2 a Illustrates twinning of the lattice under the action of twinning shear; b Schematic illus-
trating the geometric relationship between different twinning elements when an upper hemisphere
of a solid sphere is brought into a twin relationship with the lower hemisphere across the twinning
plane (K 1 ). A second plane, the K 2 plane, remains undistorted but rotated in the distorted upper
hemisphere. The shear plane is parallel to the plane of the paper
the twinning produces comparatively a small amount. However, the twinning may
aid slip by reorienting crystals to orientations favorable for the slip relative to the
stress axis.
Stacking faults influence the plastic deformation of metal significantly. Stacking
faults are errors in the stacking sequence of close-packed planes, which can be
produced in many metals by plastic deformation or annealing. The atomic arrange-
ment of atoms on the close-packed {111} plane of an FCC structure and the close-
packed {0001} plane of an HCP structure is similar, but the two structures have
a different stacking sequence of their close-packed planes. An FCC structure is
obtained when the close-packed planes are stacked as …ABCABCABC… On the
other hand, a stacking sequence of …ABABAB… type produces an HCP structure
(Fig. 4.3). Therefore, a fault in the stacking sequence in the FCC structure makes
four layers of the HCP structure. Such a fault can be created in an FCC crystal if
atoms, say above the B plane, are moved by the glide of a Shockley partial dislocation
(1/6<112>) [1]. Such a movement of atoms would bring the C layer directly over the
A layer and thus produces a local HCP sequence. A stacking fault can be viewed as
an “extended dislocation” comprising a thin HCP region bounded by partial dislo-
cations. Since stacking fault is not the equilibrium structure of the crystal, it raises
the crystal’s energy. This energy is called stacking fault energy (SFE). Stacking fault
energy can be treated as the surface tension of the stacking fault that pulls the partial
dislocations together, which repel each other due to their nearly parallel line direc-
tions. The lower the stacking fault energy, the greater the separation between the
partial dislocations and the wider the stacking fault.
The stacking fault energy plays a vital role in the deformation of the metal.
Stacking faults in FCC metals can also be considered sub-microscopic twins of four
Fig. 4.3 Schematic showing the stacking of close-packed layers of atoms in an FCC lattice. a A
three-layer stacking of the close-packed {111} plane viewed along the plane normal. Layers A, B
and C, respectively, are shown by circles of decreasing diameter. b Stacking of the {111} plane
viewed perpendicular to the plane. c Formation of an HCP region after introducing a stacking fault
in the FCC stacking sequence
atom thicknesses. Deformation twinning is therefore favored in metals with low SFE,
dislocation-slip in metals with high SFE. Metals with high SFE, such as aluminum,
have a deformation substructure of dislocation tangles and cells. In contrast, metals
with low SFE are characterized by stacking faults or banded substructures comprising
planar arrays of dislocations that make cross slip and climb of dislocations difficult.
4.1.3 Deformation in Superlattice Compounds
The directional nature of bonding in ordered intermetallic phases necessitates the

displacements of large magnitudes to bring the ordered lattice back into coincidence
with itself. Burgers vectors of large magnitudes are illustrated by considering the
arrangement of N and M atoms in a close-packed {111} plane of an N3 M compound
with an L12 structure (Sect. 2.1). On each {111} plane of the L12 structure,1 two
1/2<110> displacements in each close-packed direction are required. Figure 4.4a
shows the arrangement of atoms on the (111) plane of an N3 M compound with the
L12 structure. It can be noticed that the movement of a minority atom M by <110>
displacement in all the three close-packed directions brings it into coincidence with
itself. Dislocations with such large Burgers vector are called superlattice dislocations
(or simply “superdislocations”), and the 1/2<110> dislocations are called “superpar-
tial dislocations” of the superlattice. The total Burgers vector of a superdisloca-
tion must necessarily be equal to an integral multiple of the superpartial translation
vector. The movement of superpartials of 1/2<112> type in the ordered structure
breaks its order in the slip plane as illustrated in Fig. 4.4b. This destruction of the
chemical order is associated with extra boundary energy, called anti-phase boundary
(APB) energy. Therefore, the superpartial dislocations move in pairs separated by a
1Indices for all the phases, throughout the chapter, are expressed in the FCC basis unless and
otherwise specifically mentioned or subscripted with a lattice notation.
Fig. 4.4 a Arrangement of atoms on (111) plane of the ordered L12 structure (N3 M stoichiometry).
b Schematic showing the creation of anti-phase boundary when a dislocation passes through an
ordered phase precipitate
Fig. 4.5 A TEM micrograph showing pairs of 1/2<110> dislocations in a deformed Alloy 693
containing fine precipitates of γ phase
ribbon of APB. Figure 4.5 shows a transmission electron microscopy (TEM) image
of dislocation pairs of 1/2<110> dislocations observed in lightly deformed Alloy 693
containing fine precipitates of the hardening γ phase. Further, the 1/2<110> super-
partial dislocations may decompose into Shockley partial dislocations depending
upon the stacking fault energy of the alloy. The creation of stacking faults in ordered
structures may or may not disturb the long-range order of the lattice. When they do
not disturb the chemical order of the lattice, they are termed superlattice intrinsic
stacking faults (SISFs) or simply geometric stacking faults (GSFs). When stacking
faults destroy the chemical order locally, they are termed complex stacking faults
(CSFs) and are associated with very high energy. For this reason, CSFs are usually
not observed. On the other hand, SISFs are commonly observed in intermetallic
compounds with low stacking fault energies. In such alloys, the dissociation of a
superdislocation into Shockley partial dislocations may be represented by a reaction
like:
[011] → 1/2[011] + APB + 1/6[121] + SISF + 1/6[1̄12] (4.2)
where SISF represents the stacking fault bounded by Shockley partials. Such a config-
uration of superdislocations involving an APB and a stacking fault is quite common
in ordered L12 structures [3]. At high temperatures, such decomposition reactions
allow the APB to be located on the low energy {001} plane while the SISF remains
on the {111} plane. This results in a sessile dislocation configuration known as Kear
and Wilsdorf lock [4].
4.2 Deformation Crystallography of Hardening Phases

in Alloy 625
As presented in Chap. 3, various intermetallic and carbide phases may form in Alloy
625 depending upon the temperature and time of exposure. The primary hardening in
age-hardened conditions of the alloy comes from γ and Ni2 (Cr,Mo) phase particles,
and comparatively much lesser from the δ phase particles. Carbide phases behave
as non-deformable particles but contribute little to hardening in this alloy. This
section is therefore restricted to understanding dislocations and defect structures
in γ , Ni2 (Cr,Mo) and δ phases. Further, due to the non-cubic nature of these phases,
their deformation behavior depends on the orientation of their variants with respect
to the stress axis.
4.2.1 γ Phase
The deformation characteristics of the γ phase are illustrated considering a particle
whose c-axis is oriented along the [001] direction of the matrix. Figure 4.6 shows the
arrangement of atoms on (111) closed-packed plane of the D022 structure when its c-
axis is oriented along the [001] direction of the matrix. Neglecting distortions due to
tetragonality, FCC (111) plane would become (112)γ " of the D022 structure. All the
four {111} planes of the disordered lattice would become {112}γ planes of the D022
structure and have similar arrangements of N and M atoms. The minority element
atoms (M atoms) would be arranged in a rectangular array in the closed-packed plane,
and each layer maintains the N3 M stoichiometry. Such an arrangement of minority
atoms destroys the three-fold rotational symmetry of the FCC {111} planes in the
D022 structure. That is why the close-packed <110> directions of the FCC structure
(e.g., [1̄10], [1̄01] and [011̄] in Fig. 4.6) are not equivalent in the D022 structure.
The stacking of six close-packed layers, one above the other as
…A1 B1 C1 A2 B2 C2 A1 B1 C1 … in a manner that every successive layer is displaced
by a vector 1/3[1̄21̄] (or 1/3[21̄1̄]) with respect to the previous layer would make
up the D022 structure. For example, layer B1 is displaced with respect to layer A1
Fig. 4.6 The atomic arrangement on (111) planes and their stacking sequence in the D022 lattice.
The arrows shown represent the displacement vector. Circles, squares and triangles represent the
atom positions on the 1st, 2nd and 3rd layers. Atom positions on the 4th, 5th and 6th layers coincide
with those of the 1st, 2nd and 3rd layers such that superimposition of minority atoms occur only
after every six layers. The open and grey symbols represent N and M atoms of the N3 M D022
phase. Delineated rectangle shown by broken lines indicates the rectangular ordering nature in
D022 structures
by a vector 1/3[1̄21̄], layer C1 is displaced by the same vector with respect to the
B1 layer, etc. A1 and A2 layers (and similarly B1 and B2 layers as well as C1 and
C2 layers) contain atom positions vertically above (or below) one another along the
[111] direction in such a way that the superimposition of the minority atom occurs
only after six layers.
Different dislocations that can be encountered in the γ phase can be inferred
from an inspection of the possible lattice translation vectors on the (111) plane of
the [001] variant of the D022 structure (Fig. 4.6) and are listed in Table 4.1. The table
also lists dislocations in other octahedral planes and for all the planes for the other
two variants of the γ phase (Table 2.5). For the [001] variant, the Burgers vectors
of perfect dislocations are 1/2[112̄], [1̄10], [202̄], [02̄2], [24̄2] and [4̄22], and listed
in the ascending order of their magnitudes. The shortest perfect dislocations in the
D022 structure (Fig. 2.2) are [100] and [010], but they do not lie on the close-packed
plane.
The superdislocations [1̄10] and <1̄01]2 comprise doublet or quadruplets of
1/2<110> of superpartials. Therefore, superdislocations may split into pairs of super-
partials bounding an APB. Likewise, the perfect dislocation 1/2[112̄] may split into
three 1/6[112̄] Shockley partials to reduce its energy. All the three types of dislocation
2 Mixed parenthesis notation used for directions and planes in the text represents that all permutations
are possible only on the first two indices while the third index is fixed. For example, in the present
case, <1̄01] represents [1̄01] as well as [01̄1] directions.
4.2 Deformation Characteristics of Hardening Phases in Alloy 625 119
arrangements have been observed in the Ni3 V phase, which is iso-structural to the
γ phase and has the lattice parameters very close to it [5–8]. Since the stacking fault
energy of the γ phase is low, the 1/2<110> superpartial dislocations may further
dissociate into Shockley partials depending upon whether the splitting would create
a superlattice intrinsic stacking fault. For example, a minority atom, M, at a site,
say X in Fig. 4.6, in a plane above (111) plane would be shifted to a site Y corre-
sponding to the next layer, by a displacement equal to 1/6[112̄]. This displacement
corresponds to the shortest Burgers vector of the partial dislocation (Table 4.1). This
Table 4.1 Burgers vectors of possible perfect and partial dislocations in the D022 structure on the
four octahedral planes. [100], [010] and [001] represent variants of the D022 structure whose c-axis
is oriented along these directions. Note that the perfect translation vectors are applicable in their
opposite directions also
Glide plane Dislocation burgers vectors in different variants of the γ phase
Perfect translations Shortest burgers vectors of partials
bounding a pure stacking fault
[100] [010] [001] [100] [010] [001]
(1̄ 1 1̄) 1/2[211̄] 1/2[1̄2̄1̄] 1/2[1̄12] 1/6[211̄] 1/6[1̄2̄1̄] 1/6[1̄12]
[01̄1̄] [101̄] [1̄1̄0] 1/3[211̄] 1/3[121] 1/3[11̄2̄]
2[1̄1̄0] 2[01̄1̄] 2[101̄] 2/3[1̄12] 2/3[1̄12] 2/3[1̄12]
2[101̄] 2[1̄1̄0] 2[01̄1̄] 2/3[211̄] 2/3[211̄] 2/3[211̄]
2[1̄12] 2[211̄] 2[1̄2̄1̄] 2/3[1̄2̄1̄] 2/3[1̄2̄1̄] 2/3[1̄2̄1̄]
2[1̄2̄1̄] 2[1̄12] 2[211̄]
(11̄1̄) 1/2[2̄1̄1̄] 1/2[121̄] 1/2[11̄2] 1/6[2̄1̄1̄] 1/6[121̄] 1/6[11̄2]
[01̄1][01̄1] [1̄01̄] [1̄1̄0] 1/3[211] 1/3[1̄2̄1] 1/3[1̄12̄]
2[1̄1̄0] 2[01̄1] 2[1̄01̄] 2/3[11̄2] 2/3[11̄2] 2/3[11̄2]
2[1̄01̄] 2[1̄1̄0] 2[01̄1] 2/3[121̄] 2/3[121̄] 2/3[121̄]
2[11̄2] 2[2̄1̄1̄] 2[121̄] 2/3[2̄1̄1̄] 2/3[2̄1̄1̄] 2/3[2̄1̄1̄]
2[121̄] 2[11̄2] 2[2̄1̄1̄]
(1̄1̄1) 1/2[21̄1] 1/2[1̄21] 1/2[1̄1̄2̄] 1/6[21̄1] 1/6[1̄21] 1/6[1̄1̄2̄]
[01̄1̄] [1̄01̄] [1̄10] 1/3[2̄11̄] 1/3[12̄1̄] 1/3[112]
2[1̄10] 2[01̄1̄] 2[1̄01̄] 2/3[21̄1] 2/3[21̄1] 2/3[21̄1]
2[1̄01̄] 2[1̄10] 2[01̄1̄] 2/3[1̄21] 2/3[1̄21] 2/3[1̄21]
2[1̄1̄2̄] 2[21̄1] 2[1̄21] 2/3[1̄1̄2̄] 2/3[1̄1̄2̄] 2/3[1̄1̄2̄]
2[1̄21] 2[1̄1̄2̄] 2[21̄1]
(111) 1/2[2̄11] 1/2[12̄1] 1/2[112̄] 1/6[2̄11] 1/6[12̄1] 1/6[112̄]
[01̄1] [101̄] [1̄10] 1/3[21̄1̄ 1/3[1̄21̄] 1/3[112̄]
2[1̄10] 2[01̄1] 2[101̄] 2/3[12̄1] 2/3[12̄1] 2/3[12̄1]
2[101̄] 2[1̄10] 2[01̄1] 2/3[2̄11] 2/3[2̄11] 2/3[2̄11]
2[12̄1] 2[2̄11] 2[12̄1] 2/3[112̄] 2/3[112̄] 2/3[112̄]
2[112̄] 2[112̄] 2[2̄11]
shift does not produce any first nearest neighbor bond violation in the ordered lattice
but disturbs only the stacking sequence. On the other hand, the passage of partials
with Burgers vectors 1/6[12̄1] and 1/6[2̄11] on the (111) plane (Fig. 4.6) would
result in first nearest neighbor bond violations compared to the perfect lattice, which
would create a stacking fault as well as violate the nearest neighbor bond. Such
faults are termed complex stacking faults (CSFs) and are associated with very high
energy. Nonetheless, if the displacement vectors of the three partials are quadrupled,
as 2/3[2̄11], 2/3[12̄1] and 2/3[112̄], all the three partials can glide in all the three
orientations of the γ phase without violating the nearest neighbor bonds (see Table
4.1). Even though such partials are associated with high self-energies, their operation
has been reported in the deformed Ni3 V phase [9]
The passage of 1/6[112̄] dislocations on every (111) plane generate
a true crystallographic twin, and the new stacking sequence would be
…A1 B1 C1 A2 B2 C2 A1 C2 B2 A2 C1 B1 A1 …. (Fig. 4.7). A true twin retains the long-
range order of the parent crystal within the twinned crystal such that minority atoms
are also in mirror reflection across the twin plane. On the other hand, other partial
dislocations bring lattice sites in twin positions incorrectly occupied by different
atom species, breaking the long-range order. Such twins are called pseudo twin [10,
11]. Out of the 12 twinning modes of the disordered structure, only four modes
transform the γ phase lattice to true twinning modes. The remaining eight modes
transform to pseudo twinning modes. As a consequence, two of the {110} planes of
shear become {110)γ " planes for the true twinning modes of the superlattice while the
remaining four {110} become {102)γ " planes for the pseudo twinning modes of the
D022 structure. Table 4.2 gives characteristic twinning elements of the two modes of
twins. The following provides a brief description of the formation of the true twins in
the D022 structure with c-axis along [001] direction of the FCC structure. For more
details, the reader is referred to references [12, 13].
Orienting the superlattice in a manner that orients the twinning plane (111)
(i.e., (112)γ " plane) in edge-on orientation would bring the shear plane (11̄0)
parallel to the plane of the paper. Projection of the N3 M superlattice onto the
shear plane (plane of the paper) is shown in Fig. 4.7. A repeating four shearing
plane sequence of …01230… type, each containing N and M atoms in an order
Table 4.2 Twinning elements for different twinning modes in γ and Ni2 (Cr,Mo) phases, given in
terms of corresponding ordered unit cell indices
Twin type K1 K2 η1 η2
γ phase
Combined (1, 1, 2) (1, 1, 2̄) [1, 1, 1̄] [1, 1, 1]
Pseudo (1̄, 1, 2) (1.077, 1.039, 2) [2.315, 4.315, 1] [2̄, 4, 1]
Ni2 (Cr,Mo) phase
Combined (1, 0, 1) (1, 0, 1̄) [1, 0, 1̄] [1, 0, 1]
Type I-II (0, 3, 1) (0.966, 0.034, 1) [8.344, 1̄, 3] [1, 1, 1]
Pseudo (0, 3̄, 1) (0, 3̄, 1̄) [0, 1̄, 3̄] [0, 1̄, 3]
Fig. 4.7 Schematic drawing illustrating the projection of N3 M lattice onto the shear plane (11̄0).
A repeating four-layer shear plane stacking of type …01230… constitutes the D022 structure. A
twinning shear, η, of 1/6[112̄] on every (111) (i.e., (112) D022 ) plane generates a true crystallographic
twin. Note that only the zeroth and the 1/4th layers are shown, as the 1/2 and 3/4th layer positions
coincide with those of the previous two layers in such a way that the minority atoms coincide only
after four layers
…(N1/2 M1/2 )N(M1/2 N1/2 )N…, constitutes the N3 M lattice. The 1st and the 3rd layers
contain only N atoms, whereas the zeroth and 2nd layers contain N and M atoms in
an equal proportion, with the two atoms switching their positions in the two layers.
It is to be noted that, in terms of the FCC notation, even-numbered planes corre-
spond to zeroth layer projection of the shear plane in an FCC structure, whereas
odd-numbered layers correspond to that of the half layer projection. The tetragonal
axis in this projection lies within the plane of paper along [001] direction. In contrast,
the a- and b- axis are pointing, respectively outward and inward from the plane of
the paper in such a way that the projection of both the axes in the plane of paper
lie along [110] direction. It can be seen that a shear of 1/6[111̄]γ " (i.e., 1/6[11 2̄])
magnitude on this plane would bring the lattice points occupied by the right kind
of atoms at twin positions with respect to the matrix (un-twinned lattice). Since the
repeat vector along [111] direction is six times the interplanar spacing, shear of such
a magnitude would be required on at least six consecutive (111) planes to restore the
twinned lattice with respect to the matrix. This type of twinning, along with a slip of
<110] and <100] at higher temperatures (in the [001] domain), has been observed in
the Al3 Ti phase with D022 structure [14].
4.2.2 δ Phase
The ordered arrangement of atoms in the D0a structure strongly influences its defor-
mation behavior. The unit cell of the orthorhombic D0a structure is shown in Fig. 2.4.
(001)δ is its close-packed plane (Fig. 4.8) and has the same arrangement of atoms
as that in the close-packed plane of the γ phase (Fig. 4.6). However, the stacking
sequence of the close-packed plane in the D0a structure is …ABABAB… type. This
stacking sequence is similar to that encountered in hexagonal-close packed (HCP)
structures. When a GSF is introduced in the D022 structure, it brings its four layers to
the D0a type stacking sequence. Therefore, this structure is very similar to the HCP
structure with its close-packed (001)δ plane identical to that of the (0001) plane in
a hexagonal lattice. However, the ordering of M atoms in the N3 M stoichiometry
distorts the hexagonal symmetry to form the orthorhombic structure. For that reason,
the D0a structure of the δ phase can also be regarded as an ordered structure based
on the HCP lattice. Therefore, the deformation behavior of the δ phase has many
commonalities compared to D022 and HCP phases. As in a D022 structure, faults
like APB, GSF and CSF may occur on close-packed planes of the D0a structure also.
Amelinckx [15] has proposed four-fold and eight-fold dissociation of dislocations
with Burgers vectors parallel to the close-packed directions involving these faults.
The deformation behavior of the δ phase is illustrated considering the δ1 variant
orientation of the phase (Table 2.3). In this orientation of the δ phase, the (010)δ
plane of the orthorhombic structure is the close-packed plane. Several types of slip
and twinning systems, such as (001)δ [100]δ and (001)δ [010]δ slip systems and {011}δ
Fig. 4.8 Projection of atoms

on close-packed (001)δ plane
of the δ phase. The bigger
circles represent the position
of A layer atoms, while the
small circles represent the
projections of B layer atoms
¯ 7 13>δ and {012}δ <02̄1>δ twinning systems [16–22], may get

<01̄1>δ , {211}δ <10
activated depending on crystal orientation. The twins in the Ni3 Nb D0a phase have
similar characteristics to those reported in many pure HCP metals [23].
Fukuchi and Watanabe [24] have shown that Ni3 Nb single crystals can be
deformed to extensive strains even at room temperature by controlling the stress
axis even though the D0a structure has low crystal symmetry. The D0a Ni3 Nb alloy
exhibits sufficient compressive ductility mainly because of the slip on the (001)δ
plane by [100]δ or [010]δ dislocations in all orientations except for the [001]δ orien-
tation. In the [001]δ orientation, it exhibits numerous {211}δ twins. However, the
{211}δ twins cause brittle failure of the alloy in tension along the twinning planes
even at 500 °C.
The {011}δ <01̄1>δ twins are similar to the {1 0 1̄ 2} <1 0 1̄ 1̄> reported in many
pure HCP metals [23]. The twinning planes of {211}δ and {012}δ twins in Ni3 Nb
correspond to {1 0 1̄ 1} in the HCP notation. The {1 0 1̄ 1} twins are reported in
metals like magnesium, titanium and zirconium [23]. However, the formation of the
{10 1̄ 1} twins in HCP structures is associated with <1̄ 0 1 2> type shear, which
is different from an equivalent shear of <10 ¯ 7 13>δ in the orthorhombic structure
required to produce {211}δ twins in Ni3 Nb. The irrational index close to the <10 ¯ 7
13> δ shear direction in the HCP structure is <2̄ 3 1̄ 1> . This gives a relatively small
magnitude of shear (= 0.40) but does not disturb the order symmetry [22].
At low temperatures, the slip is predominantly by the (001)δ [100]δ and
(001)δ [010]δ dislocations because of their low CRSS. The pyramidal slip, similar
to the c + a dislocations in HCP crystals, is not operative. The limited-slip systems
necessitate deformation twinning to provide strains along the b-axis. That is why the
three twinning systems are operative even at room temperature despite high CRSS
values. The CRSS rapidly decreases with increasing temperature from a temperature
of around 200 °C for the {011}δ twin and from a temperature around 400 °C for the
{211}δ twin. However, deformation twins may induce fracture. The CRSS showed
orientation dependence and no significant strain rate dependence in the temperature
range for anomalous strengthening.
The δ phase exhibits anomalous strengthening at elevated temperatures when
deformed by (001)δ [010]δ slip [25]. The CRSS for the (001)δ [010]δ slip increases
with increasing temperature showing a peak between 400 and 800 °C depending upon
the crystal orientation (Fig. 4.9). This anomalous increase in the CRSS is similar to
that observed in many L12 compounds due to the formation of Kear-Wilsdorf type of
locks (Sect. 4.1). The [010]δ superlattice dislocation dissociated into two 1/2[010]δ
superpartials bound by an anti-phase boundary (APB). The 1/2[010]δ superpartial
easily cross slip from the primary (001)δ to the (100)δ plane due to its lower APB
energy on the (100)δ plane as no violation of the first nearest neighbor atoms occurs.
However, the yield stress decreases rapidly at temperatures above the anomalous
peak temperature due to a transition of the (001)δ [010]δ slip from the (001)δ [010]δ
slip to either {211}δ <10¯ 7 13 > δ twinning or (100)δ [010]δ slip depending upon
the crystal orientation.
Fig. 4.9 Temperature

dependence of the yield
strength of Ni3 Nb single
crystals with different
orientations
4.2.3 Ni2 (Cr,Mo) Phase
Two types of close-packed planes, (101)o and (031)o types, exist in the N2 M superlat-
tice of the Ni2 (Cr,Mo) phase. The subscript “o” refers to the orthorhombic structure.
Upon ordering, the four equivalent closed-packed {111} planes of the disordered
FCC phase get converted into two each of the (101)o type and the (031)o type planes
of the ordered phase. Both the planes maintain the N2 M stoichiometry of the super-
lattice. However, the ordering reduces the six-fold symmetry of the FCC octahedral
planes to half (i.e., to three-fold) of the {101}o planes (Fig. 4.10a) and to one third
(i.e., to two-fold) of the {031}o planes (Fig. 4.11a). Due to the difference in the
arrangement of N and M atoms in the two types of planes, the stacking sequence of
the planes (which constitute the N2 M lattice) is different. Figures 4.10b and 4.11b
illustrates the stacking of (101)o and (031)o closed-packed planes for an orienta-
tion corresponding to variant 2 of the Ni2 (Cr,Mo) phase. A three-layer sequence of
the {101}o type planes as …ABCABCA… makes the Ni2 (Cr,Mo) structure. On the
other hand, a nine-layer sequence of the {031}o type planes as …ABCDEFGHIA…
(or as..1234567891...), such that the superposition of atoms take place after every
three layers but the superposition of M atoms occurs every nine layers only, makes
the Ni2 (Cr,Mo) structure. Consequently, the smallest repeat vector, which brings an
atom to its correct position in the superlattice, is different in the two types of planes.
Table 4.3 lists the Burgers vectors of possible perfect and partial dislocations on
(101)o and (031)o planes of an N2 M superlattice oriented as variant 2.
In the {101}o plane (Fig. 4.10), the three close-packed directions are equivalent
and perfect superdislocations in all three directions, and would comprise triplets of
1/2<110] superpartials containing anti-phase boundaries (APBs). Further splitting
the individual superpartials into Shockley partials would lead to complex stacking
faults. The smallest perfect dislocation is of 1/2<112> type. On the {031}o plane,
the glide of a unit dislocation ½ <110> is possible parallel to the row of Mo atoms
Fig. 4.10 a Drawing illustrating how the close-packed (111) plane of the FCC structure on ordering
becomes the (101)o plane of variant 2 of the N2 M phase. b Projection of the N2 M lattice onto the
(101)o plane illustrating that a stacking of three (101)o planes in a sequence …ABCABCA…
constitutes the N2 M lattice. Open and shaded symbols represent N and M atoms, respectively.
Atoms lying in the first (A) layer are represented by circles, while squares and triangles represent
atoms in the second (B) and third (C) layers
(i.e., [11̄0] direction in Fig. 4.11). Still, superdislocations in the other two close-
packed directions would comprise triplets of the unit dislocations. Likewise, perfect
dislocations of type 3/2 <112> are possible in the {031}o plane. In addition, a perfect
translation exists along the C-axis also ([001] for variant 2) though it does not lie in
the octahedral plane. Similar glide planes and displacement vectors of dislocations
in other phase orientations can be obtained using the correspondence relationships
given in Eq. 2.8 and 2.9 in Chap. 2.
Fig. 4.11 a Drawing illustrating how the close-packed (1̄11) plane of the FCC structure on ordering
becomes the (031)o plane of variant 2 of the N2 M phase. b Projection of the N2 M lattice onto
the (031)o plane illustrating that a nine-layer stacking sequence of (031)o planes in a sequence
…ABCDEFGHIA… constitutes the N2 M lattice. Open and shaded symbols represent N and M
atoms, respectively. A, B, C, … G, H, I represent positions of M atoms on the 1st, 2nd, 3rd, … 7th,
8th, 9th layers, stacking of which constitute the N2 M structure
Twinning in the N2 M superlattice can take place in four different modes. As a

result of the cubic to orthorhombic transformation, out of the twelve <112> {111}
twinning systems of the FCC structure, only ten twinning systems transform to twin-
ning modes that give true twins in the N2 M structure. The remaining two twinning
systems produce pseudo twins in the N2 M lattice. Among the ten true twinning
modes, two twinning systems make true twins by “Combined” twinning mode, and
the remaining eight gets converted into four equivalent conjugate pairs of “Type I”
and “Type II” modes of the ordered lattice. This classification of twinning modes
is based on the classification proposed by Christian and Laughlin [26]. Table 4.2
also lists characteristic crystallographic features of different twinning modes in the
N2 M superlattice. The crystallography of the formation of true twins is illustrated
by taking one example of each of the three modes of variant 2 of N2 M superlattice
(Table 2.8). For more details, readers are referred to references [13, 27].
The combined mode of twinning is operative when both the twinning planes, K 1
and K 2 are of (101)o type and the shear acts along <101̄>o direction. The shear plane
for this mode is (010)o . Projection of the superlattice on (010)o (i.e., (11̄0)) shear
plane would orient the twinning plane (111) (i.e., (101)o ) in edge-on orientation as
illustrated in Fig. 4.12. A six-layer stacking sequence of the shear plane (010)o as
...0123450... constitute the N2 M lattice. In this orientation, only one atom species is
present in each layer with zeroth and the 3rd layer containing only M atoms and 1st,
2nd, 4th and 5th layers containing only N atoms. These layers are arranged in such
a way that atom positions in an even-numbered layer coincides with another even-
numbered layer, and an odd-numbered layer coincides with another odd-numbered
layer, or the coincidence of M atoms occurs only after six layers. The orthorhombic
axes A and C would lie within the projection plane (plane of the paper), whereas B
would be parallel to its normal. It is also apparent from atom positions on the (101)o
plane (Fig. 4.10) that there are only one species of atoms (i.e., N or M) along the
shear directions [101̄]o . It can be seen that an operation of shear of 1/3[101̄]o (i.e.,
1/6[112̄]) on a plane (say B in Fig.4.12) would restore the lattice across the projection
of the twinning plane with the right kind of atoms in twinned positions with respect
to the matrix. Displacement of such a magnitude would need to take place on at
least three consecutive planes to repeat the stacking sequence with respect to the
matrix. It is to be noted that the same twinned positions can be obtained both by
reflection across the twin plane and by rotation about the twinning (shear) axis. As
the twin and the conjugate twin plane and the twinning direction and its conjugate
Table 4.3 Burgers vectors of possible perfect and partial dislocations on (101)o and (031)o planes
of a N2 M crystal oriented according to variant 2 with respect to the FCC structure
(1 0 1)o // (1 1 1)fcc (0 3 1)o // (1̄1 1)fcc
Perfect translations 1/2[112̄] 1/2[110]
1/2[12̄1] 3/2[101]
1/2[2̄11] 3/2[01̄1]
3/2[1̄10] 3/2[211]
3/2[101̄] 3/2[1̄12̄]
3/2[01̄1] 3/2[1̄2̄1]
Shortest burgers vectors of partials bounding a pure 1/6[112̄] 1/6[211]
stacking fault 1/6[12̄1] 1/6[1̄2̄1]
1/6[2̄11]
1/3[1̄1̄2]
Fig. 4.12 Schematic drawing showing the shear plane projection for the Combined mode of twins
in N2 M lattice. N2 M lattice comprises a six-layer stacking sequence of type ...0123450... of the
shear plane (010)o arranged in such a way that atom positions in an even-numbered layer coincides
with another even-numbered layer, and an odd-numbered layer overlaps with another odd-numbered
layer. The coincidence of M atoms occurs only after six layers. Different layers have been represented
with respect to the position of M atoms in each layer. A twinning shear, η, of 1/6[112̄] on every
(111) (i.e., (101)o ) plane generates a true crystallographic twin
are crystallographically equivalent and rational, the derived mode for the ordered
structure gives the same results as the compound twinning mode of the disordered
FCC lattice [26].
The type I mode of twinning is operative when the K 1 plane is of (031)o type
and K 2 is of (101)o type. The corresponding twinning shear directions are of η1 =
[91̄3]o and η2 = [1̄ 11]o type. The associated conjugate mode (Type II) is obtained
by interchanging K 1 and K 2 , and η1 and η2 .
Projection of the superlattice on the shear plane (132̄)o (i.e., (011̄)) would reveal
that a stacking of six layers of the shear planes as …0123450… is required to construct
the superlattice (Figs. 4.13 and 4.14). The stacking arrangement of this shear plane
would such that an even-numbered layer would coincide with another even-numbered
Fig. 4.13 Schematic drawing shows the projection plane for Type I mode of twins in the N2 M
lattice. A six-layer stacking of the shear plane (011̄) (i.e., (132̄)o ) would constitute the N2 M lattice.
Different layers have been represented with respect to the position of M atoms in each layer. A
twinning shear of 1/6[211] on every (1̄11) (i.e., (031)o ) plane generates a true crystallographic twin
layer, and an odd-numbered layer would coincide with another odd-numbered layer.
The coincidence of M atoms would occur only after every six layers. Each layer
would contain both the species of atoms. This projection would bring the (031)o
(i.e., (1̄11)) and the (101)o (i.e., (111)) planes in the edge-on orientation. The A-axis
would be pointing outward from the plane of the paper at an angle of 30º, and its
projection in the plane of the paper would lie along [211] direction. In contrast, the C-
axis would point downward at 45º with the plane of paper such that its projection lies
along [01̄1̄] direction. A nine-layer stacking of (1̄11) planes, as …ABCDEFGHIA…
(Fig. 4.11b), or a three-layer stacking of (111) planes, as …ABCA…(Fig. 4.10b),
make variant 2 of this superlattice. This stacking sequence can also be inferred from
Figs. 4.13 and 4.14. It can be seen that a twinning shear of 1/36[91̄3]o (i.e., 1/6[211])
on consecutive (031)o (i.e., (1̄11)) planes would bring the sheared lattice at twin
position by Type I mode with right kind of atoms occupying the lattice positions
with respect to the matrix. Similarly, a shear of 1/6[1̄11]o (i.e., 1/6[2̄11]) magnitude
Fig. 4.14 Schematic drawing showing the plane of projection for the Type II mode of twins in
N2 M lattice. A six-layer stacking of the shear plane (011̄) (i.e., (132̄)o ) would constitute the N2 M
lattice. Different layers have been represented with respect to the position of M atoms in each layer.
A twinning shear of 1/6[2̄11] on every (111) (i.e., (101)o ) plane would bring the lattice points at
twin position, on which a true crystallographic twin can be generated by a rotation of 180° about
the twinning axis
on consecutive (101)o (i.e., (111)) planes would also bring the lattice to twin position.
The identical twin structure could be achieved by a rotation of 180º about the twinning
axis [2̄11]. Shears of such magnitude are required on at least nine consecutive planes
for Type I twins and at least three successive planes for Type II twins to restore the
lattice.
4.3 Strengthening Mechanisms in Alloy 625 131
4.3 Strengthening of Alloy 625
Superalloys, in general, are strengthened by solid-solution hardening, precipita-

tion hardening, or dispersion strengthening. Dispersion strengthening may include
strengthening by carbides or oxide particles. Other strengthening mechanisms, such
as grain size refinement and cold working, usually do not play much role due to
intended applications of superalloys at elevated temperatures. Alloy 625 achieves
its strength primarily from solid-solution hardening, but service exposure precipi-
tates out particles of various intermetallic phases, which age hardens the alloy. These
precipitates directly bear the temperature/stress capabilities of Alloy 625 compo-
nents. This section briefly describes the solid-solution and precipitation hardening
mechanisms that primarily govern the Alloy 625 strength.
4.3.1 Solid-Solution Strengthening
Solid-solution hardening is mainly related to the difference in the atomic size of solute
and solvent atoms. It is a measure of the lattice parameter (a) change of the austenite
matrix [28]. Substitutional elements whose atomic diameter differs from nickel by
about 1 to 13% solid solution harden the alloy by straining the nickel matrix [29].
Besides, a change in the electron vacancy number (N v ) also changes the yield stress
of the nickel-base superalloys. The position of solutes in the periodic table governs
their Nv values, which may differ by 1 to 7% for various solutes. For the same lattice
strain, the extent of hardening increases with an increase in the value of N v . That
is why the strengthening is more potent for aluminum, tungsten, molybdenum and
chromium and least effective for elements like cobalt, iron, titanium and vanadium.
However, the tendency of these alloys to form topologically close-packed (TCP)
phases limit the extents of tungsten, molybdenum and chromium additions. Solid-
solution strengthening in Alloy 625 is due to chromium, molybdenum, aluminum
and titanium. Niobium does not contribute much to the solid-solution hardening.
Still, it strengthens the alloy along with molybdenum at elevated temperatures by
virtue of their high melting points when the matrix strength is diffusion dependent.
A part of the solid-solution strength of Alloy 625 can also be attributed to the low
stacking fault energy (SFE) of its austenite phase. A strong correlation between Nv of
the solute and a reduction in the SFE has been well documented [30, 31]. Pure Ni has
a high SFE (~150 mJ/m2 ) [1]. The addition of solutes like chromium, molybdenum,
tantalum, titanium, etc. in nickel decrease the SFE of the austenite nickel phase
(Fig. 3.10). Further, the effect of solute elements on SFE is not the same for binary
and multicomponent alloys [32]. Therefore, alloying additions in nickel lower the
SFE of the solid solution. A low SFE leads to planar arrays of dislocations, which
inhibits the cross slip.
Other solid-solution strengthening mechanisms such as difference in the shear
moduli of solute and the solvent atoms [30] and the presence of short-range order
Fig. 4.15 A schematic illustration of the interaction of a dislocation with obstacles
[29] may also contribute to solid-solution strengthening. However, the short-range

order has never been reported in Alloy 625 though it is known to exist in many
nickel–chromium-molybdenum alloys.
4.3.2 Precipitation Strengthening
Second phase particles increase strength of the alloy by acting as barriers to dislo-
cation motion. When a dislocation encounters obstacles, it bows between them.
The extent to which dislocations can bend is governed by the strength of barriers
(Fig. 4.15). Shear stress, τ, required to bend dislocations to an angle φ is given by
[33],
Gb φ
τ∼
= cos (4.3)
λ 2
where G is the shear strength of obstacles, b is the Burger’s vector of dislocations and λ
is spacing between two obstacles in a slip plane. The angle φ is inversely related to the
obstacle strength. As the strength of barriers increases, φ approaches zero because the
dislocation doubles back on itself when particles behave like impenetrable obstacles
(particle bypassing). On the other hand, for values of φ > 0, the particles can be
sheared by the glide of dislocations. For weak obstacles, φ is very large and tend to
approach 180º. λ is another critical parameter as a decrease in its value would also
reduce φ for a given stress.
In general, strengthening by ordered phase precipitates is governed by one or
more of the following factors:
1. order hardening due to the additional energy associated with the creation of
anti-phase boundary when ordered particles are sheared;
2. coherency strain hardening;
3. modulus hardening due to the difference between the elastic moduli of the
matrix and the precipitate phases, which results in different elastic energies
around dislocations in precipitates and the matrix;
4. difference between the stacking fault energies of the precipitate and the matrix
phases;
5. surface hardening due to the energy required to create additional particle/matrix
interfaces when dislocations shear the particles.
The precipitation strengthening in Alloy 625 is brought about mainly by the
formation of the γ and Ni2 (Cr,Mo) phase particles. Both phases form in ellip-
soidal morphology due to their cubic to non-cubic transformations (Sect. 3.5). The
significant contribution comes from the coherency hardening and the order hardening
associated with the two phases. Hence, the analysis of the precipitation strengthening
here is restricted only to these two mechanisms.
4.3.2.1 Order Strengthening
The ordered precipitates impede dislocations’ movement as their passage destroys

their order structure and creates anti-phase boundaries. Passage of multiple dislo-
cations of the disordered matrix is required to restore the ordered state. Therefore,
dislocations in an ordered structure often glide in pairs bound by an anti-phase
boundary (Sect. 4.1.3). Consequently, there is a net enhancement in the alloy’s shear
strength when ordered phase precipitates are present. Ordering asymmetry in the
close-packed directions of the γ phase necessitates the passage of two dislocations
in one close-packed direction and four dislocations in the other two close-packed
directions on a {111} plane. When the γ phase particles are sheared by four, two
and single 1/2<110> dislocations, the increase in the strength of the alloy is given
by [34]:
(a) When particles are sheared by a quadruplet of 1/2<110> dislocations,
⎡⎧ √
1/2 ⎫1/2 ⎤

⎣⎨ 4 f R 6 ⎬
τ4 = − f⎦ (4.4)
4b ⎩ π T 3A ⎭
(b) When particles are sheared by a pair of 1/2<110> dislocations,

⎡⎧ √
1/2 ⎫1/2 ⎤
⎨
⎬
⎣ 4 f R 6
τ2 = − βf⎦ (4.5)
2b ⎩ π T 3A ⎭
and
(c) When particles are sheared by a single 1/2<110> dislocation,
⎡ √
1/2 ⎤1/2

⎣ 4 f R 6 ⎦
τ1 = (4.6)
b πT 3A
where τ stands for the increment in the flow stress due to precipitate shearing,
subscripts 4, 2 and 1, respectively represent the number of dislocations, b is the
magnitude of the Burgers vector, A is the aspect ratio given by the ratio of the major
and the minor axes of γ particles and R is the semi-major axis (see Fig. 3.25), T
is the dislocation line tension, β represents the fraction of γ particles in which the
passage of dislocation pairs restores the order, is the APB energy per unit area of
the γ phase and f is its volume fraction. It should be noted that in the original work
of Oblak et al. [34] R was taken as the mean of the semi-minor and semi-major axes
of the ellipsoid, while Kelly [35] assumed R as the semi-major axis for estimating
the particle bypassing strength. For the sake of simplicity, Kelly’s assumption has
been used for particle size in the present text. Such an assumption would not result in
any significant error in the shear strength measurement. When all the three variants
of the γ precipitates are present, β = 1/3. An important feature of the strengthening
by particles of the γ phase is that τ is sensitive to the specific variant of the γ
phase.
Oblak et al. [34] relationships for the contribution of order hardening by ellipsoidal
γ phase precipitates are equally applicable for treating the ordering hardening by
Ni2 (Cr,Mo) precipitates. For the Ni2 (Cr,Mo) phase β = 1/6, assuming all its variants
precipitate homogeneously throughout the matrix.
4.3.2.2 Coherency Strengthening
Tetragonality associated with coherent γ precipitates produce distortions in the

matrix around them. Dislocations interacts with the strain field surrounding the parti-
cles. Oblak et al. [34] have derived an expression for the increase in the critical
resolved shear stress due to the interaction of edge dislocations with the coherency
strain associated with ellipsoidal shape particles.
1/2
fR
τ = 1.7με 3/2
(1 − β) (4.7)
2 A2 b
where ε is the tetragonal misfit strain and β is the fraction of particles whose c-axis
is normal to b. β = 1/3 when all the three precipitate variants of γ are present. The
coherency contribution is directly proportional to the shear modulus μ. Therefore,
the coherency strength decreases with increasing temperature. Coherency hardening
effects may also depend strongly on the alloy composition as the lattice mismatch
between the matrix and the precipitate changes with composition. Oblak et al. [34]
have shown the contribution of the coherency strengthening (~221 MPa) due to γ
phase particles is more than their order strengthening (~183 MPa) in Alloy 718.
4.3.2.3 Particle Bypassing
Particle bypassing by dislocations limits the strength achievable by precipitation.

Bypassing occurs beyond a specific particle size by either forming dislocation loops
(Orowan looping) or by a climb of dislocations at the matrix-precipitate interface.
Kelly [35] has derived an expression for the stress necessary to initiate the bypassing
process for plate-shaped particles of a given orientation in the matrix:

0.85μb C 4R
τ = π
ln (4.8)
2π (1 − ν)1/2 2R 1 − 2A
C r0
where τ is the shear stress increment associated with precipitate bypassing, ν is

the Poisson ratio for the matrix, r 0 is the dislocation core radius, R is the semi-major
axis of the ellipsoidal, and the following relation gives the value of C:

2 π
C = ( f A) +
1/2
− fA (4.9)
π 2A
Other terms have the usual significance. The stress required for the onset of the
particle bypassing mechanisms decreases with increasing particle size. Kelly has
shown that the stress necessary for Orowan bypassing to operate is much higher
for needle-shaped and plate-shaped precipitates than for spherical ones. When the
Orowan process operates, the alloy work hardens rapidly because every dislocation
passing the particles leaves a loop around them, decreasing the effective interparticle
spacing λ.
Equation 4.8 is valid only at low temperatures. At high temperatures, dislocations’
climb over particles becomes the rate-controlling mechanism for the dominant creep
phenomenon [36]. At stresses σ > μb/λ, dislocations move past particles by Orowan
looping. Built-up dislocation loops exert back-stresses to prevent further looping
until they climb to the nearest particle. When this process occurs, the creep rate, ˙ ,
is given by
π σ 4 λ2 D
˙ = (4.10)
Rμ3 kT
where σ is the stress applied, D is the self-diffusion coefficient, k is the Boltzmann

constant, and T is temperature. At σ < μb/λ, dislocation can climb over the particles
without piling up or bowing, and the corresponding creep rate is given by:
π σ b3 D
˙ = (4.11)
8kT R 2
A decrease in the diffusivity and an increase in the size of the second phase particle
reduce the creep rate. In addition, a low value of λ reduces the creep rate at high
stresses. These parameters are usually achieved by adding slow diffusing species,
like molybdenum, niobium, etc. in the alloy and by increasing the volume fraction
and size of precipitates by suitable aging treatments.
4.4 Deformation Micromechanisms in Alloy 625
Several studies on the deformation behavior of alloys containing ordered strength-

ening phases of tetragonal or orthorhombic symmetry [12, 37, 38] show a transition
in the deformation mode from slip to twinning in ordered particles owing to their low
symmetry and low stacking fault energies. Such a transition implies that the defor-
mation mode changes from the glide of unit dislocations (or superdislocations) to the
movement of Shockley partials when they enter the ordered phase precipitates and
vice versa. The slip to twinning transition is governed by the stacking fault energy
of the ordered phases.
The main hardening phases in Alloy 625, namely γ and Ni2 (Cr,Mo) phases, have
properties similar to those studied by Sundararaman et al. [12] in Inconel 718 and
by Kumar and Vasudevan in Haynes 242 [38], respectively. Frequent observation of
stacking faults within γ precipitates in deformed and un-deformed Alloy 718 has
been reported by many workers. The frequent observations of stacking faults indicate
that the stacking fault energy (SFE) of the γ phase is relatively low. Ni3 V phase
is the only equilibrium D022 structure with lattice parameters very close to that of
the γ phase. The SFE of the Ni3 V phase is reasonably low (~22 mJ/m2 [39]) and
frequently exhibits stacking faults without disturbing the long-range order [13, 40,
41]. The low stacking fault energy of the metastable γ phase is also consistent with
SFE of the Ni3 V phase as the two phases are isostructural and niobium and vanadium
belong to the same group (VB) in the periodic table.
Figure 3.10 shows that adding chromium and molybdenum to nickel reduces its
stacking fault energy. The SFE of the Ni2 Mo phase lies in the range of 20 to 30 mJ/m2
[42]. It is, therefore, reasonable to deduce that the Ni2 (Cr,Mo) phase has very low
SFE. The low SFE of the Ni2 (Cr,Mo) phase is consistent with the observation of
frequent splitting of unit dislocations into partials in Alloy 625 containing a high
density of uniformly distributed γ and Ni2 (Cr,Mo) precipitates [43]. This obser-
vation also agrees with frequent twinning and stacking faults within Ni2 (Cr,Mo)
precipitates reported by Kumar and Vasudevan [38].
As mentioned in Sect. 4.2, the two phases are sheared by pairs of unit dislocations.
The dislocation pairs may further dissociate into Shockley partials by reactions like
Eq. 4.2. Each pair of partials is connected by a superlattice intrinsic stacking fault
(SISF) in the appropriate variant and a complex stacking fault in others. The formation
of SISF in the two phases energetically favors the deformation process due to their
low stacking fault energies. The formation of the SISF neither violates the nearest
neighbor bonds nor disturbs the long-range order of the phase. Therefore, the unit
dislocations tend to dissociate and create SISFs in the ordered phase. Sundararaman
et al. [12] and Kirman and Warrington [44] have reported the frequent occurrence of
stacking faults within γ precipitates in deformed Alloy 718. Such stacking faults,
4.4 Deformation Behavior of Alloys Containing … 137
lying on adjacent glide planes, eventually lead to the formation of twins within the
precipitates. The following discusses, in brief, the transition in the deformation mode
from slip to twinning in such ordered particles. This behavior is examined considering
the case of γ particles, but the same principles are applicable for the Ni2 (Cr,Mo)
particles also owing to similar crystallography of their deformation noted in Sect. 4.2.
4.4.1 Deformation of Particles by Shearing and Twinning
The creation of SFs within γ phase precipitates is energetically favorable owing to
its low SFE, which in turn promote the formation of true deformation twins within
γ particles. Sundararaman et al. [12] have shown profuse deformation twinning in
particles of size larger than 10 nm in deformed Alloy 718, indicating twinning to
be the predominant mode of deformation in γ particles of size larger than 10 nm.
Though deformation in the γ phase can occur in any of the four {111} plane favored
by Schmid factor values, the crystallography of the ordered phase constrains the
continuity of deformation by twinning in the ordered precipitates without disturbing
their order. For a given shear on a specific {111} plane in the matrix, true twins on
that plane in the γ phase would form only in a particular variant of the γ phase,
which has the twinning shear compatible with the shear direction in the matrix. The
compatibility of the shear is required because true twins on a given {111} plane
in the D022 structure form only by one specific 1/6<112> shear while the other two
shears destroy the chemical order (Sect. 4.2). Therefore, a precipitate would be easily
sheared by twinning if its orientation were favorable to the incoming shear. This
mode of deformation would thus create different types of twins (i.e., with a different
twinning plane and shear) in different precipitate variants for a given tensile stress
direction. Such twins nucleate when the stress concentration at the precipitate-matrix
interface exceeds critical stress, followed by easy growth as the ordered structure is
retained.
Despite this restriction, the twinning along different {111} planes of γ particles
corresponding to all variants of the phase has been shown to occur to give homo-
geneous macroscopic deformation. Sundararaman et al. [12] have rationalized this
observation considering dislocation decomposition reactions at the particle/matrix
interface. In principle, twins on any specific {111} plane can propagate through all the
γ variants, though the directions of the twinning shear would be different in precip-
itates belonging to other variants. As a result, the orientations of the twinned crystals
formed in different variants would also be different. The difference essentially arises
because of the direction of ordering in each particle. If the ordered atomic arrange-
ment is ignored, the underlined lattice is identically twinned in all variants. Therefore,
for the deformation to propagate by twinning on a specific {111} plane across parti-
cles of all orientations, appropriate shear directions compatible with orientations of
the precipitate variants are required to conserve the D022 ordering within twin bands.
Shear compatible with different variants can be created if dislocation dissociation
reactions of the following type are assumed to occur at the particle/matrix interface:
1/6[12̄1] → 1/6[21̄1̄] + 1/6[1̄1̄2] (4.12)
where an incoming shear front consisting of a set of incompatible 1/6[12̄1] dislo-

cations on every plane split into sessile 1/6[21̄1̄] and glissile (compatible) 1/6[1̄1̄2]
components at the precipitate-matrix interface. The glissile partials with the appro-
priate shear vector would glide through a precipitate, leading to the formation of a
twin within it. Even though such dislocation reactions are energetically not favor-
able, they are feasible under externally applied stress. The energy savings accrued
by preserving the order during the propagation of deformation twin outweigh the
energy spent in creating a set of sessile partials at the precipitate-matrix interface.
Shearing by deformation twinning is associated with a drop in the work hard-
ening because these twins, once nucleated, form an easy passage of the shear across
the matrix-precipitate interface. Deformation twinning, therefore, does not increase
the dislocation density at the interface and consequently does not work-harden the
matrix. Moreover, since the deformation twins in γ particles remain confined within
precipitate particles on only one crystallographic plane, work hardening associated
with the interaction of twins on different planes is also not there [1, 45].
4.4.2 Effect of Particle Size on the Deformation Mode
During the deformation of two-phase aggregates comprising a homogeneous distri-

bution of hard particles in a softer matrix, two distinct deformation modes, particle
shearing and particle bypassing, are commonly observed. The dislocations bypass
overaged precipitates by creating loops around them. However, alloys containing
overaged ordered precipitates of tetragonal or orthorhombic crystal symmetry do not
show dislocation looping around them. Sundararaman et al. [12] have explained this
type of behavior by invoking the order hardening and particle bypassing models for
the interaction of dislocations with ordered particles in conjunction with deformation
by twinning.
Equation 4.5 gives increase in the shear strength of the alloy when a pair of dislo-
cations shear ordered particles. As noted earlier, a pair of the matrix dislocations can
shear γ and Ni2 (Cr,Mo) phase particles without disturbing their order. Figure 4.16
shows the functional dependence of the critical resolved shear stress (CRSS) as a
function of particle size for the different deformation mechanisms. This dependence
indicates that the stress required for shearing of particles increases with increasing
particle size, which is directly related to an increase in the destruction of the order
within particles. On the other hand, the stress associated with particle bypassing
decreases with increasing particle size for a constant volume fraction. An increase
in the mean particle size accompanies a concomitant increase in the interparticle
spacing. Therefore, the stress necessary to initiate bypassing decreases according to
the relation given by Eq. 4.8. A crossover point is observed in terms of the size of the
precipitates. Operation of the bypassing mechanism has a lower stress requirement
4.4 Deformation Behavior of Alloys Containing … 139
than the shearing mechanism beyond a critical precipitate size. Yet these alloys do
not show dislocation looping around the precipitate particles.
As mentioned earlier, shearing of particles by deformation twinning occurs only
for particles of size bigger than a critical size. These twins are true twins of respective
ordered phases as the twinned lattice retains their original order. For this mode of
particle shearing to begin operating, the stress concentration at the precipitate-matrix
interface should exceed the resolved shear stress required to propagate Shockley
partial dislocations and nucleate deformation twins within the ordered particles.
These Shockley partials create SISFs, which act as nuclei of the true twins. Once
nucleated, the growth of the twin nuclei does not disturb the order and, hence, does not
require stresses greater than that required for their nucleation. This implies that once
the required threshold stress concentration builds up, the shear propagates through
the precipitate catastrophically. A stress concentration above the threshold can easily
build due to dislocation pilling at the particle/matrix interface in alloys characterized
by planar slip. An approximate estimation of the stress necessary for nucleation of
deformation twin within an ordered precipitate can be made by equating the critical
stress required for twinning, τ T , to the critical stress, τ C , generated at the interface
by a pile-up of dislocations of pile-up length λ. This critical stress can be expressed
as [46].

τC 1/2 λ −1/2
τa = μ (4.13)
π αμ b
Fig. 4.16 Theoretical

increment in the shear stress,
τ, as a function of γ
precipitate size for different
deformation mechanisms in
Inconel 718 [12]. Rc is the
critical radius above which
the particle’s deformation
mechanism changes from
shearing to twinning
where τ a is the applied shear stress and α is a geometrical factor which assumes
a value of l for a screw dislocation pile-up or (1-ν) for an edge dislocation pile-up.
Expressing in terms of R, A and f , and putting τ C = τ T , relation 4.13 can be expressed
as [35]:

15bτT 1/2 f A π 1/2 1/4
τa = μ (4.14)
16π μ 2R 2 2
For fixed values of b, μ, τ T , f and A, τ a becomes inversely proportional to R1/2 .

This dependence of the shear stress increase for twinning as a function of precipitate
size is also shown in Fig. 4.16, along with the shear stress increase for shearing and
bypassing. This analysis shows that, like particle bypassing, the twinning shear is
also size-dependent. There is a critical particle size above which the stress required
for deforming ordered precipitates by twinning is lower than the stress by unit dislo-
cations shearing. Besides, the twinning stress for ordered particles is always lower
than the bypassing/looping stress for all the particle sizes.
4.5 Tensile Behavior of Alloy 625
The tensile behavior of Alloy 625 may change significantly depending upon its
thermal history. This change is due to the dominant hardening mechanisms associated
with the microstructural condition. This section gives a brief account of the tensile
properties of the alloy in different microstructural states. As the alloy does not exhibit
a well-defined yield point phenomenon, the reported yield strength values correspond
to 0.2% proof stress.
4.5.1 Solution Annealed Alloy
The tensile properties of the annealed alloy may vary significantly depending upon
the annealing condition and the product form. The alloy possesses a minimum room
temperature yield strength of about 276 MPa in fully solution annealed conditions.
However, a minimum room temperature yield strength of 414 MPa is achievable
in cross-sections up to 100 mm and 345 MPa in cross-sections from 100–250 mm
without extensive mechanical working. Table 4.4 gives nominal room temperature
tensile properties of wrought Alloy 625 in different conditions [47, 48]. The inherent
solid-solution nature of Alloy 625 limits its hardness3 below about 100 HRB (~240
3 The hardness of a material refers to its ability to resist local plastic deformation during indentation
or scratch. Its value depends highly upon the type and geometry of the indenter tool being used and
the applied load range [1]. Many hardness testing techniques are available, and all have their scale to
rate the hardness based on the type of indenter and the capacity of the load that is applied. Each scale
4.5 Tensile Behavior of Alloy 625 141
Fig. 4.17 A correlation

between the hardness and
strength of the Alloy [47].
YS = Yield strength; UTS =
Ultimate tensile strength
BHN) [47, 48], which can only be increased further by prolonged aging or by cold or
warm working. Cold working can increase the hardness of Alloy 625 up to about 45
HRC with a drastic decrease in ductility to about 5% [48]. Warm or cold working may
be combined with prolonged aging to age harden the alloy, but such warm or cold
working operations becomes less practical as the cross-section of the working piece
increases. Figure 4.17 shows a direct correlation between the hardness and strength
of the alloy [47]. The plots in Fig. 4.17 can be used for engineering relationships
correlating alloy’s hardness with yield and ultimate tensile strengths:

(H − 59.84)
YS(MPa) = 200 + 3.65 × 10−5 exp
0.87

(H − 59.84)
+ 272.6 exp (4.15)
9.31

H
UTS(MPa) = 730.24 + 0.34 exp (4.16)
9.31
gives a hardness value using a particular indentation tool under specific loading conditions. The
use of a particular scale depends upon the material’s strength, its work hardening behaviour and the
employed test technique. The most commonly used hardness tests are Rockwell hardness, Vickers
hardness, Brinell hardness and the Knoop hardness. The Rockwell hardness tests can measure
hardness over a wide range and rate it on multiple scales depending upon the load required. Each
Rockwell hardness scale is identified by a letter indicating A, B, C, D, etc. depending on the
size and type of the indenter and the load applied during measurement. For example, HRA refers to
Rockwell hardness scale A, HRB refers to Rockwell hardness scale B, and so forth, which are being
used in the increasing hardness order. However, no direct relationship between different hardness
scales exists because (i) hardness represents the local strength of a material and (ii) all the tests use
different types of indenters. Nonetheless, some empirical hardness conversion relationships have
been developed for some scales, particularly for hard steels. For the ease of the readers, standard
hardness conversion tables at various sources are summarized in Appendix E. For more details,
readers are referred to reference [1].
Fig. 4.18 Engineering

stress-engineering strain plot
of a solution annealed Alloy
625
where YS and UTS refer to yield and ultimate tensile strengths of the alloy (in MPa),
respectively and H is the hardness of the alloy on the Rockwell A scale [47].
Figure 4.18 shows the engineering stress versus engineering strain curve of Alloy
625 in solution annealed condition. Alloy’s typical stress–strain curve is charac-
terized by rapid strain hardening due to predominant planar slip in the alloy (see
Fig.3.23b). Sundararaman [49] has studied the deformation microstructure of the
alloy in solution-treated conditions and shown that dislocations invariably remain
in planar arrays confined within the primary slip plane even after extensive defor-
mation. The planar arrangement of dislocations causes rapid strain hardening of the
alloy. Features like cross slip of dislocations, tangling of dislocations, and cell forma-
tion are primarily absent in deformed annealed alloys. However, dislocations do not
show any resolvable splitting into partials. Such a deformation microstructure is a
typical feature of alloys with low stacking fault energy (SFE) or when alloys exhibit
short-range order (SRO) or both. As no SRO is reported in Alloy 625, the observed
deformation behavior of the alloy in solution annealed condition can be attributed to
its low stacking fault energy. Based on the effects of adding elements like chromium,
molybdenum, aluminum and titanium on the SFE of nickel reported by different
researchers [31, 50–53], the SFE of Alloy 625 is expected to be between 50 and
75 mJ/mm2 . This range of the stacking fault energy is consistent with the values
estimated by Yang et al. [54] for various nickel binary alloys using the first-principle
calculations (Fig.3.10).
Figure 4.19 shows the yield strength, ultimate tensile stress, and elongation prop-
erties of Alloy 625 in solution annealed condition as a function of temperature, tested
over a temperature range from room temperature to 1000 °C [47]. The yield strength
falls slightly up to about 600 °C, followed by an increase up to 700 °C. Above 700 °C,
the yield strength decreases again. The ultimate tensile strength follows a uniform
behavior of a slight decrease up to the test temperature of 600 °C followed by a sharp
reduction at temperatures above 700 °C. The ductility remains almost constant up
Fig. 4.19 High-temperature

tensile properties of a
hot-rolled Alloy 625 rod in
solution annealed condition
[47]
to about 550 °C, after which it increases sharply till a maximum of about 120% is
reached.
A peak and a plateau in the yield and ultimate tensile strength of an alloy at elevated
temperatures are manifestations of dynamic strain aging (DSA). DSA is characterized
by a jerky/serrated flow behavior, known as Portevin–Le Chatelier (PLC) effect.
Such a deformation behavior in the intermediate temperature range is commonly
observed in many alloys [54–64]. Many authors have reported DSA in Alloy 625 at
temperatures over 250–600 °C and strain rates ranging from 10−5 to 10−3 s−1 [56,
65–68]. This DSA behavior is observed in the solution annealed as well as aged
Alloy 625. The alloy exhibits a normal PLC behavior at lower temperatures due to
locking of dislocations by interstitial carbon atoms, and an inverse PLC behavior at
higher temperatures because of the pinning of dislocations by molybdenum atoms.
In the DSA regime, the alloy exhibits negative strain rate sensitivity [56].
4.5.2 Age-Hardened Alloy
Alloy 625 can be age-hardened to achieve higher levels of strength. But the alloy’s
age-hardening response is sluggish and sensitive to the annealing temperature. In
smaller cross-section specimens, a higher annealing temperature makes the alloy
less responsive to direct aging. For example, hot-rolled bars of diameter larger than
100 mm, annealed at 1149 °C for 1 h, can be age-hardened directly by subjecting
them to aging treatment at about 650 °C. However, bars of diameters less than
100 mm require an intermediate treatment of 1 h at about 760 °C before the same
age-hardening treatment. Even for a prolonged time, direct treatment is not sufficient
to induce age hardening at 649 °C [69]. Figure 4.20a shows a comparison of the age-
hardening response of a hot-rolled bar annealed at about 1150 °C for 1 h. Samples
that did not receive an intermediate nucleation treatment did not show any increase
in the hardness even after 96 h of aging at 649 °C. On the contrary, the hardness of the
Fig. 4.20 a Age hardening response of an Alloy 625 solution treated at 1149 °C for 1 h and a
subsequent nucleation treatment at 760 °C for 1 h [69]. b Effect of annealing on the yield strength
of the alloy at intermediate temperatures for different periods [69]
samples with intermediate annealing increased by about 11 HRA points within 96 h

of aging at 649 °C [69]. This difference in the age-hardening response of different
size rods is because of the slower cooling rate experienced by the thicker section
alloy from the annealing temperature. The slower cooling allows the alloy to dwell
more to nucleate γ particles in the intermediate temperature range. The nucleation
of γ particles allow faster growth of subcritical γ nuclei permitting their normal,
though slow, precipitation during subsequent treatment at about 650 °C. Eiseilstein
and Tillack [69] have noted that a time between 2–4 min in the critical temperature
range of 760–788 °C is necessary to cause more rapid aging at 649 °C.
The age-hardening response of Alloy 625 is the fastest in a narrow window, around
650 °C, with the highest response within 48 h [69]. Figure 4.20b shows a plot of room
temperature yield strength of an Alloy 625 bar subjected to annealing at 1149 °C for
1 h followed by aging treatments at intermediate temperatures for various times up to
1000 h. Age hardening in the temperature range 780–925 °C for about 100 h imparts a
minimum yield strength of 414 MPa, while an aging treatment of approximately 10 h
is sufficient at about 650 °C. At 650 °C, the age hardening can achieve a minimum
yield strength of 552 MPa within 24–48 h [69]. Warm working accelerates the age-
hardening response, but the inhomogeneous strain may cause considerable variation
in the properties across the cross-section.
Figure 4.21 depicts the tensile properties of Alloy 625 age-hardened at 540, 700
and 850 °C temperatures for periods ranging from 10 to 1200 h. Microstructures of
the aged alloys showed the predominant formation of Ni2 (Cr,Mo), γ and δ phases,
respectively at 540, 700 and 850 °C [70]. At all the three aging temperatures, the
room temperature yield and ultimate tensile strengths increased with aging time
and a concomitant decrease in ductility, albeit with different trends at the three
temperatures. Interestingly, increase in the strength was maximum at 540 °C and
least at 850 °C. The alloy aged at 540 °C exhibited more ductility than those aged
at 700 and 850 °C. Moreover, unlike the monotonous decrease in the ductility of
alloys aged up to 1200 h at 700 and 850 °C, the alloy’s ductility at 540 °C increased
Fig. 4.21 Variation in the tensile properties of Alloy 625 with ageing time: a yield and ultimate
tensile strength; b Uniform and fracture strain [70]
after aging for 1200 h, apparently due to growth and coarsening of precipitates. This
behavior of the alloy indicates that the precipitation of the Ni2 (Cr,Mo) phase is most
effective in increasing the alloy’s strength, while the formation of δ phases particles
is the least.
Chakravartty et al. [71] have studied the tensile behavior of the alloy as a function
of microstructure developed during service exposure for prolonged periods. These
studies were carried out over a temperature range from room temperature to 700 °C.
Figure 4.22 shows three microstructures of the alloy developed along with a 12 m
long tube service exposed at temperatures over a range of about 600 to 750 °C for a
prolonged period. The three microstructures, respectively contained: (1) a uniform
distribution of fine precipitates of γ as well as Ni2 (Cr,Mo) phases in comparable
volume fractions (Fig. 4.22a); (2) coarse γ particles distributed uniformly within
the γ matrix (Fig. 4.22b); (3) very coarse γ particles (Fig. 4.22c) along with δ
particles predominantly at grain boundaries (Fig. 4.22d). The three microstructures
were designated as Top, Middle and Bottom, respectively according to regions of
the tube in which they formed. A detailed description of the development of this
microstructure is given later in Sect. 8.6.1 of Chap. 8.
All microstructures showed uniform distribution of three variants of the γ phase
and six variants of the Ni2 (Cr,Mo) phase precipitates (only in Fig.4.22a). Table
4.5 shows the average size of the γ and Ni2 (Cr,Mo) phase particles in the three
samples. Particles of both the phases maintained coherency with the matrix even
when they grew to large sizes. Precipitation of these phases significantly increased
the alloy’s yield and ultimate tensile strengths with an enormous reduction in the
attendant ductility and impact toughness compared to the alloy in solution annealed
condition.
Figure 4.23 shows the flow stress behavior of this service exposed alloy at different
test temperatures. The Top samples showed a much larger elongation, particularly
at 25 and 300 °C temperatures, than those in the Middle and Bottom samples. The
Bottom specimens exhibited the lowest properties in terms of both strength and
Fig. 4.22 Microstructures of the service aged samples. a–c TEM micrographs of Top, Middle and
Bottom samples showing the formation of γ and Ni2 (Cr,Mo) (only in Top sample) phase particles
in the three microstructures and corresponding electron diffraction patterns in their insets. d Optical
micrograph of the Bottom sample showing the formation of δ phase particles along grain boundaries.
Reprinted from Ref. [72], Copyright (2013), with permission from Elsevier
elongation. Variations in tensile properties of the three samples, as a function of

the test temperature, are shown in Fig. 4.24. While the UTS of Bottom and Middle
specimens showed similar trends of slight increase with test temperature up to 600 °C
followed by a sharp drop, the Top specimens showed a slight decrease up to about
450 °C before its sharp drop. In general, the YS of all the samples showed a decreasing
trend with increasing test temperature except in the temperature range 300–550 °C
where it showed either a plateau or a slight increase within the temperature range.
However, the ductility first improved gradually with temperature, followed by a
rapid rise for all the samples. The Top sample showed a much higher elongation,
particularly at 25 and 300 °C, than Bottom and Middle specimens. The Bottom
specimen showed the lowest properties in terms of both strength and elongation.
The three samples exhibited relatively low Charpy impact energies, in the range
of 10–40 J, at room and 300 °C temperatures compared to a typical value of about
110–150 J for the virgin wrought Alloy 625 [47]. Thomas and Tait [73] reported
similar low impact values for superheaters tubes of Alloy 625 service exposed at
Table 4.4 Nominal room temperature mechanical properties of Alloy 625 in different product
forms and thermal conditions [47]
Alloy product Yield strengtha Ultimate Ductility (%) Brinell
and condition (MPa) tensile Elongation Area hardness
strength reduction (BHN)
(MPa)
Rod, Bar, Plate
As-rolled 414–758 827–1103 60–30 60–40 175–240
Annealed 414–655 827–1034 60–30 60–40 145–220
Solution 290–414 724–896 65–40 90–60 116–194
annealed
Sheet and strip
Annealed 414–621 827–1034 55–30 - 145–240
Cold-drawn tube and pipe
Annealed 414–517 827–965 55–30 - -
Solution 276–414 689–827 60–40 - -
annealed
a 0.2% offset value
Table 4.5 Average size of

Sample γ particles Ni2 (Cr,Mo) particles
particles in Top, Middle and
Bottom samples shown in Top 13 ± 21.8 nm 20.2 ± 25 nm
Fig.4.22 [71] Middle 38.9 ± 65.6 nm –
Bottom 206.7 ± 177 nm –
temperatures between 480 and 560 °C. The service exposed alloys also exhibited very
low resistance to crack propagation, particularly in the Bottom samples
√ as reflected
in its very low fracture toughness, KIC , (in the range 35–40 MPa m) for the fatigue
√ sample at room temperature. However, the KIC value recovered to about
pre-cracked
140 MPa m at 600 °C.
The plastic flow in the temperature range 250–550 °C exhibits a plateau or an
increase in the yield strength due to the dynamic strain aging (DSA) [56]. The flow
behavior in this temperature range is characterized by serrated plastic flow. The alloy
exhibits a transition from a normal to an inverse PLC behavior at a temperature above
350 °C. Deformation microstructure of the Top samples showed shearing of precipi-
tates due to the passage of dislocation pairs (Fig. 4.25a) in the normal PLC regime and
a high density of shear bands in the inverse PLC regime (Fig. 4.25b). On the other
hand, deformation microstructure of Middle and Bottom samples showed similar
features comprising shear bands with a high density of dislocations (Fig. 4.25c) and
twinning (Fig. 4.25d) in the inverse PLC regime.
The change in the deformation mechanism from shearing in the Top samples
to twinning in the Bottom samples appears to result from the difference in their
microstructure. The Top samples contained very fine particles of γ and Ni2 (Cr,Mo)
Fig. 4.23 True stress versus true plastic strain plots of Top, Middle (Mid) and Bottom (Bot) samples
at 25, 300, 450 and 600 °C test temperatures. Reprinted from Ref. [72], Copyright (2013), with
permission from Elsevier
Fig. 4.24 Tensile behaviour of Top, Middle and Bottom samples as a function of the test temperature
phases, while the Middle and Bottom samples both contained coarse particles of the
γ phase in the matrix. As noted in Sect. 4.2, alloys containing γ and Ni2 (Cr,Mo)
phase particles exhibit a transition in the deformation mode from slip to twinning
above a critical precipitate size. Independent studies on the deformation behavior
of Inconel 718 by Sundararaman et al. [12] and on Haynes 242 alloy by Kumar
Fig. 4.25 Deformation microstructures of service aged alloys in different PLC regimes. ashows
pairs of dislocations and b heavy shearing in Top samples in normal and inverse PLC regimes,
respectively. c, d samples show heavy deformation by twinning in Bottom samples in the inverse
PLC regime. Inset in (d) shows an electron diffraction pattern from twins in the region. Reprinted
by permission from Springer Ref. [56]. Copyright (2015)
and Vasudevan [38] have shown that the two alloys exhibit a transition from shear
to the twinning mode when the sizes of γ and Ni2 (Cr,Mo) particles in the two
alloys are above 10 nm and 70 nm, respectively. Indeed, the critical size of the
particle would be a function of many factors like anti-phase boundary energy, shear
modulus, stacking fault energy, etc., which are directly related to the composition
of the phase. The composition (in atomic per cent) of the Ni2 (Cr,Mo) in the Top
sample was Ni-22%Cr-10.5%Mo-3%Fe-1.4%Nb, while that of the γ precipitates
in the Middle samples was Ni-9%Nb-8%Mo-5.6%Cr-1.5%Ti-1%Al-0.9%Fe [74].
The composition of the Ni2 (Cr,Mo) phase is very close to that in Haynes 242 alloy
studied by Kumar and Vasudevan [38]. Therefore, the critical size of the Ni2 (Cr,Mo)
precipitates in Alloy 625 can also be assumed to be 70 nm. However, the composition
of the γ phase particles in Alloy 718 contain about 19% niobium [75], significantly
different from its composition in Alloy 625. This difference in the composition of
the γ phase in Alloy 625 and 718 would affect stacking fault energy of the γ
phase in the two alloys. Such a difference in the stacking fault energy of the γ
phase was suggested by Sundararaman [49] who reported the formation of profuse
faults and twins within γ phase particles in Alloy 718 and very few in γ phase
of Alloy 625. A difference in the stacking fault energy of the γ phase particles in
the two alloys would affect their critical size in the two alloys above which their
deformation mode would change from shearing to twinning. This change in the
critical size agrees with the deformation microstructure of an Alloy 625 (aged for
200 h at 650 °C), subjected to 29% deformation [49]. The aged alloy contained
γ particles of about 60 nm diameter (Fig. 4.26). The deformation microstructure
exhibited the formation of extensive deformation bands containing a high density
of dislocations due to the slip activity. Dark-field transmission electron microscopy
imaging revealed the presence of very few γ particles within the bands (Fig. 4.26c),
Fig. 4.26 Deformation microstructure of an Alloy 625 aged at 650 °C for 200 h showing defor-
mation by shearing [49]. a, b, Respectively are bright field and dark field TEM micrographs of a
deformed region. Inset in (a) shows a electron diffraction pattern showing superlattice reflections
of the γ particles. c Shows near absence of γ particles within deformation bands with heavy
deformation. d A high magnification image of sheared γ particles. Reprinted from Ref. [49] by
permission from Dr. M. Sundararaman
which indicated that the deformation within the band sheared particles to such an
extent that either their order was nearly destroyed or their orientation was changed
that they did not image in the dark-field mode (Fig. 4.26d).
4.5.3 Work-Hardening Behavior
The flow stress of a material can be correlated with strain hardening parameter, n, by
the Crussard – Jaoul formulation, given by [76]:
σt = σ0 + kεtn (4.17)
where σ t and εt are true stress and true plastic strain, respectively, σ 0 is the true stress
at εt = 0 and k is a constant.
In their studies, both Sundararaman et al. [12] and Kumar and Vasudevan [38]
have correlated the dominant deformation mechanisms with n. They have shown
that the shearing of precipitates by dislocations is accompanied by a high value of n
(~0.85–0.95).
In contrast, a change in the deformation mechanism from shearing to the twinning
of particles above the critical size is accompanied by a significant drop in the value
of n (<0.57). This is because the passage of deformation by twinning through large
precipitates is controlled by the nucleation of twins, which occurs at a stress value
higher than that required for their growth. Therefore, nucleation of twins is immedi-
ately followed by a “burst” of flow resulting in the easy propagation of deformation
twins across the precipitates (Sect. 4.4).
Table 4.6 Work-hardening parameters obtained by fitting flow stress curves to the Crussard and
Jaoul’s formulation
25 °C 300 °C 450 °C 600 °C
Top sample σ 0 (MPa) 808 700 713 597
K (MPa) 2325 2142 1908 1415
n 0.761 0.785 0.761 0.788
Middle sample σ 0 (MPa) 708 682 702 600
K (MPa) 1118 1650 1537 1517
n 0.499 0.707 0.707 0.564
Bottom sample σ 0 (MPa) 569 537 528 480
K (MPa) 1070 1492 1445 1469
n 0.379 0.485 0.535 0.486
Solution treated σ 0 (MPa) 423
K (MPa) 1305
n 0.792
Singh et al. [72] have analyzed the work-hardening behavior of service aged
samples shown in Fig. 4.22. Table 4.6 gives the values of σ 0 , k and n obtained
by fitting the flow curves in Fig. 4.23 to Eq. 4.17. The Top specimens showed a
much higher value of n than that in Middle and Bottom samples, except for the
values at 300 and 450 °C temperatures for the Middle sample. The values of n
indicate that the Top samples were sheared by the passage of dislocations across
particles, while Middle and Bottom samples were sheared by deformation twinning.
Interestingly, n for the Top sample at room temperature was close to solution-treated
alloy (Table 4.6). A drop in the value of n to about 0.57 in Middle and Bottom
samples indicated a transition of the deformation mechanism from the shearing of
particles by dislocations to particle twinning. The low value of n also ruled out particle
bypassing as the mechanism in these samples because it is always accompanied
by an abrupt increase in the work-hardening rate because of the accumulation of
geometrically necessary dislocations in the vicinity of particles [77, 78]. The values of
n are consistent with the deformation microstructures of the three samples (Fig. 4.25).
In addition, they agree with those reported by Sundararaman et al. [12] for Alloy 718
and by Kumar and Vasudevan [38] for Haynes 242.
4.6 Fatigue Behavior of Alloy 625
Fatigue in materials may be defined as progressive, localized, permanent microstruc-

tural damage occurring under cyclic stresses and strains arising due to thermal or
mechanical loading conditions. The fatigue process is believed to begin at internal
or surface flaws where stresses are concentrated and the initial shear is along slip
planes. The repetitive tensile and compressive loading cycles generate slip intrusions
and extrusions at which cracks nucleate. A crack may initially propagate along one
of the original slip planes but may turn to propagate transversely to the principal
normal stress (Fig. 4.27). Growth of the crack to the critical size may cause frac-
ture after a certain number of cycles. The path to failure of a material under fatigue
conditions may, therefore, be divided into the following processes [79]: (1) crack
initiation due to the early development of fatigue damage; (2) slip band crack growth
due to deepening of the initial crack on planes of high shear stress; (3) crack growth
on planes of high stress in a direction normal to the maximum tensile stress; and,
(4) failure, when the crack grows to a length beyond which the cross-section cannot
support the applied load.
S–N diagrams are the simplest way to express the fatigue behavior of materials.
An S–N diagram depicts the number of cycles (N) required to fail a specimen at a
constant cyclic stress amplitude (S) (Fig. 4.28). The number of cycles to failure at
a given stress amplitude is known as fatigue life at that stress amplitude level. In
contrast, the minimum stress amplitude that can fail the material for a given number
of cycles represents its fatigue strength. The value of the S decreases with increasing
N and tend to flatten out eventually to a stress level below which failure does not
occur. This stress level is termed as fatigue “endurance limit” or simply “fatigue limit”
4.6 Fatigue Behavior of Alloy 625 153
Fig. 4.27 Crack initiation

and propagation under
fatigue loading
Fig. 4.28 Typical S–N

curves for materials with and
without endurance limit
of the material. Certain materialas, like carbon steels and titanium, have a fatigue
limit below which they do not fail and can be cycled infinitely (Curve A). However,
many non-ferrous metals and alloys, like aluminum, copper and magnesium alloys,
do not exhibit well-defined endurance limits. These materials, instead, display a
continuously decreasing S–N response (Curve B). However, a practical endurance
limit may be defined, typically at 108 cycles (Fig. 4.28).
Factors like mean stress, specimen temperature, surface roughness and stress
concentration significantly affect the fatigue life [80]. Stress concentration affects
fatigue strength too. Stress concentrations may arise due to a change in the configu-
ration of a component, surface discontinuities like scratches and notches or inherent
metallurgical discontinuities like inclusions and micro cracks. An increase in the
surface area increases the probability of fatigue crack initiation.
The fatigue loading conditions may involve a combination of tensile and compres-
sive stresses to impose a completely reversed cycle with a zero mean stress value
(Fig. 4.29a). However, the loading cycles are often repeated between a maximum
stress, σ max , and a minimum stress, σ min , with a non-zero mean stress, σ m (= (σ max
+ σ min )/2), and a stress ratio R given by σ min /σ max (Fig. 4.29b). For a fully reversed
loading cycle, R = −1. The R-value strongly affects the fatigue life of a material,
which decreases with increasing mean stress [1]. Figure 4.29b also illustrates that
the maximum and the minimum stresses can be both tension or compression in
nature. In practical situations, a stress cycle may be rather complicated, which can
be approximated to a sinusoidal cycle superimposed on a mean stress.
Fatigue can be classified into high-cycle fatigue (HCF) and low-cycle fatigue
(LCF) depending upon the number of stress cycles to failure being more than or
less than 104 cycles. In principle, there is no fundamental differences between the
mechanisms of the two processes as the S–N curves for the two processes are similar.
However, the important distinction between the two comes from the dominant part
of the fatigue life spent in the damage process. In HCF, most of the fatigue life is
spent in the initiation of cracks, whereas most of the fatigue life in LCF is spent
in the crack propagation. In LCF, cracks may nucleate within 3–10% of the fatigue
life [80]. The LCF condition is of more concern because the failures occur at rela-
tively high stresses and a low number of cycles. It is characterized by a high plastic
strain that fails the sample within about 104 cycles. Moreover, the HCF exposure
is usually accommodated during the design of a component itself. The LCF load-
ings in a plant may arise from the fluctuating workload due to power transients and
temperature-gradient induced thermal strain during its operation and start-ups and
shut-downs. The low-cycle fatigue failure considerations are essential in designing
critical components like nuclear pressure vessels, steam turbines, and other power
machinery.
Figure 4.30 shows the fatigue behavior of Alloy 625 as a function of stress concen-
tration and temperature [80]. An increase in temperature reduces its fatigue limit as
Fig. 4.29 Typical fatigue stress cycles under a reversed stress loading and b repeated stress loading
[1]
Fig. 4.30 S–N curves of

Alloy 625 subjected to
fatigue at different
temperatures [80]
well as fatigue strength. The presence of a notch further reduces fatigue limit of the
alloy significantly.
As the LCF involves cyclic plasticity, the material may respond by hardening
or softening under cyclic loads when the strain amplitude is changed at a given
temperature. The hardening or softening would cause an increase or decrease in the
stress amplitude, respectively. In general, under strain-controlled conditions, an alloy
subjected to a cyclic stress response (CSR) test initially hardens during early fatigue
cycles. Still, it may reach a period of either cyclic saturation or cyclic softening
later, depending upon the microstructure, temperature and total strain range. Well
annealed polycrystalline metals of high purity usually show cyclic hardening due
to dislocation multiplication. At the same time, work-hardened materials undergo
cyclic softening due to rearrangement of pre-strain induced dislocation networks
with the fatigue cycles [1].
Bashir et al. [81] have shown a continuous hardening before failure and a decrease
in the fatigue life with increasing temperature in cast Alloy 625 subjected to LCF at
room and elevated temperatures (Fig. 4.31). Suave et al. [82] have subjected Alloy
625 to fully reversed, strain-controlled stress cycles of 0.5 Hz frequency at 600 °C to
study the effect of the precipitation of the γ phase particles on LCF behavior of the
alloy at elevated temperatures (Fig. 4.32). They have studied this behavior at 0.29,
0.34 and 0.36% strain amplitudes. The alloy exhibited limited cyclic hardening for
about initial 10 cycles at all three strain amplitudes. For about 10–300 cycles, the
alloy exhibited a plateau followed by significant secondary hardening up to the final
failure after a strain amplitude of about 0.35%. The initial hardening of the alloy can
be attributed to dislocation multiplication and accumulation within the slip band. In
contrast, the secondary hardening has been attributed to the faster formation of the γ
phase particles observed under cycling at the test temperatures. Suave et al. [82] have
shown that the kinetics of the formation of the γ phase is dependent on the applied
strain amplitude. The LCF enhances precipitation kinetics due to the accumulation
Fig. 4.31 Effect of

temperature on the cyclic
stress response of Alloy 625
at 0.4% strain amplitude [81]
Fig. 4.32 Cyclic stress

response of Alloy 625 at
600 °C under fully reversed
strain-controlled mode [82]
of plastic strain, which provides numerous sites for nucleating γ particles and faster
diffusion than that in pure thermal exposure. For instance, the δ particles formed after
LCF cycling were bigger than those formed after pure thermal aging of 2000 h at
650 °C. The enhanced kinetics of the γ to δ transformation is attributed to extensive
deformation induced during LCF. The drastic decrease in CSR after the secondary
hardening could be attributed to the catastrophic propagation of microcracks under
the applied load.
The flaw tolerance behavior of an alloy under cyclic loading conditions can be
understood from the crack growth rate, which is a function of: (1) the stress intensity
factor range, ΔK = K max – K min; (2) the stress ratio, R = K min /K max (=σ min /σ max ); and
(3) history of stress in the material, where K max and K min refer to the maximum and
minimum stress intensities for each cycle. Figure 4.33 shows the relationship between
fatigue crack growth rate and K. The curve follows a sigmoidal behavior, divided
into three regions. In region I, when K is small, the crack growth rate is low or below
Fig. 4.33 Schematic

diagram showing the
primary fracture mechanisms
associated with the
sigmoidal variation of
fatigue crack propagation
rate (da/ dN) with alternating
stress intensity (K)
the threshold crack growth region. In this region, the crack propagation depends on
the material’s microstructure, flow properties, and environmentally induced fracture
modes.
For intermediate magnitudes of K (region II), the crack growth rate is governed
by a power-law relationship given by [83],
da
= CK m (4.18)
dN
where C and m are assumed to be material constants, da/ dN is the fatigue crack
growth rate per cycle. In region II, the crack growth is stable and follows a linear
relationship between log da/ dN and log K and is commonly known as the Paris’
Law [83]. The crack growth rate is largely insensitive to the microstructure and the
stress ratio R [84, 85]. The failure generally occurs by a transgranular ductile striation
mechanism [86]. In region III, at very high values of K, the striation growth of
crack is replaced by a high crack growth rate till the fracture occurs [84, 86, 87]. The
superimposition of multiple static damage mechanisms, like cleavage, intergranular
and microvoid coalescence, accelerate the crack growth rate. This behavior of fracture
is somewhat sensitive to microstructure and flow properties of the material.
Figure 4.34 illustrates the difference between regions II and III of the fatigue
fractur in an Alloy 625 sample [88]. Figure 4.34a shows the surface corresponding
to region II characterized by fatigue striations formed during the stable crack growth.
Fig. 4.34 Fractographs of a fatigue fractured Alloy 625 sample failed after 1,10,067 cycles under
maximum stress of 472 MPa: a fractured surface characterized by the propagation of stable crack
growth (region II); b fractured surface characterized by accelerated crack growth in region III.
Reprinted from open-source Ref. [88] under the terms of Creative Commons CC by license
Striations are formed due to the opening and blunting of the crack with the progres-
sion of the fatigue cycle. Each time the crack is opened by a stress cycle, the
crack’s tip deforms plastically and blunts the region that appears as a striation on the
ruptured surface. Figure 4.34b shows the fatigue fractured surface corresponding to
region III, characterized by the coalescence of microvoids, and the sample failed by
intergranular cleavage when it could no longer sustain the load.
James [89, 90] has studied the fatigue crack propagation behavior in Alloy 625 and
compared it with that in Alloy 600 and Alloy 718 over the temperature range of 24–
703 °C [91–93]. He has shown that the fatigue crack propagation rate increases with
increasing temperature (Fig. 4.35). Most alloys exhibit similar behavior. Figure 4.36
shows da/ dN vs K plots of the Alloy 625 at different temperatures and compared
with the results of Alloy 600 and Alloy 718 for comparison [92, 93]. James [89] has
also studied the effect of the stress ratio, R, on the crack propagation rate in the stress
ratio range 0.05 < R < 0.667. Although the slope of all the plots is nearly parallel for
different stress ratios (Fig. 4.37), an increase in the fatigue crack propagation rate
with increasing stress ratio is observed. Still, the effect diminishes at higher values
of R. This has been attributed to the decreasing influence of crack closure with an
increase in the stress ratio [94]
Long [95] has studied the fatigue crack growth rate in welded metal in air and arti-
ficial seawater (3.5% NaCl solution) (Fig. 4.38). The study has shown that the fatigue
crack resistance in Alloy 625 weld metal depends on grain size and its orientation.
The resistance to crack growth increases with decreasing grain size in the plane of
crack propagation. It also increases when the crack propagates at the transverse direc-
tion of the dendritic structure rather than along the dendritic structure (Fig. 4.39).
This indicates that finer grain size improves the fatigue crack growth resistance in
Fig. 4.35 Fatigue crack

propagation rate in annealed
Alloy 625 in air at 24 and
316 °C
Alloy 625. In addition, the crack growth rate under fatigue loading is sensitive to the
morphology and volume fraction of second phase particles. The presence of inclu-
sions, like carbide and TCP phase particles and other microstructural abnormalities
that restricts the plastic flow, reduces the fatigue life. At such inclusions, cracks may
form due to the accumulation of dislocations induced during the cyclic loading.
4.7 Creep Behavior of Alloy 625
Creep is time-dependent plastic deformation at constant load/stress and is a crucial

design consideration at high temperatures (T /T m > 0.5), where T m is the melting point
temperature in Kelvin. A creep curve (creep strain vs. time) consists of three distinct
regimes caused by two competing factors: hardening due to strain and softening due
to recovery. In the primary regime, hardening dominates over recovery and strain
rate decreases with time. The hardening process is balanced by a recovery process in
the secondary regime, and nearly a constant creep strain rate (or steady-state creep
rate) is observed. A general expression for the steady-state creep can be given as a
power-law relation between the applied stress (σ) and minimum creep rate (˙min ) as:
Fig. 4.36 The fatigue crack propagation rate, da/dN, as a function of K in annealed Alloy 625
in air at a 427 °C, b 538 and 593 °C and c 649 and 704 °C [89–91] in comparison to the crack
propagation rates in Alloy 600 and Alloy 718 [92, 93]

−Q C
˙ min = Aσ exp
n
(4.19)
RT
where A is a constant, n is the stress constant, QC is the activation energy for creep
deformation, R is the universal gas constant, and T is the temperature. Usually, at T
> 0.5T m , QC corresponds to the activation energy for self-diffusion. The value of n
may vary considerably with temperature as creep mechanisms change
4.7 Creep Behavior of Alloy 625 161
Fig. 4.37 The effect of

stress ratio R on the crack
propagation rate in annealed
Alloy 625 fatigue tested in
air at 538 °C and 6.67 Hz
[90]
Fig. 4.38 Crack growth

resistance curve (da/dN vs.
K) of an Alloy 625 plate
fatigue tested in air and
3.5%NaCl solution [95]
Fig. 4.39 Growth rate

(da/dN vs. K) of weld
metal cracks parallel and
normal to the dendrite
growth direction in a welded
Alloy 625 metal sample in
air [95]
The creep phenomenon can be classified into two broad categories, diffusion
creep and dislocation creep, depending upon the controlling mechanism. Diffusion
creep involves the migration of atoms and vacancies under the influence of applied
stress. It becomes rate-controlling at high temperatures and relatively lower stresses
(σ /G < 10–4 , where σ is the applied stress and G is the shear modulus). Diffusion
creep can be further classified into two mechanisms: (1) Nabarro-Herring (N–H)
creep [96, 97], when the migration of atom is through the crystal lattice; and (2)
Coble creep [98] when the migration of atom is through grain boundaries. On the
other hand, dislocation creep is controlled by the climb of dislocations and typically
follow a power-law behavior between the minimum creep rate and the applied stress.
Dislocation creep may start at T > 0.4T m and at intermediate to high stresses (10–4 <
σ /G < 10–2 ). At higher stresses (σ /G > 10–2 ), the power-law breaks down due to the
transition from dislocation climb controlled to dislocation glide-controlled process.
Limited work is reported on the creep behavior of Alloy 625. Mathew et al. [99]
have studied the creep behavior of a service exposed Alloy 625 after subjecting it
to a solution annealing treatment. These studies were over the temperature range
600–950 °C at stresses ranging from 50 to 290 MPa. The creep damage in Alloy 625
occurs predominantly in the form of microstructural changes rather than the mechan-
ical damage in the form of cracks and cavities. The rate-controlling deformation
mechanism is dislocation creep.
Typical creep curves obtained at a stress level of 105 MPa at 760, 800 and 815 °C
are shown in Fig. 4.40. However, Alloy 625 exhibits a two-slope behavior with a
slope change at temperatures around 800 °C, around which formation of the δ-phase
dominates. Figure 4.41 shows an iso-stress plot of the rupture life versus temperature
at 105 MPa with a change in the slope at 802 °C [99]. The alloy also exhibits a
minimum rupture elongation at around 777 °C for all the stress and temperature test
conditions (Fig. 4.42). The rupture ductility exhibits a minimum with 10 and 20%
at around 777 °C, after which it increases significantly to reach a value as high as
65% at 875 °C. This minimum in the rupture ductility is observed around the same
temperature at which the iso-stress plot of temperature versus rupture life showed a
change in the slope (Fig. 4.41).
This behavior of the rupture ductility is related to the precipitation behavior of γ
and δ phases. The γ precipitation occurs below 727 °C and above this temperature
Fig. 4.40 Typical creep

curves of solution annealed
alloy obtained at a stress of
105 MPa [99]
Fig. 4.41 Iso-stress plots of

the alloy in solution annealed
condition [99]
Fig. 4.42 Plots showing the

rupture ductility as a function
of test temperature [99]
transforms to the δ phase. The size and morphology of the δ-phase particles increases
with an increase in temperature. The γ phase fully dissolves in the matrix at high
temperatures. The temperature range of precipitation of the γ phase and its transfor-
mation to the δ phase also depend on the duration of aging. In addition, it is a function
of applied stress as it controls the rate at which defects are created, which in turn
helps in diffusional transformations. The alloy exhibits a peak in the hardness and
tensile strength at round 727 °C. Above 727 °C, both hardness and tensile strength
decrease with an increase in aging temperature due to γ particle coarsening and the
δ phase precipitation [100] (Sect. 4.5.2).
Figure 4.43 compares the rupture life of the solution annealed alloy with that of the
Fig. 4.43 LMP data of the

solution annealed alloy [99]
superimposed on the
LMP plot of the virgin
annealed alloy [47]
virgin alloy (in annealed condition) using the Larson–Miller parameter (LMP) rela-
tionship. A value of 20.7 has been used for the constant C in the LMP equation [101],
LMP = T(C + log t r ), where t r is the rupture life in hours, and T is the test temper-
ature in Kelvin. The solid line in Fig. 4.43 represents the stress versus LMP plot of
the virgin alloy plotted using Alloy 625 datasheet of the Special Metals Corporation,
USA [47]. The experimental data of the solution annealed service exposed material
is shown separately. The creep data of the solution annealed service exposed material
falls within a scatter band of ±20% of the rupture strength of the virgin material.
4.8 Fracture Behavior of Alloy 625
The fracture behavior of Alloy 625 changes significantly with microstructural condi-
tions. In solution annealed condition, the alloy exhibits transgranular ductile behavior
typically observed in most face-centered cubic metals. The fractured surface of
solution annealed samples is characterized by locally very high plastic deforma-
tion visible as large dimples (Fig. 4.44) that form due to the nucleation, growth, and
coalescence of voids during deformation culminating into fracture. The voids may
nucleate by the cracking of inclusions like blocky primary-carbides or debonding
of the particle–matrix interface when dislocations in the matrix accumulate in the
vicinity of the interface due to strain incompatibility between the two. With the
build-up of dislocations, the interfacial stress peaks near the particle/matrix interface,
which causes fracture when the stresses become large enough to cause decohesion
of particles from the matrix.
The fractured surfaces of the aged alloy containing fine precipitates of coherent
γ and Ni2 (Cr,Mo) phase are characterized by shear facets, reduction in the depth,
and the sizes of the dimples. Precipitation of coherent γ and Ni2 (Cr,Mo) particles
enhances the planar slip. This manifests itself in shallow dimples and micro cracks
on fractured surfaces due to the high density of flow localization. Figure 4.45a show
Fig. 4.44 A typical ductile

fracture of an Alloy 625 in
solution annealed condition
Fig. 4.45 Fractographs showing transition in the fracture mode from ductile to transgranular
cleavage with the coarsening of γ particles in Alloy 625 aged at 650 °C for a 6 h; b 96 h.
Reprinted from Ref. [102]. Copyright 1997 by The Minerals, Metals & Materials Society. Used
with permission
a typical fractograph of the fractured surface of the alloy containing fine particles
of the γ phase [49, 102]. With the growth of the γ particles, the faceted region
increases and the dimpled regions decrease, and the fracture mode gradually shifts
from ductile to transgranular cleavage fracture (Fig. 4.45b) [49, 102]. When the γ
phase particles are large, the fractured surface becomes prominently faceted with
some dimple-regions because the alloy fractures only after a considerable amount of
deformation in the matrix. The faceted fractured surface with uniform micro-dimples
characterizes the rupture of the alloy containing predominantly the δ phase particles
(Fig. 4.46). Mittra et al. [70] have shown these facets to be along {111} planes.
The formation of carbide precipitates at the grain boundaries significantly influ-
ences fracture behavior of the alloy. As noted above, carbide particles are very hard
and behave as nondeformable inclusions. These particles have little effect on the
Fig. 4.46 Typical fractured

surface of Alloy 625
containing predominantly
the δ phase particles
4.8 Fracture Behavior of Alloy 625 167
Fig. 4.47 Intergranular

failure of Alloy 625 with a
continuous or
near-continuous layer of
carbides at grain boundaries
fracture mode when they are discrete and fine in size. The fracture mode remains
predominantly transgranular even when the δ phase particles co-precipitate with
discrete particles of the carbide phase at the grain boundaries. However, the precip-
itation of grain boundary carbides as a continuous or near-continuous layer changes
the fracture mode from transgranular to predominantly intergranular (Fig. 4.47).
The carbide films act as nucleation sites for the initiation of microcracks due to the
localization of the slip, which causes the intergranular fracture. The frequency of
the occurrence of microcracks associated with such intense, localized slip is nearly
independent of the orientation of the grain boundary with respect to the axis of
straining. Many researchers have shown the formation of such microcracks around
the points of impingement of deformation bands on grain boundary carbide particles
in heavily deformed Alloy 625 and other alloys [102, 103]. When the carbide parti-
cles are very closely spaced, the distances separating neighboring microcracks are
very small. These microcracks can join up to facilitate an easy intergranular fracture
path, similar to when the film is continuous.
Under fatigue loading conditions, the repeated cyclic straining leads to different
amounts of net slip on other glide planes responsible for fatigue crack initiation and
further slipping [1]. Carbide particles near the surface acts as a stress raiser and aid
the initiation of fatigue cracks. Figure 4.48a, c depicts the fracture behavior of a
wrought Alloy 625 subjected to high-cycle fatigue at 650 °C [104]. Multiple crack
initiation was observed in specimens tested under high stressed conditions, whereas
the specimen failed by initiating and propagating a single crack at low-stress levels.
In addition, carbide fracture occurs more easily in cyclic stress conditions [104].
Fracturing and debonding of brittle carbides from the nickel matrix reduces the
fatigue life.
Fig. 4.48 High cycle fatigue fractured surfaces of wrought Alloy 625 at 650 °C; a–b
600 MPa(14,761 cycles) and c–d 575 MPa (38,563 cycles). Sites of fatigue crack initiation are
pointed by black arrows. Reprinted from Ref. [104], Copyright (2020), with permission from
Elsevier
The fractured surface of samples subjected to creep at intermediate temperatures

exhibits wedge type of cracks [99]. Figure 4.49a, b shows typical creep damage, and
the fractured surface of a sample crept at 750 °C that ruptured after a period of 170 h.
Fig. 4.49 Micrographs of a creep tested Alloy 625 sample tested at 650 °C for 170 h: a typical
creep damage; b fractured surface. Reprinted from Ref. [99], Copyright (2004), with permission
from Elsevier
4.8 Fracture Behavior of Alloy 625 169
The fracture during creep occurs due to the growth and linkage of microcracks leading
to plastic instability or ligament tearing between the intergranular cracks [99].
4.9 Summary
Alloy 625 has an excellent combination of strength and ductility in the annealed
condition. The strength of the alloy in the annealed condition is due to the solid-
solution effects of various alloying additions. However, thermal exposure at interme-
diate temperatures causes significant hardening and concomitant loss in ductility and
toughness. This alloy’s hardening is mainly due to the formation of precipitates of γ
and Ni2 (Cr,Mo) precipitates, while the precipitation of δ and carbide phases harden
to a lesser extent though their precipitation weaken grain boundaries considerably.
γ and Ni2 (Cr,Mo) precipitates form as small and coherent particles, distributed
homogenously throughout the matrix. The ordered nature of precipitates imposes
restrictions on the continuity of deformation across them. These restrictions cause a
loss in the alloy’s ductility. The alloy exhibits a change in the precipitate deforma-
tion mechanism from shearing of particles to twinning above a critical particle size.
The twinning of intermetallic precipitates allows the passage of deformation without
disturbing the ordered atomic arrangement in precipitates. Energetically, the twinning
of large ordered precipitates by dislocation movement is favored over looping. The
transition of the deformation mechanism from particle shearing to particle twinning
is accompanied by a significant drop in the work-hardening exponent.
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Chapter 5
Alloy 625 PLUS
Alloy 625 PLUS alloy is developed as an age-hardenable variant of Alloy 625 to

impart strength superior to Alloy 718 but retaining excellent corrosion resistance
and welding properties of Alloy 625 [1–6]. The sluggish aging response of Alloy
625 constrains it for deformation-induced strengthening and precipitation for higher
strength levels. M/s Carpenter Technology, USA, patented Alloy 625 PLUS vide
a US Patent number 5556594 and market as “Custom Age 625 PLUS” alloy [6].
Alloy 625 PLUS is a highly corrosion-resistant, cobalt-free, alloy developed to be
age-hardened by the precipitation of γ phase particles to achieve high strength levels
without warm or cold working. The nominal composition of the alloy is given in Table
5.1. The corrosion resistance of Alloy 625 PLUS is similar to Alloy 625 and superior
to Alloy 718 in many environments. The alloy is designed for applications in deep
sour wells or environments containing chlorides, hydrogen sulfide and carbon dioxide
at elevated temperatures and pressures. These applications require good resistance
against pitting and crevice corrosion and stress-corrosion cracking, combined with
high strength and ductility.
5.1 Chemistry of Alloy 625 PLUS
The chemistry of alloying additions in Alloy 625 PLUS is adjusted to accelerate

the precipitation of γ particles for age hardening after a short incubation period.
Yield strength of about 825 MPa or above can be obtained within 24 h of aging
[5], while much longer aging times (>70 h) are required to obtain similar strength
levels in annealed Alloy 625 (Sect. 4.5.2). The amount of titanium in Alloy 625
PLUS is increased to about 1.3 wt%, compared to a maximum of 0.4 wt% in Alloy
625. In addition, the carbon content is reduced to about 0.01 wt% compared to a
maximum of 0.10 wt% in Alloy 625 [5]. An increase in the titanium, along with
niobium and aluminum, promotes the γ induced age hardening of the alloy. The
best combination of properties is obtained using 2.75– 4.25% Nb and 0.75–1.5% Ti
https://doi.org/10.1007/978-981-19-1562-8_5
176 5 Alloy 625 PLUS
Table 5.1 The nominal composition of Alloy 625 PLUS

Ni Cr Mo Nb Al Ti C Si Fe
Min. 59.0 19.0 7.0 2.75 – 0.75 – –
Max. 63.0 22.0 9.5 4.0 0.35 1.5 0.03 0.2 Bal
[5]. The amount of niobium and titanium elements are balanced to achieve alloy’s
hardness in the range of about 35–40 HRC using a double-aging treatment similar to
the one commonly given to Alloy 718. Even though aluminum also promotes the age-
hardening reaction in most γ bearing superalloys, it has little role in strengthening
γ bearing alloys. Niobium and titanium promotes the precipitation of the γ phase
while aluminum stabilizes the γ phase. The concentration of aluminum is therefore
restricted to a maximum of 0.35%. The minimum levels of 2.75% and 0.75% of
niobium and titanium, respectively are required to achieve a yield strength of about
825 MPa. Higher levels of the yield strength, up to about 965 MPa and even higher,
can be achieved by increasing the niobium and titanium contents, but an increase
in the titanium content reduces the resistance to stress-corrosion cracking [5]. This
effect of titanium restricts its concentration to a maximum of 1.5% titanium. On the
other hand, alloys containing less than about 0.75% titanium exhibits much lower
resistance to crevice corrosion than alloys with higher titanium contents.
Minimum levels of chromium and molybdenum are retained to preserve the excel-
lent corrosion resistance of Alloy 625. An excellent combination of properties is
obtained using 18–22% chromium and 7.5–11% molybdenum, provided that the
sum of the two elements does not exceed 31%. However, excessive chromium and
molybdenum may promote the formation of TCP phases (Chap. 3), which reduce
corrosion resistance, hot workability and toughness. A minimum of 60.5% nickel
is required for good resistance to stress-corrosion cracking in boiling 45% MgCl2 .
The carbon content is reduced to a maximum of 0.03% for the best combination of
strength and corrosion resistance and to minimize the precipitation of intergranular
carbides during aging. Low carbon and nitrogen contents reduce the formation of
niobium- and titanium-rich primary carbonitride particles ((Nb, Ti)(C, N)) during
solidification. However, even with a very low amount of carbon in the alloy, high
activities of chromium and molybdenum may cause the precipitation of undesir-
able chromium and molybdenum-rich carbides (M23 C6 , M6 C) during a subsequent
aging treatment at temperatures about 730 °C or above, which can sensitize the
alloy for intergranular corrosion. As noted later in Sect. 7.4.3, precipitation of the
niobium/titanium-rich carbide ((Nb, Ti)C) particles at temperatures above 980 °C
minimize the intergranular precipitation of M23 C6 and M6 C carbides and improves
the resistance against intergranular corrosion. With this chemistry, Alloy 625 PLUS
gives corrosion resistance, in solution annealed condition, similar to Alloy 625 and
can be age-hardened to achieve a strength better than Alloy 718, to a value of 825 MPa
and more [5].
5.2 Mechanical Properties of Alloy 625 PLUS 177
5.2 Mechanical Properties of Alloy 625 PLUS
Alloy 625 PLUS is solution annealed at temperatures in the range of about 1025 -
1050 °C to dissolve hardening precipitates and recrystallize the deformed grains to
achieve uniform properties [7, 8]. A solution annealing treatment at temperatures
above 1050 °C may coarsen the grains. On the other hand, an annealing treatment
at temperatures below 980 °C may leave some grains un-recrystallized and result in
mixed grain structures. Typical mechanical properties of Alloy 625 PLUS in fully
solution annealed condition are listed in Table 5.2 [7].
Unlike Alloy 625, solution annealed Alloy 625 PLUS can be age-hardened to
achieve hardness up to about 50 HRC [7]. The inherent solid-solution nature of
Alloy 625 limits its hardness below about 100 HRB [9, 10], which can only be
increased further by prolonged aging, as noted in Chap. 4, or by cold or warm
working. Cold working can increase the hardness of Alloy 625 up to about 45 HRC
with a drastic decrease in ductility to about 5% [10]. Warm or cold working combined
with prolonged aging may, therefore, be used to strengthen Alloy 625, but such
warm or cold working operations becomes less practical as the cross-section of the
working piece increases. On the other hand, the Alloy 625 PLUS can be age-hardened
easily without cold or warm deformation using standard age-hardening treatments
to impart higher mechanical properties across a broad section thickness range. Frank
has studied the age-hardening behavior of 625 PLUS alloy [5]. Figure 5.1 shows
variation in the hardness of the Alloy 625 PLUS as a function of time and tempera-
ture after single- and double-aging treatments. The lower curves depict the hardness
Table 5.2 Typical room-temperature tensile properties of solution annealed Alloy 625 PLUS [7]
YS (MPa) UTS (MPa) Elongation (%) Reduction in area (%) Hardness (HRB)
379 834 61 73 88

hardness of the Alloy 625
PLUS as a function of time
and temperature after
single-ageing (broken
curves) and double-ageing
(solid curves) treatments [5].
“T ” in upper curves refers to
the first (primary) ageing
temperature, while FC and
AC refer to the furnace- and
air-cooled, respectively
of the single-step aging. The upper curves show the hardness after the double-aging
treatments, where “T ” in the labels refers to the first (or the primary) aging tempera-
ture. During the double-aging treatment, the samples were furnace cooled (FC) from
the primary temperature to the second aging temperature (620, 650 or 676 °C) at
a rate of about 50 °C/h to reach the second temperature in 2 h. The samples were
air-cooled (AC) after the second aging treatment. It is evident from Fig. 5.1 that
the second aging in a double-aging treatment increases the hardness of the alloy by
about 5–6 HRC points over the hardness achieved by the single (primary) aging treat-
ment for a given aging time and temperature with little or no additional intergranular
carbides. Further, the double 8-h cycle provides slightly higher hardness than the
double 4- or 2-h cycles. Under-aging during the primary-aging treatment minimizes
the intergranular carbide precipitation [5]. This study established that a double-aging
treatment of 730 °C/8 h/FC to 620 °C/8 h/AC gives the highest hardness with minimal
intergranular precipitation [5]. This 18-h double-aging treatment is very close to the
double-age-hardening treatment usually employed for hardening of aerospace-grade
Alloy 718 as per the AMS 5662 standard [11]. The AMS 5662 treatment involves a
solution treatment at about 980 °C for 1 h, followed by air cooling, and a subsequent
18-h double-aging treatment involving 720 °C/8 h/FC and 620 °C/8 h/AC cycles.
The aging treatments mentioned above can be used to achieve a yield strength in
the range of over 690 to 1035 MPa without cold or warm working [5, 7]. Table 5.3
gives room-temperature tensile properties of the alloy age-hardened by a few single-
and double-aging treatments [7]. An 18-h double-aging treatment of 732 °C/8 h/FC
to 620 °C/8 h/AC imparts about 900 MPa of yield strength to the 625 PLUS alloy
without the cold or warm deformation.
Table 5.4 compares the room-temperature tensile properties of the double-age-
hardened 625 PLUS alloy with those of age-hardened 625 and 718 alloys [5]. The
age-hardened Alloy 625 PLUS also exhibits good hardenability as evidenced by
similar tensile properties of the annealed alloy bars of various diameters subjected to
the double-aging of 730 °C/8 h/FC to 620 °C/8 h /AC (Table 5.5) [7]. The solution
Table 5.3 Age-hardening effect on room-temperature tensile properties of a solution annealed

Alloy 625 PLUS solution annealed at 1038 °C/2 h/AC [7]
Aging treatment YS (MPa) UTS (MPa) Elongation (%) Reduction in Hardness
area (%) (HRC)
732 °C/4 h/AC 710 1117 48 63 30
732 °C/8 h/AC 779 1145 41 59 34
718 °C/8 h/FC to 827 1220 37 57 35.5
620 °C/8 h/AC
732 °C/8 h/FC to 896 1248 32 54 38
620 °C/8 h/AC
746 °C/8 h/FC to 952 1269 32 51 39.5
620 °C/8 h/AC
Table 5.4 A comparison of room-temperature tensile properties of Alloy 625, Alloy 625 PLUS
and Alloy 718 [5]
Alloy Solution treatment Aging treatment YS UTS Elongation Reduction
(MPa) (MPa) (%) in area (%)
Alloy 925 °C/1 h/AC 640 °C/64 h/AC 552 972 46 58
625 885 °C/1 h/AC 650 °C /70 h/AC 869 1186 31 37
1150 °C/0.5 h/AC Cold Rolled 25% 889 1048 29 59
(No Age)
Alloy 1040 °C /2 h/AC 730 °C /8 h/FC to 917 1262 32 53
625 620 °C/8 h/AC
PLUS
Alloy 1025 °C/2 h/WQ 788"C/8 h/AC 910 1227 26 33
718 970 °C/1 h/AC 720 °C/8 h/FC to 1200 1400 16 30
620 °C/8 h/AC
Table 5.5 Room-temperature tensile properties of bars of various diameters of Alloy 625 PLUS
alloy subjected to a double ageing treatment of 730 C/8 h/FC to 620 °C/8 h/AC after an annealing
treatment 1040 °C/2 h/AC
Bar diameter (mm) YS (MPa) UTS (MPa) Elongation (%) Reduction in area (%)
25 917 1310 33 55
38 896 1282 31 56
70 862 1250 35 53
102 924 1282 33 54
127 931 1262 32 53
152 917 1262 32 53
184 910 1276 32 51
annealed and age-hardened 625 PLUS alloy exhibit similar tensile properties and
impact energies in the longitudinal and transverse orientations [7].
A hardness of over 50 HRC can be achieved within 4 h of single-aging in the
temperature range 675 to 690 °C (Fig. 5.2) [12]. A secondary aging treatment for 4 h
at about 580 °C results in a further increase in the hardness. Cold working the alloy
before age-hardening significantly improves its strength. Tensile strengths above
1790 MPa, along with good ductility, has been reported in the 38% cold-worked alloy
subjected to direct aging for 4 h at 732 °C [12]. Cold working of the alloy before
aging nearly doubles the yield strength. It increases the ultimate tensile strength by
about 550–620 MPa compared to the solution-treated and double-aged conditions
[2]. Table 5.6 gives room-temperature tensile properties of a cold-worked 625 PLUS
alloy subjected to various single and double-aging treatments [12]. A single age-
hardening treatment to the cold-worked alloy results in about 180–240 MPa increase
in the tensile strength of the cold drawn bar of 625 PLUS alloy. Tensile strengths of
over 1790 MPa can be obtained with about 9% elongation. A second (final) aging
Fig. 5.2 Effect of single-and double-ageing on the hardness of 38% cold-worked Alloy 625 PLUS
[12]
Table 5.6 Room-temperature tensile properties of cold-worked Alloy 625 PLUS Alloy after
various age-hardening treatments
Age treatment YS (MPa) UTS (MPa) Elongation (%) Reduction in Hardness
area (%) (HRC)
As cold drawn 1269 1613 12.5 52 45.5
649 °C/4 h/AC 1772 1820 9.4 39 50
691 °C/4 h/AC 1793 1848 8.8 38 50
732 °C/4 h/AC 1724 1793 9.1 33 50
649 °C/4 h/FC to 1820 1862 9.0 37 50
579 °C/4 h/AC
677 °C/4 h/FC to 1855 1896 8.4 35 51
579 °C/4 h/AC
718 °C/8 h/FC to 1806 1869 8.2 32 51
621 °C/8 h/AC
FC = Furnace cooled at rate of 56 °C per hour; AC = Air-cooled
The alloy was given 38% cold drawn before ageing treatments [12]
treatment increases its strength by an additional 35–70 MPa without significantly

reducing ductility. A double-aging treatment of 650 °C/4 h/FC to 580 °C/4 h/AC to a
38% cold-worked 625 PLUS alloy produces high tensile strength of about 1862 MPa
and maximum ductility of 9%. Similar strength levels are obtained in Alloy 718
solution annealed at 1025 °C alloy followed by an over-aging treatment at about
790 °C as per NACE MR0175 specifications [11]. This treatment of Alloy 718
provides better uniformity and toughness compared to that obtained by the standard
aerospace double-aging treatment of 720 °C/8 h/FC to 620 °C/8 h/AC. However,
the over aging of Alloy 718 at 790 °C imparts relatively a lower strength than that
Table 5.7 Effects of prolonged thermal exposure on the room-temperature tensile properties of
cold-worked and aged Alloy 625 PLUS at various intermediate temperatures [12]
Thermal YS (MPa) UTS (MPa) Elongation (%) Reduction in Hardness
exposure area (%) (HRC)
As aged 1820 1862 9.0 37 50
427°/1000 h 1841 1882 8.8 36 50
482 °C/1000 h 1889 1917 8.3 37 50.5
538 °C/1000 h 1875 1931 8.0 35 51
538 °C/2000 h 1903 1944 7.7 34 51
593 °C/1000 h 1924 1979 6.7 29 51.5
649 °C/1000 h 1827 1924 7.0 27 50.5
FC = Furnace cooled at rate of 56 °C per hour; AC = Air cooled
The alloy was 38% cold drawn and aged 649 °C/4 h/FC to 579 °C/4 h/AC
by the AMS 5662 treatment [11, 13]. Pronged thermal exposure of the double-aged
Alloy 625 PLUS further enhanced its tensile strength by about 125 MPa (Table 5.7),
particularly at temperatures in between about 500–600 °C, which is the temperature
range known to form Ni2 (Cr, Mo) phase particles in Alloy 625 (Sect. 3.5.3).
A 10-h double-aging cycle of 650 °C/4 h/FC to about 580 °C/4 h/AC gives
Alloy 625 PLUS the best combination of strength and ductility. This combination of
strength and ductility is better than about 1731 MPa strength and about 10% ductility
of the age-hardened cold-worked Alloy 718 aged by an 18-h long 720/620 °C double-
aging cycle [12]. Increased grain boundary precipitation, which occurs with primary-
aging temperatures above 650 °C, may be responsible for the lower ductility levels.
The impact energy of the double-aged 625 PLUS alloy showed a higher value (~
19.4 J) compared to ~10 J of Alloy 718 [12]. The elevated temperature tensile prop-
erties of the two alloys show a similar trend of a slight reduction in the strength with
increasing temperature and a ductility minimum at about 538 °C (Fig. 5.3).
5.3 Microstructure of Alloy 625 PLUS
Alloy 625 Plus is likely to possess all the phases of Alloy 625 noted in Chap. 2.
However, the increased titanium concentration in Alloy 625 PLUS affects the
precipitation behavior and composition of titanium-containing phases. Thermo-
dynamic computations using the MatCalc 6.03 Pro software and accompanied
nickel-database (ME-Ni 1.3) predict increased titanium partition in niobium bearing
phases, which may, in turn, affect their lattice parameters and thermal stability.
For example, the thermodynamic calculations predict the composition of the γ
phase to be Ni3 (Nb0.60 Ti0.27 Mo0.04 ) in Alloy 625 PLUS against its composition of
Ni3 (Nb0.69 Ti0.05 Mo0.12 Al0.03 ) in Alloy 625, while its thermal stability increased up
to about 900 °C in the former against up to about 725 °C in the latter. In addition,
Fig. 5.3 A comparison of the elevated-temperature tensile behaviour of 625 PLUS and 718 alloys
subjected to double ageing treatments [7]. Alloy 625 PLUS was subjected to a 10-h long double-
ageing 650 °C/4 h/ FC to 580 °C/4 h/AC cycle while Alloy 718 was subjected to its standard 18-h
720 °C/8 h/ FC to 620 °C/4 h/AC cycle
increased titanium enhances the precipitation kinetics of the γ phase in the former
as reflected by its Time-Temperature-Transformation (TTT) curves in the two alloys
(Fig. 5.4).
The limited reports available on microstructure-properties relationships for the
Alloy 625 PLUS pertains to the formation and evolution of the γ phase because
of its primary contribution to the age hardening of the alloy. Most of the studies
above are related to the effect of the formation of the γ phase on mechanical and
corrosion properties of the alloy subjected to various heat treatments. Apart from the
γ phase, Yu and Marquis [14] have reported the precipitation of the titanium and
Fig. 5.4 Calculated time–

temperature-transformation
curves for the precipitation
of γ phase in Alloy 625 and
Alloy 625 PLUS. The curves
represent a 5% volume
fraction of the γ phase
5.3 Microstructure of Alloy 625 PLUS 183
aluminum rich γ phase particles after aging of more than 300 h at 650 °C. They have
argued that the formation of the γ phase after prolonged aging is due to reduced
concentration of the niobium in the matrix because of Ni3 (Nb, Ti) γ precipitation.
The formation of the γ phase increases the concentration ratio of (Al + Ti) to Nb,
which promotes its precipitation similar to that reported in Alloy 718 [15, 16]. A
higher (Al + Ti)/Nb ratio in Alloy 625 Plus (~0.9) compared to Alloy 625 (~0.3)
appears to stabilize the γ phase. The γ and γ phases in Alloy 625 PLUS form
with compositions close to Ni3 (Nb0.39 Ti0.26 Mo0.22 Al0.02 ) and Ni3 (Ti0.4 Al0.4 Nb0.2 ),
respectively [14], which are in close agreement with Ni3 (Nb0.60 Ti0.27 Mo0.04 ) and
Ni3 (Ti0.49 Al0.28 Nb0.23 ) compositions predicted for the two phases by thermodynamic
calculations using the MatCalc 6.03 Pro software.
Vander Voort et al. [8] have studied the growth/coarsening of ellipsoidal shaped
γ phase particles in Alloy 625 PLUS solution annealed at 1038 °C for 2 h, followed
by single-aging or double-aging treatments. Figure 5.5 shows variation in the length
(diameter) of γ particles (Fig. 3.20) as a function of time in Alloy 625 PLUS aged
at 732, 774 and 802 °C for periods ranging from 20 to 1800 min. The growth of
the γ particles is a function of temperature and time, though the effect of the time
on the size reduces somewhat with an increase in the aging temperature. An 18 h
double-aging treatment involving 732 °C/8 h/FC and 620 °C/8 h/AC aging produced
particles of average diameter 14.9 ± 1.3, which increased to 26.5 ± 1.7 nm during
a subsequent prolonged exposure of 500 h at 650 °C [8]. Over aging during the
first aging produces much bigger particles. For instance, a double-aging treatment
involving the first aging of 8 h at a higher temperature of 788 °C, followed by furnace
cooling to 620 °C for the second aging of 8 h, producing particles of average size
55.2 ± 3.7 nm [8].
Yu and Marquis [14] have reported the formation of γ precipitates after aging for
8 h at 650 °C, which increased in the size with increasing aging time, in agreement
with Vander et al. [8]. However, Yu and Marquis have also reported the formation
of the γ phase particles after aging of more than 300 h, though their density was
Fig. 5.5 Variation in the size

of γ particles as a function
of time during single ageing
at different temperatures [8]
Fig. 5.6 Proxigrams showing partitioning behaviour of different solutes in a γ -γ phase, and b
γ -γ phase in the 625 PLUS alloy after ageing for 1000 h at 650 °C. Reprinted from Ref. [14],
Copyright (2019), with permission from Elsevier
much lower than the γ particles [14]. Figure 5.6 shows the partitioning behavior of
different constituent species in γ -γ and γ -γ phases [14]. It is clear from Fig. 5.6 that
nickel, niobium and titanium partitioned to γ precipitates while chromium and iron
remained in the γ matrix. Aluminum partitions strongly to the γ phase compared
to slight enrichment in the γ phase. Molybdenum significantly depletes from the
γ phase, while its distribution remains unchanged in the γ phase. The cuboidal γ
phase particles forms on the flat surface of the disk-shaped γ phase particles in two
configurations as γ -γ doublets and γ -γ -γ triplets comprising two γ particles
bounding a γ particle (Fig. 5.7), though doublets are observed more frequently. The
formation of the “piggyback” configuration of γ and γ phase particles have been
attributed to the low energy of the coherent γ /γ interface owing to good atomic
matching between the {100} planes of the L12 structure of the γ phase and the
(001) plane of the D022 structure of the γ phase [15]. The γ /γ interface favors the
heterogeneous nucleation due to smaller lattice misfit than the γ /γ interface. Similar
arrangements of γ and γ precipitates have been reported in many studies on Alloy
718 [15–21]. Theska et al. [18] have also reported γ -γ -γ triplets in addition to
γ -γ -γ triplets in Alloy 718 under different aging conditions.
5.3 Microstructure of Alloy 625 PLUS 185
Fig. 5.7 Atom probe

tomography reconstructed
maps illustrating the
formation of γ -γ duplets
and γ -γ -γ triplets in Alloy
625 PLUS. Reprinted from
Ref. [14], Copyright (2019),
with permission from
Elsevier
In principle, either of the two phases can heterogeneously nucleate on the other
depending upon the relative precipitation kinetics of the two. Unlike the present
case, heterogeneous nucleation of the γ phase particles on pre-existing γ has been
reported in some cases where the γ particles form first [15, 16, 19]. However, the
formation γ -γ -γ triplets in Alloy 625 PLUS is rather surprising as the γ phase
forms first in Alloy 625 PLUS, while the γ phase particles nucleate much later, as
observed only after about 300 h of aging [14]. Therefore, it is reasonable for the γ
phase particles to form γ -γ doublets by nucleating onto the existing γ particles to
reduce the interfacial and elastic strain energy. Similar nucleation sequence involving
the nucleation of the γ phase followed by that of the γ phase has been reported
earlier [17, 20]. Miller [17] has postulated that aluminum rejection in the adjacent
matrix during the formation of the pre-existing γ precipitates favor the nucleation
of γ precipitates by increasing the (Al + Ti)/Nb ratio. However, the low amount of
aluminum and its slight partitioning in the γ precipitates in Alloy 625 Plus appears
less convincing for the formation process of γ -γ -γ triplet. Alternatively, such
configurations may form as a result of the impingement of independently nucleated
adjacent γ and γ precipitates as suggested by Sundararaman et al. [20]. Nonetheless,
the formation of the γ phase particles during prolonged aging may be the reason for
further increase in the strength of the alloy, as reported by Frank and Grimes [12]
(Table 5.7).
The γ phase in Alloy 625 PLUS also exhibits different composition and precip-
itation behavior than Alloy 625. The main difference in the composition of the γ
phase in two alloys is the concentration of niobium and titanium. The amount of
niobium is reduced to about 9.5 at% in Alloy 625 Plus compared to about 13 at% in
Alloy 625. In contrast, the titanium concentration increased significantly to about 7
at% in Alloy 625 Plus compared to about 1.5 at% in Alloy 625 [14].
Figure 5.8 illustrates the partitioning behavior of constituent elements in γ and γ
phases during aging at 650 °C up to 1000 h [21]. The figure depicts the difference in
the composition of various elements in the γ phase (C γ ) and γ matrix (C γ ) along
the x-axis, against the difference in their compositions in the matrix compared to
the average alloy composition (C n ) on the y-axis. Figure 5.8 indicates that nickel
and niobium preferentially partition to the γ phase and the phase becomes richer in
nickel and niobium during their evolution with increasing aging time. The titanium
also partitions to the γ . However, its concentration in the phase remains more or less
unchanged with time. This partitioning of titanium is consistent with the composition
of the γ phase, Ni3 (Nb>0.5 Ti<0.5 Al<0.5 ), proposed much earlier by Floreen et al. [22]
(Sect. 3.2.2). On the other hand, molybdenum initially partitions to the γ phase, but
the phase tends to reject it during prolonged aging, consistent with Yu and Marquis
[14] (Fig. 5.6). This result is also in agreement with a small amount of molybdenum
(~6 at%) in the γ phase reported by Floreen et al. [22]. Aluminum has a slight
preference for the partitioning to the γ phase. On the contrary, chromium and iron
partition to the γ matrix and enrich the phase with time. Notwithstanding that, Floreen
et al. [22] reported a small amount of chromium (~4 at%) in the γ phase. In Alloy
625 Plus, however, chromium reduces to nearly half, ~2 at% [14], indicating its
enhanced partitioning to the matrix phase in Alloy 625 Plus.
The γ phase in Alloy 625 Plus forms with a composition close to
Ni3 (Ti0.4 Al0.4 Nb0.2 ). The partitioning of nickel, titanium, aluminum and niobium
solutes to the γ in Alloy 625 Plus agrees with that reported for Alloy 718. However,
the γ phase in Alloy 625 Plus contains slightly higher titanium and less niobium
than their concentrations in the same phase in Alloy 718. The composition of the γ
phase in Alloy 718 is reported as Ni3 (Ti0.24~0.36 Al0.36~0.43 Nb0.22~0.36 ) [16, 23, 24].
Yu and Marquis [14] have also compared the evolution of the of γ precipitates
in Alloy 625 Plus and Alloy 625 and have shown that the volume fraction and the
number density of the γ phase precipitates are nearly an order of magnitude higher in
the former for the same aging conditions for the two alloys [14]. The coarsening rate
of γ precipitates are slower in Alloy 625 Plus than Alloy 625, owing to the higher
partition coefficients of niobium and titanium in the former [14]. A high partition
coefficient reduces the coarsening rate [25]. The precipitation of the γ phase particles
do not significantly influence the coarsening kinetics of γ precipitates, as the γ phase
forms after a prolonged period and in low volume fraction and number density [14].
5.4 Summary 187
Fig. 5.8 Lever rule plots depicting partitioning behaviour of constituent elements in the γ and γ
phases during ageing of Alloy 625 at 650 °C for 10, 100 and 1000 h. The figure shows the difference
in the composition of various elements in γ phase (C γ ) and the γ matrix (C γ ) along the x-axis
against the difference in their composition in the γ matrix with respect to average composition (C n )
of the analysed volume along the y-axis. Reprinted from open-source Ref. [21] under the terms of
Creative Commons CC by license
5.4 Summary
Even though Alloy 625 age hardens significantly at elevated temperatures, its sluggish
aging response constraints it to exploit commercially. Alloy 625 Plus differs from
Alloy 625 by about 1% extra titanium. Increasing the titanium concentration in Alloy
625 to about 1.3% significantly increases the alloy’s age-hardening response by γ
precipitates. This allows Alloy 625 Plus to achieve higher strength levels without
warm or cold working. Age-hardened Alloy 625 Plus shows mechanical properties
better than Alloy 718 with equivalent ageing treatment.
References
1. Frank RB, DeBold TA (1986) Custom age 625 PLUS—A new age-hardenable, corrosion-
resistant alloy. In: ASM materials conference, Orlando
2. Frank RB, DeBold TA (1988) Properties of an age-hardenable, corrosion-resistant, nickel-based
alloy. Mater Perform 27:59–66
3. Frank RB, DeBold TA (1990) Heat treatment of an age-hardenable, corrosion-resistant alloy—
UNS NO7716. In: Paper No. 59, NACE corrosion conference, Las Vegas, NV
4. Cieslak MJ, Headley TJ, Frank RB (1989) Welding metallurgy of custom age 625 PLUS alloy.
Weld J (Miami, FL) 68
5. Frank RB (1991) Customage 625 plus alloy—a higher strength alternative to alloy 625. Loria
EA (ed) Superalloys 718,625 various derivative
6. Frank RB, DeBold TA, Widge S, Martin JW (1996) Corrosion resistant age hardenable nickel-
base alloy. US Patent no. 5556594
7. Data Sheet Custom Age 625 PLUS. https://f.hubspotusercontent20.net/hubfs/7407324/Mat
erial%20Saftey%20Data%20Sheets/625%20Plus.pdf; Data Sheet Custom Age 625PLUS alloy
8. Vander Voort G, Bowman JW, Frank RB (1994) Microstructural characterization of Custom
Age 625 Plus alloy. https://doi.org/10.7449/1994/Superalloys_1994_489_498
9. Data Sheet Inconel alloy 625, Special Metals Corporation (2013) https://www.specialmetals.
com/documents/technical-bulletins/inconel/inconel-alloy-625.pdf
10. Data Sheet HAYNES ® 625 alloy, HAynes International (2020) https://www.haynes
intl.com/docs/default-source/pdfs/new-alloy-brochures/high-temperature-alloys/brochures/
625-brochure.pdf?sfvrsn=967229d4_26#:~:text=HAYNES%C2%AE%20625%20alloy%
20(UNS,other%20solid%2Dsolution%20strengthened%20alloys.
11. Data Sheet Inconel alloy 718, Special Metals Corporation (2007) https://www.specialme
tals.com/documents/technical-bulletins/inconel/inconel-alloy-718.pdf; Special Metals Corpo-
ration, Publication No. SMC-045
12. Frank RB, Grimes R (1994) Properties of ultra-high-strength Custom Age 625 Plus alloy.
Superalloys. 718:625–706
13. Onyewuenyi OA (2012) Alloy 718: alloy optimization for applications in oil and gas production.
345–362. https://doi.org/10.7449/1989/superalloys_1989_345_362
14. Yu LJ, Marquis EA (2019) Precipitation behavior of alloy 625 and alloy 625 plus. J Alloys
Compd 811:151916. https://doi.org/10.1016/j.jallcom.2019.151916
15. Cozar R, Pineau A (1973) Morphology of y and y precipitates and thermal stability of inconel
718 type alloys. Metall Trans 4:47–59. https://doi.org/10.1007/BF02649604
16. Detor AJ, DiDomizio R, Sharghi-Moshtaghin R, Zhou N, Shi R, Wang Y, McAllister DP, Mills
MJ (2018) Enabling large superalloy parts using compact coprecipitation of γ and γ . Metall
Mater Trans A 49:708–717
17. Miller MK (2001) Contributions of atom probe tomography to the understanding of nickel-
based superalloys. Micron 32:757–764. https://doi.org/10.1016/S0968-4328(00)00083-4
18. Theska F, Stanojevic A, Oberwinkler B, Ringer SP, Primig S (2018) On conventional versus
direct ageing of Alloy 718, Acta Mater 156:116–124. https://doi.org/10.1016/j.actamat.2018.
06.034
19. Shi R, McAllister DP, Zhou N, Detor AJ, DiDomizio R, Mills MJ, Wang Y (2019) Growth
behavior of $γ$ /$γ$ coprecipitates in Ni-base superalloys. Acta Mater 164:220–236
20. Sundararaman M, Mukhopadhyay P, Banerjee S (1992) Some aspects of the precipitation of
metastable intermetallic phases in INCONEL 718. Metall Trans A 23:2015–2028. https://doi.
org/10.1007/BF02647549
21. Gardner H, Pedrazzini S, Douglas JO, De Lille D, Moody MP, Bagot PAJ (2019) Atom probe
tomography investigations of microstructural evolution in an aged nickel superalloy for exhaust
applications. Metall Mater Trans A 50:1862–1872. https://doi.org/10.1007/s11661-018-5098-x
22. Floreen S, Fuchs GE, Yang WJ (1994) The metallurgy of alloy 625. In: Superallovs 718, 625,
706 various derivative. The Minerals, Metals & Materials Society, Pittsburgh, PA, USA, pp
13–38
23. Drexler A, Oberwinkler B, Primig S, Turk C, Povoden-Karadeniz E, Heinemann A, Ecker W,
Stockinger M (2018) Experimental and numerical investigations of the γ and γ precipitation
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03.013
24. Lawitzki R, Hassan S, Karge L, Wagner J, Wang D, von Kobylinski J, Krempaszky C, Hofmann
M, Gilles R, Schmitz G (2019) Differentiation of γ - and γ -precipitates in Inconel 718 by a
complementary study with small-angle neutron scattering and analytical microscopy. Acta
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25. Kuehmann CJ, Voorhees PW (1996) Ostwald ripening in ternary alloys. Metall Mater Trans A
27:937–943. https://doi.org/10.1007/BF02649761
Chapter 6
Fabrication
Superalloy ingots are usually fabricated into sheets, bars, tubes, and various other
wrought products and shapes. Standard fabrication techniques involve casting, metal-
forming, machining, welding, etc. Some superalloys of highly alloyed compositions,
like IN-100, Rene 95, Stellite 31, etc. or oxide-dispersion strengthened alloys that
are difficult or impractical to fabricate by the conventional techniques are gener-
ally processed into wrought shapes by powder metallurgy processing. Advance-
ments in powder metallurgy and laser technologies have evolved a new approach
commonly known as “additive manufacturing” as an alternative to conventional fabri-
cation. The significant advantage of additive manufacturing is it lowers the produc-
tion cost by reducing the input weight of expensive raw materials and the number
of secondary machining operations. This chapter gives an overview of essential
fabrication techniques used to fabricate Alloy 625 products.
6.1 Hot Forming of Metals
Forming of metals and alloys refers to the processes involved in their plastic deforma-
tion to affect changes to achieve desired shape and properties. When the deformation
is performed at a temperature above which recrystallization occurs, the process is
termed as “hot working”. Deformation at low temperatures is called “cold working”.
Hot-working allows imparting large deformation in successive steps because the
metal remains soft and ductile, requiring less deformation energy. But, most metals
experience some surface oxidation that results in metal loss and a poor final surface
finish. The strain accumulated during hot deformation is removed by recrystallization
of the grains. On the other hand, cold-working operations work hardens the material
and significantly reduce ductility. Yet, cold-working produces the finished product
with a closer dimensional control and a higher quality surface finish.
https://doi.org/10.1007/978-981-19-1562-8_6
190 6 Fabrication
Hot-working is usually done at temperatures above about 0.5T m (T m is melting

temperature in Kelvin). Most hot working operations involve forging, rolling, extru-
sion or drawing, which differ in how they impose stress on the workpiece. During
forging, the shape change is achieved by applying successive blows or continuous
squeezing. Forged products have outstanding grain structures and the best combina-
tion of mechanical properties. Rolling is usually used for reducing thickness under
compressive stresses when a piece of metal is passed between two rolls. In an extru-
sion process, a metal bar is forced through a die orifice to reduce its cross-section
by a compressive force applied through a ram. On the other hand, a metal piece in a
drawing operation is pulled through the die with a tapered bore, using a tensile force
applied on the exit side. These techniques have inherent limitations and advantages,
as well as the ability to produce specific products.
The main objectives of all hot forming processes are to optimize properties of the
alloy in all sections of the component by achieving (i) uniform grain refinement; (ii)
control of second-phase particles; (iii) controlled plastic flow; (iv) structurally sound
components. A necessary requirement of successful operations of all hot deformation
processes is the uniform flow of the metal and the complete recrystallization of
grains of desired size. The nonuniform or inhomogeneous flow of the metal may
lead to failure. Recrystallization of grains is required to obtain the strain-free grains.
6.1.1 Rate Controlling Phenomenon
A crystalline material starts deforming plastically when the shear stress due to the
applied force reaches a value above the yield stress. At elevated temperatures, dislo-
cations overcome obstacles under the combined applied stress and thermal energy.
When the external stress is low, the energy required to overcome the barriers (activa-
tion energy) comes from the thermal energy, and the thermally activated climb alone
dominates the deformation. At high temperatures, the lattice-diffusion controls the
climb of dislocations for which the activation energy is high. In contrast, the diffusion
through the dislocation’s cores controls the climb at low temperatures for which the
activation energy is less. The influence of the stress (σ ) and temperature on the strain
rate (ε̇) can be represented by a constitutive equation of the type [1]
ε̇ = A[sinh(ασ )]n exp(−Q/RT) (6.1)
where A and α are material constants, α is the stress multipliers, Q is the deformation
activation energy, R is the universal gas constant, T is the absolute temperature, and
n is the stress exponent. In principle, A and Q are independent of temperature, but
their independence is restricted to the temperature range of no phase transformation.
Dislocation climb plays a significant role in the plastic flow of the material at high
temperatures. Even though dislocation glide produces almost all the plastic strain,
the climb controls their velocity at high temperatures because climb allows them to
6.1 Hot Forming of Alloy 625 191
surmount obstacles whenever they obstruct the glide. The mechanism that controls
the climb process is governed by the Power-law creep (Eq.4.19, Chapter 4). At high
temperatures (≥ 0.6 T M ), the deformation may be accompanied by repeated waves
of recrystallization [2]. Each wave removes or drastically changes the dislocation
substructures allowing a period of primary creep so that the strain rate oscillates
at a constant load. At higher strain rates and temperatures, the power-law breaks
down when a recovery process different from that of the climb-controlled creep
occurs. When the power-law breaks down, the activation energy may exceed that of
the self-diffusion.
Though hot working shares many commonalities with a creep phenomenon, it
differs significantly from creep because of:
(i) the stress, which is a function of both strain rate and strain, unlike in creep
where it is a function of strain rate only;
(ii) the strain rate or the total energy of deformation controls the stress applied,
which can vary with the strain, unlike in creep, where a fixed stress is applied.
(iii) much higher strain rates during hot working (typically 10−3 to 103 s-1 )
compared to that in creep (~ 10−8 to 10−5 s-1 ), which results in higher flow
stresses, and in turn, alters microstructure significantly;
(iv) the working stresses are relatively high in hot working.
6.1.2 Microstructural Changes during Hot Deformation
The alloy undergoes dynamic recovery or recrystallization of grains during hot

working. Recovery refers to removing work-hardening defects without disturbing
the high-angle grain boundaries. In contrast, recrystallization refers to forming new,
strain-free grains from the existing deformed grains containing work-hardening
defects. The prefix “dynamic” refers to the recovery/recrystallization coinciding with
hot working. Figure 6.1 depicts the structural changes occurring during a typical hot-
working process. During hot-working, either dynamic recovery, or dynamic recrystal-
lization, or both may occur depending upon the stress and strain rates. For materials,
like Alloy 625, with a low or intermediate stacking fault energy, the dynamic recovery
process is slow as the low stacking fault energy resist the climb of dislocations. The
slow recovery process reduces the recovery rate, and grains attain a sufficiently high
density of dislocations within a short period to initiate dynamic recrystallization.
Immediately after hot working, the dynamic recovery is followed by static recrys-
tallization before quenching. This static recrystallization commences without any
incubation period, and dynamically recrystallized grains continue to grow at the
expense of uncrystallized grains [3]. This process is termed “meta-dynamic” recrys-
tallization. The meta-dynamic recrystallization is extremely quick and can cause the
rapid growth of recrystallized grains.
During dynamic recovery, the overall level of the flow stress increases with an
increase in the strain rate and decreases in temperature, or both, because of the build-
up of dislocation networks and small-angle grain boundaries till a steady state in
192 6 Fabrication
Fig. 6.1 A schematic illustrating the structural changes occurring during a typical hot-working
operation. Boundaries in black represent grain boundaries, while boundaries in red represent small-
angle boundaries that form due to the dynamic recovery process
the stress value is reached (σ ss ). The steady-state microstructure is characterized by

grains elongated in the primary direction of strain and contracted in other directions.
The substructure of these grains comprised equiaxed sub-grains whose size decreases
with increasing stress.
The material’s response during dynamic recrystallization depends upon the
temperature of deformation or the strain rate applied. At higher strain rates (or lower
temperatures), the overall flow stress level is higher than at lower strain rates (or
higher temperatures). At higher strain rates, the flow stress increases after yielding
till a maximum value (σ max ) is reached, after which the stress decreases and even-
tually attains a steady-state value (σ ss ). The dynamic recovery occurs until the σ max
is reached. The stress level drops after the σ max as dynamic recrystallization starts
dominating. On the other hand, at low strain rates and higher temperatures, the overall
level of the flow stress is less because of the dominance of the dynamic recrystalliza-
tion soon after yielding. In addition, the stress–strain curve may exhibit oscillatory
behavior, cycling above and below an approximate steady-state stress, which tends
to dampen out at larger strains.
The difference in the flow stress behavior is the manifestation of the development
of different substructures during dynamic recovery and recrystallization. For recrys-
tallization to begin, a critical dislocation substructure needs to be developed within
a grain. Deformation at a high strain rate (and the correspondingly high stress) or
low temperature causes the heterogeneous distribution of deformation levels within
different grains. Because of the high strain rate (and higher stress), the time needed
to attain the critical structure is short for an individual grain. As a result, grains
possessing a well-developed substructure with a high density of dislocations recrys-
tallize while other grains continue to deform. This substructure is invariant to the
strain even though the structure within each grain is continuously changing. By the
time the deformed grains recrystallize, other grains accumulate sufficient disloca-
tions for recrystallization. Simultaneously, the dislocation density in just recrystal-
lized grains reaches a low value, continuing the process. This process of dynamic
recrystallization of some grains is stochastic but develops a steady-state structure
throughout the material volume. On the other hand, the deformation at low strain
rates, at a given time, is uniform with approximately the same substructure within all
grains throughout the material because the low strain rates provide sufficiently long
time and greater strain to accumulate the critical dislocation density within grains
to begin recrystallization. The uniform recrystallization reduces the stress levels to
deform the strain-free new grains. Thus the flow curve is characterized by oscillatory
stress where the accumulation of dislocations harden and the dynamic recrystalliza-
tion softens the flow. The repeated wave of recrystallization continuously removes or
drastically changes the dislocations substructures within the individual grain. Each
local minimum in the stress level represents the end of a recrystallization wave when
a low density of dislocations characterizes individual grains.
6.1.3 Hot Working of Alloy 625
The hot deformation behavior of Alloy 625 has been studied by different research
groups over the temperature range of 900–1200 °C at constant strain rates ranging
from 0·001 to 80 s−1 [4–9]. Experimental details of individual work are listed in Table
6.1. The flow stress behavior of the alloy compares well among different groups and
follows typically a thermally induced behavior discussed above. The flow stress
increases with increasing strain rate and decreasing temperature. An increase in
Table 6.1 Experimental details of hot deformation experiments and the kinetic parameters
estimated during studies on hot deformation of Alloy 625
Authors Temperature Strain rate α (MPa−1 ) A (s−1 ) Q (kJ/mol) n Reference
range (°C) range (s−1 )
Lopez 950–1150 0.17–5.3 0.0036 2.65 × 400 4.0 [4]
and 1015
Urcola
Zhou 950–1150 0.001–5 0.0044 1.05 × 421 3.92 [6]
et al. [6] 1015
Jia et al. 900–1200 0.01–10 0.0033 5.82 × 474 4.87 [8]
[8] 1017
Sun 950–1200 0.1–80 0.0023 1.35 × 680 7.65 [7]
et al. [7] 1018
194 6 Fabrication
the strain rate at low temperatures results in flow softening. A fully dynamically
recrystallized microstructure is achieved at a temperature above 1050 °C.
Figure 6.2 shows the typical flow behavior of Alloy 625 at temperatures above
950 °C for strain rates between 0.1 and 5.5. The alloy achieves steady-state flow
stress at strains between 1 and 1.5 [4, 9]. Figure 6.3 shows the variation of the peak
stress with temperature and strain rate. The peak stress increases with decreasing
temperature and increasing strain rate. The amount of strain is uniquely related to
the peak flow stress, which increases with decreasing temperature and increasing
strain rate. This behavior is similar to many other alloys ([for example, Alloy 718
[10], Alloy 693 [11]) and is attributed to an increase in grain boundary mobility
and a decrease in the critical dislocation density for dynamic recrystallization with
increasing temperature, resulting in a reduction of the peak strain [9]. An increase
in the strain rate has the opposite effect. All the authors in Table 6.1, except Sun
Fig. 6.2 Stress–strain flow curves of Alloy 625 as a function of temperature and strain rates: a at
a fixed temperature of 1100 °C; b at a fixed strain rate of 0.52 s−1 [4]
Fig. 6.3 Dependence of

peak flow stress on the
temperature at a given strain
rate [4]
et al. [7], reported similar kinetic behavior of the alloy during hot deformation and
estimated the values of Q in the range 400–474 kJ/mol and n in between 3.9 and 4.9,
indicating that the climb-plus-glide power-law creep controls the hot deformation
behavior of Alloy 625. Table 6.1 also lists the kinetic parameters (Eq. 6.1) estimated
by these authors. However, the power-law mechanism appears to break down under
the processing conditions used by Sun et al. [7], as indicated by high values of the Q
and n. The breakdown of the power-law mechanism is possible due to the high strain
rate, which requires higher stress for deformation.
The fraction of dynamically recrystallized grains increases with temperature. The
alloy exhibits nearly complete recrystallized microstructure at temperatures above
1050 °C. At lower temperatures, the recrystallization is usually incomplete. The
size of the dynamically recrystallized grain, d rex , is related to fracture stress σ f by a
−0.75
relationship given by σ f ∝ drex [4].
For a given strain rate, the alloy exhibits maximum ductility at temperatures
between 1050 and 1100 °C, followed by a rapid decrease at higher temperatures
(Fig. 6.4). An increase in the strain rate decreases the ductility and shifts the ductility
maxima to lower temperatures. This strain rate effect on the ductility is consistent with
other superalloys [12]. McQueen et al. [12] have associated the highest ductility to the
optimum conditions for the occurrence of significant recovery and recrystallization
without encountering grain growth. Low ductility at lower temperatures is attributed
to increased work-hardening and the material’s inability to recover or recrystallize
dynamically. On the other hand, the reduced ductility at temperatures above 1100 °C
is due to the grain coarsening effect. At much higher temperatures, close to the
incipient melting, the synergistic effects of grain coarsening and grain boundary
embrittlement appear to reduce the ductility further [12].
Fig. 6.4 Variation in

ductility of Alloy 625 with
the temperature at a given
strain rate [4]
196 6 Fabrication
6.2 Heat Treatments
Heat treatment refers to heating or cooling the alloy to obtain desired properties
by removing internal stress, changing microstructure, precipitating or dissolving
the second-phase particles. Heat treatment of nickel-based alloys is typically
performed in reducing atmosphere. The terminology of different heat treatments
may vary among shop floors, but the purpose remains mostly the same, as noted in
this section. This section briefly describes various heat treatments Alloy 625 may
undergo during processing or fabrication. Representative annealing temperatures,
holding times, and cooling procedure for Alloy 625 are listed in Table 6.2 [13].
Primary carbides in the alloy are usually not affected by any heat treatment though
some dissolution may occur during the homogenization treatment.
6.2.1 Types of Heat Treatments
6.2.1.1 Stress Equalizing Treatment
Stress equalizing treatment balances stresses in work-hardened alloys. It is a low-

temperature heat treatment, usually in the temperature range of 260–370 °C [1]. Stress
equalizing is by partial recovery of the cold-worked material without detectable
microscopic structural changes. This treatment results in a slight increase in the
hardness, yield strength and tensile strength with little change in the ductility.
6.2.1.2 Stress Relieving Treatment
Stress-relieving treatment reduces stresses in the work-hardened alloy without

producing a recrystallized grain structure. This treatment removes more internal
stresses than are released by the stress equalizing treatment without appreciably
decreasing the strength. The stress-relieving temperature is usually below the
annealing temperature. The typical stress relieving temperature for Alloy 625 is
Table 6.2 Typical heat

Heat treatment Temperature a (°C) Time b (h)
treatment temperatures for
Alloy 625 [13] Stress relieving 870 1
Annealing 980 1
Solution annealing 1150 2
a To provide an adequate quench after the treatment, it is necessary
to cool below about 600 °C rapidly enough to prevent sensitization
of the alloy
b Holding time per inch of section
6.2 Heat Treatments 197
about 870 °C (Table 6.2). However, it may vary depending on the alloy’s microstruc-
ture and the magnitude of stresses accumulated during thermo-mechanical treatment.
Stress-relieving requires careful control of time and temperature. The stress-relieving
treatment may cause slight decreases in yield strength, tensile strength and hardness,
and a slight increase in elongation.
6.2.1.3 Annealing Treatment
Annealing refers to a heat treatment at a suitable temperature, followed by cooling at

a suitable rate. An annealing treatment is given to soften a work-hardened material.
The treatment is used to increase alloy’s ductility for forming or machining, relieve
stresses before and after welding and simultaneously produce other desired proper-
ties and changes. The treatment involves alloy’s exposure to an elevated tempera-
ture to cause recrystallization of the work-hardened microstructure. Recrystalliza-
tion removes all the stresses and softens the material but decreases the mechanical
strength. The typical annealing temperature for Alloy 625 is about 980 °C (Table
6.2). However, it may vary considerably as the recrystallization temperature depends
on time, temperature, and the amount of cold work. Figure 6.5 illustrates a typical
variation in the recrystallization temperature of Alloy 600 with the amount of cold
work [14]. The annealing time and temperature of the alloy must be controlled care-
fully. Otherwise, grain growth may occur if the temperature and time exceed those
required for recrystallization.
Alloys with coarse grains are less desired for many cold-forming operations and
service conditions requiring good fatigue strength. If grains coarsen, a repeat of
Fig. 6.5 Variation in the recrystallization temperature of Alloy 600 with percentage cold work [14]
198 6 Fabrication
Fig. 6.6 Grain size of a hot

rolled Alloy 625 annealed at
different annealing
temperatures for 10 min [15]
the cold working, followed by a recrystallization treatment on the alloy is the only
solution to produce a fine-grained structure. The average grain size of Alloy 625 does
not change significantly when the alloy is annealed for 10 min at temperatures up
to 1000 °C (Fig. 6.6) [15]. The grain size increases at temperatures above 1000 °C
as the grain boundary carbides dissolve above this temperature. Above 1100 °C,
the grains grow considerably. The beginning of the grain growth at temperatures
above 1000 °C coincides with the maximum temperature (1040 °C) up to which
carbides are stable (Sect. 3.2.5 and 3.5.4). Sometimes, imprecise terms like “final
annealing” and “full annealing” are used to describe specific annealing conditions.
“Final annealing” refers to the last annealing treatment given to the alloy before the
shipment. “Full annealing” refers to the annealing cycle that produces alloy with
entirely recrystallized microstructure and the lowest hardness and strength.
6.2.1.4 In-Process Annealing Treatment
Cold working markedly increases the strength and lowers the ductility of the alloy.
Therefore, imparting a high cold working often requires intermediate annealing oper-
ations. The intermediate annealing reduces the stress and improves ductility for
adequate formability of the metal. However, the in-process annealing temperatures
may vary widely depending on working operations. Even during hot working, most
nickel-based superalloys begin to accumulate defects, particularly toward the final
stages of deformation, that are removed by intermediate heating the alloy for subse-
quent deformation. Similar in-process annealing treatments are required even during
multistep forging, except for isothermal operations. The heat supplied to maintain the
constant temperature is sufficient to cause the annealing of the forged alloy simulta-
neously with forging. In general, in-process annealing is usually done for complete or
nearly complete recrystallization of grains and the dissolution of all or most secondary
phases. However, temperature control is critical when varying degrees of recrystal-
lization are desired during the final stage properties. The in-process annealing is
restricted to temperatures that do not dissolve all secondary phases but retains some
to pin the grain boundaries to limit the grain growth during the final steps of the
desired product.
6.2.1.5 Solution Annealing Treatment
The solution annealing temperature is higher than the annealing temperature. Solu-
tion heat treatment refers to heating an alloy to a suitable temperature and holding
for a time that causes the dissolution of one or more of the “second-phase” particles
into the matrix solid solution. A solution heat treatment is followed by cooling the
alloy rapidly enough to retain the constituents of the dissolved phases in the solid
solution. The solution annealing aims to produce a fully disordered microstructure
for maximum corrosion resistance or prepare the alloy for subsequent aging. The
typical solution annealing temperature for Alloy 625 is carried out at about 1150 °C
(Table 6.2). A higher solution treating temperature will result in grain growth in
wrought alloys.
Solution annealing treatment is sometimes confused with the “full annealing”
treatment. The two treatments appear identical but are distinguished based on their
purpose. Solution treating intends to dissolve the second-phase precipitate parti-
cles and applies to age-hardened materials. In contrast, full annealing refers to the
annealing cycle that produces the fully recrystallized microstructure.
6.2.1.6 Homogenization Treatment
Homogenization treatment eliminates or decreases chemical segregation by diffusion

when the alloy is heat treated at temperatures above the solution annealing tempera-
ture. However, the homogenization temperature must be restricted below the alloy’s
incipient melting temperature. The incipient temperature is governed by equilibrium
and non-equilibrium phases formed by segregating elements during solidification.
The incipient melting temperature of Alloy 625 is 1288 °C and its homogenization are
recommended at about 1200–1250 °C. The inhomogeneity level decides the period
of homogenization. However, homogenization becomes increasingly uneconomical
with a temperature above 1200 °C. The homogenization is explicitly done on the
cast structures where thermo-mechanical processing is impossible.
200 6 Fabrication
6.2.1.7 Precipitation/Age-hardening Treatment
Precipitation treatments are intended to precipitate desirable strengthening phases

from the supersaturated matrix and control carbide phases. Unlike other heat treat-
ment temperatures mentioned above, selecting the precipitation temperature and
periods for a given alloy may vary significantly, depending on the size, distribution,
volume fraction, and density of precipitating phase particles. When more than one
phase precipitates from the matrix, as in Alloy 625, judicious selection of an aging
temperature is essential.
As per the design of the alloy, Alloy 625 is a solid-solution strengthened alloy.
However, as noted in Chaps. 3 and 4, precipitation of various hardening phases
occurs at intermediate temperatures. These phases precipitate out homogeneously as
sub-microscopic particles throughout the grains and cause a substantial increase in
the hardness and strength. Precipitation reactions and their temperature range for the
formation of various phases in Alloy 625 are summarized in Table 6.3. Unlike many
γ strengthened alloys, such as Alloy 693 [16], precipitation of the hardening phases
in Alloy 625 is delayed because of their large incubation periods. Nonetheless, their
incubation time and precipitation temperature can be reduced by deforming the alloy
before precipitation (Sect. 3.4).
6.2.2 Prevention of Contamination
Like other nickel alloys, Alloy 625 is also susceptible to embrittlement by sulfur,
phosphorus, lead, zinc, and other low melting-point or eutectic forming elements.
These elements may be present in lubricants, marking crayons and inks, paints,
pickling liquids, dirt accumulated on the alloy during storage, furnace slag and cinder,
or temperature-indicating sticks, pellets, lacquers, etc. It is therefore important that
the alloy be cleaned before heating. In addition, the alloy must be protected from
Table 6.3 Precipitation

Temperature range Precipitation reaction Aging duration
sequence of different
intermetallic phases in Alloy T ≤ 600 °C γS → Prolonged aging
625 γ + Ni2 (Cr, Mo)
600 °C < T ≤ 650 °C γ S → Prolonged aging
γ +Ni2 (Cr, Mo)+γ
650 °C < T < 750 °C γ S → γ + γ Short aging
650 °C < T < 750 °C γ S → γ + γ + δ Prolonged aging
750 °C < T < 800 °C γ S → γ + γ + δ Short aging
750 °C < T < 800 °C γ S → γ + δ Prolonged aging
T > 800 °C γS → γ + δ Short aging
γ S Refers to supersaturated γ phase
contamination while in the furnace by placing in metal baskets or on a metal floor,

trays, rider bars or any other material that avoid the alloy’s direct contact with the
refractory heart.
6.2.3 Fuels
In general, gaseous fuels are preferred for heating nickel-based alloys because of: (i)
their high calorific values and good heating; (ii) their easy mixing with air; (iii) better
control of their supply. However, any low sulfur gaseous and oil fuel or electricity can
be used to heat Alloy 625. Natural gas is the best fuel as it is free of sulfur compounds
and primarily contains methane and smaller amounts of ethane, propane, and butane.
Manufactured gases produced from coal or oils may contain substantial amounts of
sulfur. Manufactured gases should, therefore, be used only after reducing their sulfur
compounds to an acceptable level. Oil is a good fuel for heating the alloy if its sulfur
content is not more than 0.5% by weight of sulfur [14]. When the use of a high-
sulfur fuel cannot be avoided, the detrimental effect of sulfur can be minimized by
maintaining a slightly oxidizing atmosphere of the furnace. However, this may cause
some oxidation of the alloy surface. Solid fuels like coal and coke are not preferred
because of their excessive sulfur content, comparatively low calorific values and poor
heating control.
6.2.4 Protective Atmosphere
A protective atmosphere for annealing is required for all materials to maintain a

reducing environment for a bright surface of the annealed alloy. Protective atmo-
spheres of helium, nitrogen or dissociated ammonia gas is generally used for treating
nickel-based alloys. However, these gases must be dry for the bright finish of the heat-
treated surface. Water vapor present in gases decomposes into hydrogen and oxygen
at high temperatures when they come into contact with hot metal surfaces. The
oxygen produced oxidizes the surface resulting in the loss of brightness. Therefore,
the water content in gas must be reduced to an acceptable level.
Dew point gives a measure of the moisture in natural gases. Dew point is the
temperature and pressure at which the first drop of the water vapor condenses into
a liquid. With a decrease in the amount of water vapor, the dew point of the gas
decreases. At lower temperatures, lower dew points are required.
Chromium, molybdenum and niobium are the main oxides forming elements in
Alloy 625. The best protective atmosphere for Alloy 625 is a dry 100% hydrogen
environment. If the hydrogen is prepared by catalytic gas reactions instead of elec-
trolysis, residual hydrocarbons, such as methane, must be limited to about 50 ppm to
prevent carburizing [14]. The significance of the dew point of the gas in controlling
the oxidation of the surface can be understood considering the oxidation behavior
202 6 Fabrication
Fig. 6.7 The metal/metal oxide equilibria of chromium, molybdenum and niobium in hydrogen
atmospheres as a function of temperature and dew point [14]
of chromium in a 100% hydrogen atmosphere. Figure 6.7 shows the metal/metal-

oxide equilibria of chromium, molybdenum and niobium elements in hydrogen atmo-
spheres as a function of temperature and dew point. The area on the left of each curve
is the oxidized condition, and on the right is the reduced condition. At a temperature
of 1100 °C, a dew point of less than −30 °C of the hydrogen gas is required to
reduce chromium oxide to chromium. For example, at 800 °C, the dew point must
be below −50 °C. Though this dew point is for the chromium element, the same
would avoid molybdenum oxidation also because of its higher dew point. Though a
lower dew point of the gas is required to prevent niobium oxidation, it would play
an insignificant role due to niobium’s much lower concentration. Though these dew
point values are derived from the thermodynamic relationships of pure metals and
their oxides at thermal equilibrium, the same has been shown to work as a guide
to the oxidizing behavior of complex alloys under non-equilibrium conditions [14].
Therefore, a protective environment of 100% hydrogen gas of dew point −50 °C or
lower is required for bright annealing of Alloy 625. As the dew point decreases at
lower temperatures, the alloy must be cooled rapidly in the protective atmosphere
to minimize its oxidation during cooling. Environments like nitrogen or dissociated
ammonia may not protect Alloy 625 adequately because it tends to form nitride.
It is important to note that the protective atmosphere of hydrogen within the
heating chamber or the furnace must be maintained at a positive pressure throughout
heating and cooling. Hydrogen forms explosive mixtures with air over a wide range of
compositions. Any infiltration of the air at high temperatures may cause severe fires or
explosions. The same precautions are also required while preparing the atmosphere
for heat treatment. The chamber must be thoroughly purged with an inert gas to
remove all air before heating.
6.3 Machining 203
6.3 Machining of Alloy 625
6.3.1 Conventional Machining
The machining behavior of Alloy 625 in conventional machining processes is

governed by its rapid work-hardening characteristics (Sect. 4.5.1). The machining
properties are similar to those of other nickel-base alloys like Inconel 901, 900, 617,
706, 718, X 750, Nimonic 75 and 80 A, Waspaloy, etc. [17].
During the machining process, intense friction is generated at the tool-workpiece
interface. This friction causes localized severe plastic deformation of the workpiece
and generates excessive heat. This heat coupled with work-hardening may cause
debonding of the tool substrate. Debonding of the tool may lead to machining related
failures like poor surface finish, excessive tool wear, frequent tool change, produc-
tivity loss, high power consumption, etc. all of which makes machining of the Alloy
625 less economical. Moreover, the high pressures developed during machining
work hardens the alloy surface rapidly, which retards further machining. The work-
hardening produces stresses even under optimum machining conditions and, subse-
quently, may distort the workpiece, particularly parts with small cross-sections. High
temperature and mechanical stresses at the tip of the tool in contact with the hardened
machined surface layer may cause notch wear of both the flank and the rake of the
tool. The predominant mechanisms of wear during machining are abrasive and diffu-
sive [18]. Such wear may result in chipping, formation of the built-up edge (BUE)
and built-up layer (BUL) and even fracture the tool. An increase in the cutting speed,
cutting temperature or cutting depth tends to increase the tool wear rate. The tool’s
wear causes deterioration in the quality of the machined surface and increases the
surface roughness. Due to these limitations of Alloy 625, only a low cutting speed
is used in a chip-removing operation for acceptable machined surface quality and
reduced tool wear [19]. In addition, the machining of the alloy produces long and
continuous chips independent of the cutting conditions. Therefore, the machining
process has to be interrupted often to remove the long chips from the process zone.
Automatization of conventional machining is, therefore, rather difficult for Alloy 625.
Despite these limitations, conventional chip-making processes are often employed
because they offer much higher metal removal rates.
During machining, the work-hardening effects can be reduced by using work-
hardened and stress-relieved material or using sharp tools with positive rake angles.
Tools with a positive rake angle cut the metal instead of pushing it, as occurs with
the negative rake angle. For example, it is easier to machine the alloy in a hot-rolled
condition than an annealed one. Tools with positive rake angles help to avoid rubbing
the work. Hot machining is another approach to improve the machinability of Alloy
625. In hot machining, the machining is performed at a raised temperature, which
does not affect the material’s metallurgical properties [20]. The material may be
heated before or during the machining operation. Heating the material reduces its
shear strength and allow easy machining without affecting the metallurgical behavior
of the material [20]. Hot machining prevents material’s strain hardening, reduces the
204 6 Fabrication
cutting force and tool wear, and improves the material removal rate and the surface
finish.
Cutting fluids play an important role in machining operations. They reduce friction
and power consumption, chip removal, and cool and lubricate the cutting zone. These
benefits of cutting fluids improve the efficiency of chip removal operations. Other
benefits of cutting fluids include protecting the cutting tools from oxidation. Due
to these benefits, cutting fluids is vital during the turning operation of Alloy 625.
Almost all cutting fluids can be used in the machining of Alloy 625. Cutting fluids
also help in improving the cutting tool life. Another way to enhance the life of the
cutting tool is to select a suitable cutting tool geometry.
Judicious control of the cutting parameters helps reduce the limitation of Alloy
625 machining. The rake angle of the main tool’s cutting edge substantially affects
its notch wear. An angle of 45° evenly distributed the mechanical force in three direc-
tions, which improves the tool’s life [21]. Using the minimum quantity lubrication
(MQL) technique has also been shown to be quite effective in reducing the tool’s
wear when turning Alloy 625. In the MQL system, the cutting fluid/oil at an average
flow rate of 10–100 ml/h is mixed with air and sent to the tool-work region as an
aerosol [22]. The cutting oil provides lubrication, while the cooling is achieved by
the compressed air at high pressure.
Hacksawing of Alloy 625 is somewhat difficult by standard hand and power
hacksaw tools. Blades made of high-speed tool steel with 14 to 18 teeth per inch
(TPI) raker set may be used for general hand saw works. Blades with 24 to 32 TPI
wavy set are used for sawing thin-wall tubes. The band saw can be used to cut the
alloy sections to a certain thickness. A cutting speed of about 18 m/min can be used as
a guide for bandsawing the alloy using blades containing 32 TPI at medium feeding
pressures. The saw should constantly bite into the work; otherwise, the blade may
work harden the material. The blade and workpiece should be flooded with soluble
oil.
Cutting speed is most significant for the surface roughness parameter followed by
the feed rate. An increase in the cutting speed increases the surface roughness. The
depth of cut has an insignificant effect on the surface roughness [23]. The feed rate
and the depth of the cut affect the cutting force most, while the cutting speed has a
minor effect. A medium level of cutting speed (~ 75 m/min) is preferred for a good
surface finish (low roughness value and low peak-to-valley height) in the machining
of Alloy 625 using a TiAlN/TiN coated carbide tool. MQL also contributes to the
improvement of surface roughness. For maximum dimensional stability, it is best to
rough out the part almost to the size, stress relieve, and then finish it to the final size.
Stress-relieving remove stresses with little effect on dimensions which, in turn, ease
the final machining.
Conventional machining methods that are most commonly used are: turning,
grinding, milling and broaching. Other methods may include planning, drilling, screw
machining and tapping. Single point turning is the most frequently used machining
process for superalloys.
Carbide tools are recommended for uninterrupted cuts for most turning operations
and the high cutting rates. High-speed steel tools should be used for machining, like
6.3 Machining 205
Table 6.4 Typical machining parameters for different types of machining operations on Alloy
625[17] (sfm = surface feet per minute)
Machining operation Roughing speed Finishing speed Feed
m/min sfm m/min sfm mm/rev in/rev
Turning by HSS 8 20 8 25 – –
Turning by carbide brazed 15 50 27 90 – –
Turning by carbide indexable 18 60 30 100 – –
Drilling by twist drill 6 20 – – 0.04–0.1 0.002–0.004
Drilling by carbide gun drill 24 80 – – – –
Reaming by HSS 6 20 4.5 15 0.075–0.4 0.003–0.015
Reaming by carbide tools 12 40 8 25 0.075–0.4 0.003–0.015
Thread milling by HSS 6 20 – – 0.038 0.0015
roughening uneven surfaces. They are also used for cutting with the least work-
hardening and finishing operations to close tolerances and the smoothest surfaces.
Recommended feeds and speeds for everyday machining operations of Alloy 625
are given in Table 6.4 [17]. The centers of the ranges in Table 6.4 may be used as
starting points in establishing the best conditions for specific jobs.
Tapping of the alloy is recommended with serial taps using a surface speed in the
range of 1.5–3 m/min with 50% thread engagement. Serial taps are similar to standard
taps with modified diameters to increase the thread diameter proportionately with
each successive tap. Lathe tools for thread-cutting are ground as per the principles
of turning tools, but the angles on threading tools are kept smaller than those on
turning tools to support their small nose. Because of the limitation of the tool nose to
dissipate heat, threading using single-point tools must be done at lower speeds and
feeds than those used for turning. The threading speed for Alloy 625 is recommended
to be 0.9–1.1 m/min.
The essential requirements of milling are accuracy and a smooth finish. High-
speed tool steel sharp cutters and rigid machines and fixtures are recommended for
interrupted milling of Alloy 625. Recommended feeds and speeds for milling by
high-speed steel (HSS) cutters are also listed in Table 6.4. It must be ensured that
the feed should not be too light, like just rubbing the surface, as it may generate an
excessively work-hardened layer. Down milling is more advantageous for tool life
than conventional up milling because the cutting tool can withstand impacts better
than friction. In down milling, the cutting conditions that generated the lowest impact
energy favored tool life [18]. In addition, the downward motion of the cut assist
rigidity and reduces the chatter. Face milling is preferred to slab milling because the
former reduces the work-hardening and chatter. The chip problem and the tool wear
during milling of Alloy 625 are similar to those in a turning operation. A standard
milling cutter with adequate clearance for chips can be used for milling Alloy 625.
Aluminum oxide wheels or grinding belts are recommended for surface grinding
of Alloy 625. Rough grinding can be done dry, but a lubricant based on a machine oil
of high-flowing characteristic is recommended. For semi-finish and finish grinding,
206 6 Fabrication
cottonseed oil or a similar lubricant, with the addition of kerosene oil, may be used.
The addition of kerosene imparts a high-flowing characteristic to the oil.
Heavy-duty high-speed steel drills with a heavy web are recommended for drilling
Alloy 625 using steady feed rates. Care must be taken not to allow the drill to dwell
for long to avoid excessive work-hardening of the alloy at the bottom of the hole.
Excessive hardening may cause jamming of the drill, which would make it difficult to
resume cutting and may break the drill. Thinning the web at the chisel point reduces
the cutting pressures and maintain an effective positive rake angle. An increase in
the point angle to l35° is beneficial. Recommended speed and feed rates for drilling
by twist drill and carbide gun drill are given in Table 6.4.
Reaming should be done at about two-thirds the speed for drilling (Table 6.4).
Standard fluted reamers of high-speed tool steel characterized by the right-hand
cut positive axial rake (right-hand helix) and positive radial rake are recommended
for reaming of Alloy 625. The reamer feed should be 0.038–0.l mm per flute per
revolution. Too low a feed rate may glaze the workpiece and wear the tool excessively.
On the other hand, an excessive feed rate may reduce the accuracy of hole dimensions
and the quality of the finish. Conventional fluted reamers and flat solid reamers are
recommended for reaming the alloy. In addition, insert tools for built-up reamers
made of high-speed tool steel and composite tools having steel shanks tipped with
carbide can also be used. Speeds of about two-thirds of those turning with similar
tools and feeds of 0.20–0.25 mm/rev are recommended for starting the operation.
6.3.2 Hot Machining of Alloy 625
Hot machining of Alloy 625 may reduce many machining problems associated with
alloy work-hardening. It prevents strain hardening and improves machining and
surface finish. In hot machining, the material is heated before or during machining to
reduce its shear strength, allowing easy machining. Parida et al. [19] have studied the
effect of hot machining on various machining parameters of different nickel-based
superalloys and reported significant ease in the machining at elevated temperatures.
Table 6.5 gives the improvement across multiple machining parameters during hot
turning of Alloy 625 at 30, 300 and 600 °C, using a cutting speed of 100 m/min, a
feed rate of 0.13 mm/rev and 0.3 mm depth of cut. The hot machining significantly
enhances the tool life, apparently due to the softening of the alloy and hard carbide
particles that cause abrasive wear by exerting more pressure on the tool during the
cutting operation. The alloy machined at high temperatures exhibits a softened thin
layer beneath the machined surface. Alloy’s hardness beneath the machined surface
decreases with an increase in the machining temperature due to the annealing of the
defects. However, it increases beyond a certain distance away from the surface due to
strain hardening. Machining at much higher temperatures may cause grain growth,
as reported at 600 °C [19, 24]. The chip morphology changes from discontinuous
and helical at room temperature to continuous and spiral at elevated temperature
(Fig. 6.8).
6.3 Machining 207
Table 6.5 Change in the tool

Parameter Change (%)
life, cutting force, feed force,
radial force and surface finish Tool life + 238
of the machined alloy during Cutting force − 29
hot machining of Alloy 625 at
Feed force − 28
600 °C compared to those at
30 °C, when machined using Radial force − 36
a cutting speed of 100 m/min, Surface roughness − 42
feed rate of 0.13 mm/rev and
0.3 mm depth of cut. “+” and
“− ” refer to an increase and
decrease in the parameter
Fig. 6.8 The morphology of chips formed during hot machining of Alloy 625. Reprinted from
[19], Copyright (2018), with permission from Elsevier
6.3.3 Non-conventional Machining
Most conventional means of improving machinability are not effective with Alloy 625
and most other superalloys. Several non-conventional, electrically assisted machining
techniques have evolved, which are more effective in shaping superalloys than by
conventional methods. These techniques are termed “non-conventional” because they
do not employ conventional tools for metal cutting. Instead, they directly utilize the
machining energy for machining. The machine energy may be mechanical, elec-
trochemical, chemical, or thermoelectric. Some non-conventional machining opera-
tions are electrical discharge machining (EDM), electrochemical machining (ECM),
photochemical machining (PCM), electron-beam machining, laser beam machining
and plasma-arc cutting. Some of them even supplement the conventional machining
practices for the alloy. Some of the advantages of non-conventional techniques
include high accuracy of machining, no tool wear, no burrs, good surface finish and no
stresses on the worked surface. However, advantages like no stresses may be attended
with disadvantages for some applications compared to conventional machining. For
example, ECM of a nickel-base superalloy after conventional turning reduces the
fatigue endurance stress capability by about 50% because the conventional turning
introduces favorable compressive stresses on the machined surface. However, all the
208 6 Fabrication
non-conventional techniques are limited by the low metal removal rates. Of the non-
conventional machining techniques, electric discharge machining (EDM) is the most
effective machining to overcome the constraints of the conventional processes and
can machine all sorts of difficult to machine tough and hard electrically conductive
materials.
6.3.3.1 Electric Discharge Machining
Electrical discharge machining is an electro-thermal process in which material is

removed from the workpiece by a series of continuous sparks between the tool
(wire) and the workpiece. There is no mechanical contact between the wire and the
workpiece in EDM. The gap between the wire and the workpiece usually ranges
from 0.025 to 0.050 mm and is continuously maintained by a computer-controlled
positioning system. De-ionized water floods the gap between the wire and the work-
piece. The de-ionized water acts as a dielectric and flushes the eroded particles. The
material removal mechanism is based on the melting and evaporation of materials
by a series of electrical discharges (or spark erosion) by voltage pulses generated
by a pulse generator. The electrode (a thin wire of diameter ranging from 0.05 to
0.35 mm) continuously moves on a spool, feeds through the workpiece, and wound
on a second spool. The wire electrode may be copper, brass or zinc coated. The wire
is kept straight by a mechanical tensioning device and is fed into the workpiece by
a numerically controlled mechanism or a microprocessor.
Several workers have demonstrated satisfactory machining response of the EDM
for material rate removal, cutting speed, optimum surface roughness and economical
cutting of Alloy 625 and many other superalloys [25–27]. Table 6.6 gives typical
machining parameters for optimum cutting speed and low surface roughness of Alloy
625 [27]. Singh and Singh [28] have demonstrated the effect of peak current (I P ),
pulse on time (T on ), wire feed rate, and wire tension on the performance of material
removal rate and surface roughness during EDM of Inconel 625. They have concluded
that T on time is the most controllable influential factor, followed by peak current,
wire feed rate, and wire tension.
Table 6.6 Optimum EDM machinability parameters for cutting speed and low surface roughness
of the machining of Alloy 625 [27]
Parameters High cutting speed Minimum Ra Both high cutting speed and minimum
Ra
Wire tension 10 N 10 N 10 N
Wire speed 110 mm/s 305 mm/s 305 mm/s
Flushing pressure, 16 kg/mm2 8 kg/mm2 16 kg/mm2
Discharge current 7A 7A, 21 A,
Spark time on (T on ) 28 μs 14 μs 28 μs
6.3 Machining 209
Garg et al. [26] have studied the effect of pulse on time, pulse off time, spark gap
voltage (SV) and wire feed (WF) parameters on cutting speed (CS), gap current (I g ),
and surface roughness (Ra ) of the machined surface. An increase in T on from 0.85 to
1.35 μs increases the cutting speed by about 80%. On the contrary, a decrease in T off
from 36 to 18 μs increases by 85%. The cutting speed increases marginally with a
decrease in the SV. Garg et al. achieved a maximum cutting speed of 1.27 mm/min
with parameters T on = 1.35 μs, T off = 18 μs, SV = 45 V, and WF = 5 m/min.
6.3.3.2 Electrochemical Machining
Electrochemical machining (ECM) removes metal by an electrochemical process. It

involves electrolytic “deplating” or “reverse electroplating” of the workpiece [29]. A
high current is passed between the workpiece (anode) and a tool (cathode) through
a conductive fluid (electrolyte) to selectively dissolve (machine) the workpiece
submerged in the electrolyte by the electrochemical reaction of the type.
M = M2+ + 2e− (6.2)
where M refers to the metal of valency 2. The electrons (e− ) lost by the dissolution of
M atoms travel to the cathode, where it reacts with water molecules forming gaseous
hydrogen and hydroxyl ions (anions) as per the reaction
H2 O + 2e− = H2 + 2OH− (6.3)
The cations and the anions react in the aqueous solution to form insoluble metal
hydroxide
M2+ + 2OH− = M(OH)2 (6.4)
The flowing electrolyte removes the insoluble hydroxide.

During ECM, the tool is moved into the workpiece at the machined area, and
the pressurized electrolyte is injected at a set temperature. The gap between the
tool and the workpiece typically varies within 80–800 μm [30]. As electrons cross
the gap, material from the workpiece is dissolved, as the tool is guided along the
desired path close to the work. No tool wear occurs in ECM [30] because the cutting
tool does not touch the workpiece. For nickel alloys, salt solutions of sodium or
potassium nitrate or chloride or dilute sulfuric acid may be used as electrolytes. The
high corrosion resistance of Alloy 625 does not seem to retard its electrochemical
dissolution. However, alloy’s high corrosion resistance may cause a voltage drop
during ECM and necessitate higher power and electrolyte heating. The ECM can
be used for machining intricate and odd-shaped angles and cavities in materials of
varying strength and hardness, usually complicated to machine using conventional
methods [30]. However, the technique is limited to electrically conductive materials.
210 6 Fabrication
6.3.3.3 Chemical and Photochemical Machining
Chemical and photochemical machining (PCM) is a chemical milling process using

a photoresist and corrosive etchants to machine away selected areas by selective
etching. The tooling is inexpensive and can be quickly produced. The machining
maintains dimensional tolerances and does not create burrs or sharp edges. However,
the high corrosion resistance of Alloy 625 requires strong acids for metal removal,
which can cause intergranular attack if not correctly used. The process is an econom-
ical alternative to stamping, punching, laser or water jet cutting, etc. for thin gauge
precision parts and can accurately produce highly complex components with minute
details. However, it is limited to materials with a thickness of 0.013 to 2.032 mm
[31]. It also lowers the fatigue life slightly even under optimum conditions.
6.3.3.4 Plasma Cutting
Plasma cutting is a process that utilizes an accelerated jet of hot plasma (ionized gas)
to cut electrically conductive materials. When compressed gas is blown through a
focused nozzle at high speed toward the workpiece, an electrical arc forms within the
gas between an electrode and the workpiece itself. The electrode may be placed very
near or integrated into the gas nozzle. The electrical arc ionizes the gas, creating an
electrically conductive hot plasma channel. The plasma channel forms a complete
electrical circuit from the plasma cutter through the workpiece and back to the plasma
cutter through a grounding clamp. The electricity from the cutter torch travels down
the plasma to melt the workpiece at the point of contact. At the same time, the
high-velocity plasma and compressed gas blow away the hot molten metal from the
workpiece. Plasma-arc torches can cut thick and thin sections of Alloy 625 and other
nickel alloys at very high speed. Plasma cutting is an efficient method for rough
cutting of plates, sheets and angles compared to other cutting methods.
6.3.3.5 Laser Beam Machining
Laser beam machining (LBM) uses heat directed from a laser beam to remove mate-
rial from metallic or non-metallic surfaces. When a high frequency of monochromatic
light falls on a surface, photons transfer the energy to heat, melt and vaporize the
material. Laser beam machining is best suited for brittle materials with low conduc-
tivity but can be used on most materials [32]. The cutting depth of a laser is directly
proportional to its power and inversely proportional to the cutting speed and the
diameter of the laser beam. The depth of the cut is influenced by the reflectivity,
density, specific heat, and melting point of the workpiece. Laser beam machining
can drill holes through all types of materials and superalloys in a very short time. For
example, a 0.5 mm diameter hole can be drilled through a 2.5 mm thick superalloy
sheet within 3 seconds.
6.4 Welding of Alloy 625 211
6.4 Welding of Alloy 625
This section describes the joining of Alloy 625 by fusion welding. In principle, metals
can be joined by various types of non-mechanical techniques, like fusion welding,
solid-state welding, and brazing. Of these, fusion welding is the principal technique
for producing high strength joints for all types of superalloys. The section focuses
on the welding metallurgy, weldability and post welding heat treatment of the fusion
welds in Alloy 625.
6.4.1 Common Welding Practices for Alloy 625
Welding is the joining of two or more components of similar or dissimilar metals,

using a metallurgical bond to form a single piece. A metallurgical bond involves the
diffusion of the material across the interface. It relies on melting and solidification
of either the base alloy or the base alloys and the filler material (i.e., welding rod).
During welding, the workpieces that are to be joined and the filler material are
heated to a sufficiently high temperature to melt the metal. An electric arc or a
gas may do the heating. The molten metal solidifies to form a fusion joint between
the work-pieces. The filler materials are characterized by: (i) the same nominal
composition of the base alloys for similar metal components; or (ii) a composition
compatible with the chemistry of the components being joined to produce a joint
with acceptable environmental and mechanical properties. Alternatively, the joint
may have properties similar to the base metal but may not necessarily have the
composition of either of the component. Welding, however, introduces a cast structure
of variable size and properties, which may vary based on the metals being welded
and the welding technique employed.
Alloy 625 is readily joined by conventional Gas Tungsten Arc Welding (GTAW),
Gas Metal Arc Welding (GMAW) and Shielded Metal Arc Welding (SMAW) welding
techniques. Besides, other welding techniques like plasma arc welding, resistance
spot welding, laser beam welding, and electron-beam welding can also be used. Alloy
625 exhibits a sluggish welding and shallow penetration than steels and austenitic
stainless steels. Therefore, extra care is required in the joint design and weld bead
placement to ensure sound welds with the proper tie-in of the weld beads.
Several common filler metals for gas tungsten arc and gas metal arc can be used for
welding Alloy 625 with other metals. A list of these filler metals, as per the American
Welding Society (AWS) classification, is given in Table 6.7 [33]. Recommended use
of these filler metals for the welding of Alloy 625 with itself or with other metals is
shown in Table 6.8.
Many advanced welding techniques can be used as alternate welding techniques.
A few frequently used advanced techniques are laser welding, electron-beam welding
and solid-state welding. In laser beam welding, a highly focused and intense laser
beam melts the base metal, and a fusion joint is formed upon solidification, often
212
Table 6.7 Nominal compositions of filler metals used for welding of Alloy 625
AWS class UNS No Chemical composition a
C Cr Fe Mn Ni Mo Si Other
ERNiCrMo-3 N06625 0.1 20–23 5.0 0.50 58.0 min 8–10 0.5 Nb 3.15–4.15, Al0.4, Ti0.4
ENiCrMo-3 W86112 0.10 20–23 7.0 1.0 55.0 min 8–10 0.75 Nb3.15–4.15
ERNiCrWMo-1 N06231 0.05–0.15 20–24 3.0 0.3–1.0 Bal 1–3 0.25–0.75 Al0.2–0.5, Co 5.0, W13–15
ERNiMo-3 – 0.12 4.0–6.0 4.0–7.0 1.0 Bal 23.0–26.0 1.0 Cu0.50, Co2.5, W1.0, V0.60
ER 3556 R30556 0.15 21.0–23.0 Bal 0.5–2.0 19.0–22.5 2.5–4.0 0.8 Co16.0–21.0, W2.0–3.5
a Single number refers to the maximum value
6 Fabrication
Table 6.8 Filler metals for fusion welding of Alloy 625 with other metals
Alloy type Typical alloys Filler metal alloy
Self Alloy 625 ERNiCrMo-3, ENiCrMo-3
Fe-base, Fe–Ni-based, ferritic Carbon steels, HSLA steels, ERNiCrMo-3, ER3556,
alloys Ferritic- and austenitic- ENiCrMo-3
stainless steels, Alloy 330,
800, 800H, etc
Ni-based, low alloy Alloy 825, 600, 601, 75, and ERNiCrMo-3, ENiCrMo-3,
80–20 alloys ER NiMo-3
Ni-based, high Mo/W Hastelloy B,N,S,W and X, ERNiCrMo-3, ERNiMo-3,
Alloy 230, 242, 617 ERNiCrWMo-1
Ni-based, high Al, Ti and Nb Haynes R-41, 214, 262, Alloy ERNiCrMo-3, ERNiMo-3
718, X-750, Waspaloy alloys
Cobalt-based & high cobalt Haynes 25, 31, 150 and 188 ERNiCrMo-3, ER3556
alloys
without filler metal. Since the energy input to the workpiece is low, the fusion zone
size is small and very precise, and the heat-affected zone size is minimal. Laser beam
welding produces porosity-free welds having a strength equal to or better than the
base metal. It is an automated and noncontact process that eliminates mechanical
distortion of the workpiece.
Electron-beam welding (EBW) is similar to laser welding, in which a beam of
high-velocity electrons is utilized to make the fusion joint. When electrons with
high kinetic energy strike the workpiece, they transfer their kinetic energy into heat,
which melts the metal. The electron-beam welding offers all the advantages of laser
welding, but it needs to be performed under vacuum to prevent the dissipation of the
electron energy. This technique is quite effective in welding similar and dissimilar
joints of different types of solid-solution strengthened superalloys including Alloy
625.
In solid-state welding, two pieces of metals are bonded under pressure providing
intimate contact between them and at a temperature below the melting point of
the base material. It creates the same result as fusion welding without melting the
contacting surfaces. The bond forms when the interface atoms from one metal diffuse
into the other due to the high pressure and temperature. The solid-state bonding does
not require consumables like filler metal, fluxes or shielding gas but often need a
thin interlayer of third metal when bonding two dissimilar metals with negligible
solid solubility. The third metal should have sufficient solid solubility in the two
work-pieces of different metals to be joined. The weld is excellent and free from
defects like pores, non-metallic inclusions, segregation of alloying elements, etc.
as no melting and solidification is involved. The mechanical properties of the weld
are similar to those of the parent metals. Solid-state welding allows the joining of
precipitation-hardened superalloys without the need for post-weld aging.
214 6 Fabrication
Table 6.9 Solid-solubility, partitioning coefficients and terminal eutectic temperatures of sulfur,
phosphorous, boron and silicon in their binary alloys with nickel. Their maximum limit in
superalloys to avoid impurities related liquation-type hot cracking is also given [13]
Element Maximum Partitioning Terminal eutectic Recommended
solubility (wt%) coefficient, k temperature (°C) solubility (wt%)
Sulfur ~0 ~0 637 0.015
Phosphorus 0.02 0.02 870 0.015
Boron 0.7 0.04 1093 0.7
Silicon 8.2 0.70 1143 0.02
6.4.2 Pre-welding Treatment of Alloy 625
The solid-solution strengthening of Alloy 625 makes its welding straightforward and
can be welded without special preheat or post-heat treatment. However, the cleanli-
ness of the Alloy 625 is essential because contaminations by machining greases and
oils, corrosion products, and low melting point elements like lead, sulfur, etc. may
hinder achieving welds free of defects. Introducing oils and greases to the fusion
zone causes fissuring and porosity, leading to severe cracking problems. The pres-
ence of low melting elements and alloys in the heat-affected zone (HAZ) may cause
fissuring by liquation cracking, as discussed later in Sect. 6.4.5.2. Sulfur, phosphorus,
lead, and boron in alloy chemistries are potential sources of liquation cracking. In
addition, oxygen and nitrogen have also been reported to have a deleterious effect on
the welds. Table 6.9 gives the maximum limit of these impurities to restrict liquation
cracking in superalloys [13]. A pre-weld heat treatment is necessary for cold-work
or work-hardened alloy, which must be done in a limited temperature range to avoid
annealing of the metal. The inter-pass temperature should be kept low during welding.
If needed, auxiliary cooling methods may be used between weld passes, provided
they do not introduce contaminants.
6.4.3 Welding Metallurgy of Alloy 625
6.4.3.1 Microstructural Evolution in The Fusion Zone
Microstructural evolution in fusion weld zones of Alloy 625 is very sensitive to

the concentration of niobium and carbon [34–40]. The basic principles of the parti-
tioning behavior of solutes during solidification of Alloy 625 have been mentioned in
Sect. 3.3. The same principles govern the distribution of solutes during the solidifica-
tion of the fusion zone. The last liquid that solidifies is enriched with niobium, carbon
and silicon. The solute rich liquid tends to form the Laves and NbC phases due to
eutectic-like reactions in the interdendritic and intergranular regions. These phases
form as the concentration of niobium, carbon and silicon in the dendrites exceeds the
Fig. 6.9 The schematic

illustrates the formation of
typical boundaries in the
fusion zone of a single phase
austenitic weld
solid solubility of the γ matrix. Likewise, impurity elements like phosphorous, sulfur
and boron tend to segregate aggressively to the liquid and form low melting eutectic
phases during solidification. The formation of low melting eutectic phases in the
interdendritic and grain boundary regions significantly increases cracking suscepti-
bility of the weld [41]. The elements boron and sulfur are more harmful because they
lower the solid/liquid surface energy and promote extensive wetting of boundaries
by the eutectic liquid films. Silicon also forms a low melting point nickel silicide,
but it is less harmful than other impurities unless present in relatively large amounts.
The fusion zone of a single phase austenitic weld is typically characterized by
the formation of three types of boundaries (Fig. 6.9) [42]. These boundaries are: (i)
solidification sub-grain boundaries, that separate cells and dendrites and are char-
acterized by low-angle boundaries; (ii) solidification grain boundaries, that separate
packets of sub-grain boundaries forming as a result of competitive growth at the end
of solidification and are characterized by high-angle boundaries with high concentra-
tions of solute and impurity elements; the grain boundaries have both compositional
and crystallographic components; and, (iii) migration grain boundaries, that form
when the crystallographic components of the solidification grain boundaries migrate
away from the composition component.
6.4.3.2 Heat Affected Zone
A region of the base metals, adjacent to the fusion zone experiences microstructural
and properties alterations. This region is termed the “heat-affected zone”. The heat-
affected zone stretches from base metal to the edge of the fusion zone. As all superal-
loys solidify over a range of temperatures, a part of the heat-affected zone adjacent to
the fusion zone is characterized by solidified intergranular liquid. This zone is called
“partially melted” or “mushy zone”. The heat-affected zone of all superalloys’ welds
contains a mushy zone, including all or a part of the partly melted/solidified zone.
216 6 Fabrication
The mushy zone liquid generally does not affect the weldability of the alloy because,
during the normal course of solidification, it is always open to the fusion zone.
Several metallurgical reactions in the heat-affected zone influence properties and
weldability of an alloy. These reactions may include one or more of the reactions like
recrystallization, grain growth, grain boundary segregation, precipitation of second-
phase particles and grain boundary liquation. But the HAZ of Alloy 625 welds
does not usually exhibit these reactions because of the alloy’s solid-solution nature,
except for some grain growth. However, welding the alloy in cold-worked or hot-
worked conditions containing some “residual strain” may cause the recrystallization
of grains. The degree of grain growth depends upon the initial microstructure of the
base metal and the weld heat input.
The alloy may also undergo grain boundary liquation in the region of the HAZ
adjacent to the fusion boundary due to eutectic reactions. Such liquation may result
from impurity, solute segregation, or both along the grain boundary or due to a
phenomenon known as “constitutional liquation. For this reason, high heat input
welding processes are usually not recommended for solution annealed materials. The
segregation of sulfur, phosphorous and boron has the most profound effect on grain
boundary liquation if their concentration is not restricted to very low levels. Their
segregation to grain boundaries causes a local depression of the melting temperature
and promotes continuous liquid film formation [43–45]. Likewise, the presence of
TiC, NbC and TCP phases in the base metal may lead to constitutional liquation at
their interface with the austenitic matrix. [46, 47]. Rapid heating associated with the
weld thermal cycle does not dissolve these phases. But an interfacial liquid film of
eutectic composition forms at particle/matrix interfaces at temperatures above the
eutectic temperature. This liquid can subsequently penetrate the grain boundaries.
This type of liquation has been observed at carbides and intermetallic phases in
several nickel-base alloys [48–52]. Both of these liquation mechanisms promote
cracking in the HAZ.
6.4.4 Mechanical Properties of Weldments
In general, the solid-solution strengthened alloys retain near base metal properties
in the as-welded condition because the loss in the solid-solution strengthening due
to segregation in the fusion zone is compensated by the second-phase strengthening
due to particles that form inter-dendritically. Similarly, the mechanical properties of
the HAZ do not deviate significantly from those of the base metal because of limited
grain growth. However, the HAZ in the cold worked welded structures may lose
strength due to recrystallization and grain growth. Therefore, little degradation in
the strength and ductility of solid-solution alloys is expected due to welding. The
weld metals for Alloy 625 (the ERNiCrMo-3 types) exhibit a tensile strength of about
90% of the base metal [41]. However, a loss in the weld metal ductility may occur
when the welding is conducted with shielding gases containing > 1% hydrogen [53],
as in the gas tungsten arc welding using argon–hydrogen gas mixtures for improving
the wetting and flow characteristics of the weld metal. This loss in ductility is due to
hydrogen pickup in the weld metal, which causes hydrogen embrittlement. Young
et al. [53] have shown that an increase in the hydrogen levels from 3 to 12 ppm
reduces the UTS of filler metal 82 multi-pass deposits from about 760 to 620 MPa,
and the ductility from 50 to 20%. Changing shielding gas to 100% helium or argon-
helium mixtures restored the mechanical properties of the filler metal deposits. A
similar effect on the mechanical properties of the welds is when the flux absorbs
moisture while welding with a flux-based welding process.
6.4.5 Weldability of Alloy 625
The weldability of an alloy is related to its hot cracking susceptibility. Hot cracking
occurs to varying degrees, depending on the amount of weldment restraint, welding
condition, alloy composition, etc. The cracking susceptibility is primarily controlled
by the solidification temperature range and the amount and distribution of the terminal
liquid at interdendritic regions [34, 35, 36, 54, 55–58]. The terminal liquids in Alloy
625 form Laves and carbide phases by eutectic reactions at temperatures lower than
the alloy’s solidus temperature. The formation of these eutectics lowers the melting
temperature at interdendritic and intergranular regions, making the alloy susceptible
to cracking at high temperatures. Similarly, the liquation of low melting eutectics
formed by the segregation of sulfur, phosphorous and boron at grain boundaries
influences the susceptibility of intergranular hot cracking. These two hot-cracking
mechanisms also influence hot cracking susceptibility in the heat-affected zones
during reheating or post-weld heat treatment of the weld. A detailed description of
these mechanisms is given below.
6.4.5.1 Fusion Zone Solidification Cracking
Alloy’s susceptibility to fusion zone cracking is a function of metallurgical factors

and the local strain accumulated at the end of solidification. As noted above, solute
distribution during solidification affects the solidification temperature range and the
interfacial terminal liquid, which forms carbide and Laves phases. Either way, the
segregation of solutes promotes hot cracking. Besides, the segregation of impurity
elements like phosphorous, sulfur and boron also promote hot cracking. The distri-
bution of terminal eutectic liquid at interdendritic and intergranular regions causes
appreciable shrinkage strain across boundaries. If the terminal liquid is distributed
as a continuous film along the boundaries, the boundaries may not accommodate the
strain and may separate to form a crack. Therefore, better control of terminal stages of
solidification improves the weldability of the alloy. Figure 6.10 shows solidification
cracks along solidified grain boundaries in the fusion zone of Alloy 625, where the
218 6 Fabrication
Fig. 6.10 Solidification

cracks along solidified grain
boundaries and interdendritic
regions in the fusion zone of
Alloy 625. The figure also
shows the healing of the
cracks, indicated by arrow
marks, by backfilling the low
melting eutectic liquid.
Reprinted by permission
from Springer [41].
Copyright (2008)
solidification cracks reside along solidification grain boundaries and interdendritic

regions that solidify last.
The solidification cracking susceptibility of Alloy 625 as a function of niobium,
silicon and carbon concentration and their harmful influence on its weldability has
been investigated by Ceislak [34]. He has shown that, although Nb is added to Alloy
625 as a solid-solution strengthener, it mostly ends up forming NbC and Laves phases
in the weld metal (~ 85 to 90 wt% niobium in NbC and ~ 22 to 36 wt% niobium in
the Laves phase) because of its segregation tendency [34, 35, 36, 59]. The tendency to
form the NbC and Laves phases, and consequently cracking susceptibility of the alloy
weld, increases with the niobium content. Besides, NbC and Laves phase formation
during terminal solidification lowers the solidification temperature. The Laves phase,
in particular, reduces the solidification temperature of Alloy 625 most, up to about
1150 °C [34, 41, 42]. Similar results are reported for other niobium-bearing alloys
also [35, 56].
As noted earlier, phosphorous, sulfur and boron also form low melting point liquid
films at interdendritic regions and grain boundaries. The low melting film formation
significantly increases the alloy’s hot cracking susceptibility. The boron and sulfur are
particularly more harmful because their segregation lowers the solid/liquid surface
energy and promote extensive wetting of the boundaries by the low temperature
melting films. The cracking susceptibility increases as the amount of sulfur and
phosphorous increases. Therefore, the alloy’s sulfur and phosphorous levels are kept
low, typically below 0.003 wt% and 0.01 wt %, respectively, to minimize solidi-
fication cracking. As pointed out in Sect. 3.1.13, the presence of a small amount
of manganese is often beneficial because it reduces the tendency of sulfur to wet
the grain boundaries. Manganese combines with sulfur to form manganese-sulfide
(MnS) particles with globular morphology.
The cracking susceptibility of Alloy 625 ranges from intermediate to high [41].
Lippold et al. [41] have studied the solidification cracking susceptibility of filler
metals of 617, 625, X and W alloys using the Varestraint test. Alloys 625 was the most
susceptible among the alloys studied (Fig. 6.11). Varestraint testing is a commonly
Fig. 6.11 A comparison of maximum crack distance versus strain for different solid-solution
strengthened filler metals [41]
used technique of determining the susceptibility of the materials to solidification and

liquation cracking.
Despite its wide solidification range, sound and crack-free welds can be made
in Alloy 625 using Nb-bearing Ni–Cr–Fe–Mo consumables by carefully control-
ling weld beads. The alloy exhibits good weldability concerning weld solidifica-
tion cracking, particularly at low to medium restraints. The apparent disagreement
between the Varestraint results in Fig. 6.11 and actual practice is attributed to the
crack backfilling phenomenon in Alloy 625. The reported Varestraint data is from
samples tested at high applied strains. However, the behavior of the liquid films
along solidified grain boundaries is different at lower strains. The Alloy 625 forms
a considerable amount of low melting eutectic liquid at the end of solidification (the
light contrast region marked by arrows in Fig. 6.10). Under low strain conditions,
the eutectic liquid heals the cracks by a backfilling mechanism. However, at higher
strains, the eutectic backfilling is not effective to overcome the strain resulting in the
formation of cracks.
6.4.5.2 HAZ Liquation Cracking
As noted above, Alloy 625 exhibits broad melting and solidification temperature
ranges due to its high alloying contents. The base metal adjacent to the fusion zone
220 6 Fabrication
may also experience a temperature between liquidus and the local solidus tempera-
tures during welding. This melting may cause liquation cracking in the mushy zone
when the melt cannot sustain the applied strain. Alloys welded with high heat input
welding processes, like gas metal arc welding (GMAW) in the spray transfer mode,
tend to form such liquation cracks in the HAZ. The liquation cracking mechanisms
involve the liquation of eutectic phases formed by impurities and the carbide and
Laves phases, as mentioned in Sect. 6.4.5.1 above. The only difference here is that
the liquation of phases in the HAZ is controlled by the impurities levels and the
concentrations of niobium and titanium in the base metal.
Impurities like phosphorous, sulfur and boron aggravate the liquation cracking
by making a low-temperature film at the grain boundaries. Phosphorous generally
harms the least and boron the most, while sulfur in between the two [60]. A rule of
thumb is to maintain impurities as low as possible to avoid HAZ cracking. The total
content of sulfur plus phosphorous less than 100 ppm (0.01 wt%) causes no liquation
cracking.
Constitutional liquation of NbC and TiC phases in the austenitic Alloy 625 matrix
may also cause HAZ liquation cracking [43, 50, 52]. A particular case of HAZ liqua-
tion cracking is the cracking in multi-pass welds where the initial weld passes to
become the HAZ for the subsequent passes. In this case, liquation occurs due to
local melting along grain boundaries in the underlying weld metal. The reheating
of the initial weld makes it susceptible to cracking at segregated solutes and impu-
rities along solidification grain boundaries and migrated grain boundaries. Besides,
solidified NbC particles in regions away from grain boundaries may liquefy to form a
localized solid solution highly concentrated in niobium. The niobium enriched local-
ized areas may precipitate out the embrittling δ phase particles during subsequent
thermal exposure in the temperature range of the δ phase precipitation. Figure 6.12
shows an example of a precipitation of δ phase particles in the interdendritic regions
during subsequent heating of a welded Alloy 625 structure [61].
Fig. 6.12 SEM image of δ

precipitates at interdendritic
locations of liquated NbC
particles in Alloy 625.
Reprinted by permission
from Springer [61].
Copyright (2018)
6.4.6 Post Weld Heat Treatment
In general, a post-weld heat treatment (PWHT) is regularly performed to relieve

residual stresses, reduce hydrogen content, homogenize the microstructure, dissolve
undesirable secondary phases that may have formed in the fusion zone or HAZ.
A PWHT is also given to improve the corrosion properties of the weld. However,
cracking is sometimes observed, particularly in nickel-base superalloys containing
aluminum and titanium, like Alloy X-750, when the welded structures are heated
to temperatures within their aging temperature range or when the alloy is slowly
cooled from the solution temperature through this temperature range. Figure 6.13
schematically depicts this type of cracking. The frequency of cracking increases when
the alloys are reheated through the hardening temperature range in the presence
of residual or applied stress in constrained conditions. PWHT cracking in Alloy
X-750 occurs when aluminum and titanium induce rapid precipitation of the γ
phase particles that harden the alloy. Figure 6.14 illustrates the alloy’s behavior that
leads to PWHT cracking of such alloys. Figure 6.14a shows a typical variation in
residual stresses away from the weld centreline. After welding, the HAZ retains
high residual stresses. When the welded part experience elevated temperature during
a heat treatment or service exposure, the residual stresses first relax as the temperature
rises. But the stresses start building up again when the precipitation of the hardening
phase begins at temperatures above the precipitation temperature (Fig. 6.14b). A
reduction in ductility accompanies strengthening. As the precipitation continues,
the welded part experiences an instantaneous catastrophic failure when the built-up
stresses reach a critical stress level σ C . The higher the volume fraction of the γ
precipitates, the greater the tendency to crack.
Fig. 6.13 Schematic illustrating strain-age cracking in the heat-affected zone after a post-welding
ageing treatment of the alloy. Such cracking is common in many γ phase precipitating nickel
superalloys
222 6 Fabrication
Fig. 6.14 a Typical residual-stress distribution across a welded joint; b Schematic illustrating the
variation in the residual stress and γ phase particles induced cracking in the HAZ when a γ -bearing
nickel-based superalloy is heated to its ageing temperature range during post-weld heat treatment
The amount of aluminum and titanium in Alloy 625 is too low to cause the
precipitation of the γ phase. However, post-weld heat treatment of the alloy may
cause the precipitation of other hardening phases noted in Chap. 4. Cortial et al.
[62] have investigated the influence of post-weld heat treatment, over a temperature
range from 600 to 1000 °C, on the mechanical properties of Alloy 625 welds [62] and
reported a loss in the strength and ductility of the alloy (Fig. 6.15), consistent with
the aging behavior of the alloy presented in Chap. 4. A sharp drop in the toughness
is observed after an annealing treatment in the 750–950 °C range. This toughness
drop is associated with the formation of the δ phase (Fig. 6.16). The formation of
Fig. 6.15 Variation in room temperature mechanical properties of Alloy 625 welds as a function of
heat treatment for 8 h: a strength; b ductility; and c impact energy. The “AW” data points indicate
the property in the as-welded condition [62]
Fig. 6.16 Microstructures of Alloy 625 welds after post weld heat treatment for 8 h: a 600 °C; b
750 °C; c 800 °C; d 850 °C; e 950 °C; f 1000 °C. Reprinted by permission from Springer [62].
Copyright (1995)
M23 C6 carbides and the δ phase particles in the segregated regions of the weld may
embrittle it further. At 1000 °C, the ductility is restored due to the dissolution of δ
phase. However, grain growth occurs as the δ phase particles no longer pin the grain
boundaries. This behavior is similar to that noted in Chap. 4, where aging of the
alloy over a temperature range from 600 to 900 °C is reported to adversely affect its
mechanical properties due to the formation of γ , δ and carbide phase particles. The
224 6 Fabrication
formation of the Ni2 (Cr ,Mo) phase particles also affect mechanical properties but
their formation during a PWHT is ruled out because of its large incubation period.
Thus, there is little benefit of heat treating Alloy 625 welds from a mechanical
properties standpoint because as-welded properties are generally close to the base
metal properties (Chap. 4). However, a PWHT on Alloy 625 weld is often performed
to reduce residual stresses and improve corrosion resistance, including the resistance
against intergranular attack. Therefore, the post-weld heat treatment of Alloy 625
should be controlled carefully to prevent the loss in its ductility and toughness.
A heat treatment within a narrow temperature range of 950–1000 °C, with careful
control of the exposure time commensurate to the section thickness, is recommended
to remove residual stresses and improve resistance to stress corrosion cracking in
the welded Alloy 625. This heat treatment helps prevent the intergranular attack
(IGA) by forming stable grain boundary carbide particles as in many other solid-
solution alloys like 600, 690 and 825.
6.4.7 Welding Behavior of Alloy 625 PLUS
The solidification behavior of the age-hardened Alloy 625 PLUS is very similar to
that of Alloy 625. In is mainly related to the segregation behavior of niobium, which
is critical during the solidification of the fusion zone. The γ /Laves eutectic in Alloy
625 PLUS forms at about 1126 °C. The extra titanium in Alloy 625 PLUS does not
appear to influence the amount of eutectic constituent compared to Alloy 625. Alloy
625 PLUS therefore exhibits hot cracking susceptibility similar to that of Alloy 625,
but much superior to Alloy 718 [63].
The Alloy 625 PLUS exhibits the precipitation of the γ adjacent to the Laves
phase during cooling of the weld metal to room temperature. This precipita-
tion behavior is similar to that observed in Alloy 718 [64]. However, the slow
age-hardening response of Alloy 625 PLUS compared to γ strengthened alloys
like Waspaloy, Alloy 693, etc. dramatically reduces its susceptibility to strain-age
cracking during welding. The mechanical properties of the as-welded Alloy 625
PLUS are similar to those observed in Alloys 625 and 718. The effect of heat treat-
ment on room-temperature tensile properties of Alloy 625 PLUS welded samples
is shown in Table 6.10 [63]. Welded joints subjected to standard solution annealing
and double-aging treatments (Sect. 5.2) show yield strength and ductility similar to
the base metal. The double-aging heat treatment to Alloy 625 PLUS weld results in
a yield strength above 827 MPa with good ductility. Solution annealing the weld
before an aging treatment may improve its strength and ductility.
6.5 Additive Manufacturing 225
Table 6.10 Effect of heat treatment on room temperature tensile properties of GTA Welds of 625
PLUS Alloy a [63]
Condition b 0.2% yield Ultimate tensile Elongation (%) Reduction in area
strength (MPa) strength (MPa) (%)
As welded 510 827 41 48
Direct aged 848 1124 22 34
Solution anneal + 876 1220 26 51
aged (weld)
Solution anneal + 896 1276 31 55
aged (base metal)
a 11.68 mm thick plate with 60° V-groove GTA welded in 13 passes using matching filler metal;
6.40 mm gauge diameter all-weld-metal tensile specimens

b Solution annealed = 1038 °C/l h/AC; Age = 732 °C/8 h/FC to 621 °C/8 h/AC
6.5 Additive Manufacturing
6.5.1 Additive Manufacturing of Metals
Additive manufacturing (AM), also known as 3D printing, is an innovative way

of fabricating three-dimensional structures by progressively depositing layers of
material. It allows the creation of complex three-dimensional shapes with complex
geometries, such as internal cavities and lattice structures, where traditional manu-
facturing like casting, forging, or machining are time-consuming or incapable of
achieving desired geometries. Over the last few decades, many additive techniques
have evolved based on how the layers are deposited to create the component and
the materials used. These techniques can be categorized into seven based on the
printing technologies [65].
(I) Powder bed fusion
(II) Directed energy deposition
(III) Material Jetting
(IV) Binder jetting
(V) Material extrusion
(VI) Vat photopolymerization
(VII) Sheet lamination
Each technique has advantages and limitations associated with
printing/manufacturing processes such as speed, type of the feedstock mate-
rial, geometrical limitations, tolerances, properties, costs, etc. But all the additive
manufacturing techniques have shown the potential to lower the overall cost. They
can manufacture parts on-demand, reducing maintenance time and the need for
inventory management [66]. Additive manufacturing is being used to print tissues
[67, 68], implants and prostheses [69], mechanical components [70], electronics
226 6 Fabrication
[71], etc. using a wide range of materials, including polymeric [72] materials,
stainless steels [73, 74], nickel-based superalloys [75] and titanium alloys [76, 77].
Metal AM techniques primarily use powder bed fusion, directed energy deposi-
tion, binder jetting and sheet lamination. The powder bed fusion technique uses a
high-density power source to scan and fuse layers by selective fusion of the powder
bed in multiple layers. As a layer is built, another layer of the powder is added,
and the power source moves up to fuse it. The process is repeated until the part is
built-up. The scan speed plays a decisive role in densification and good metallurgical
bonding during selective laser melting (SLM). The printer lays down successive
layers of the metallic powder based on three dimensional computer-aided design
(CAD) models. The layers are melted together by a computer-controlled power
source of a laser or electron beam. The main factors that influence the properties of
an additively manufactured component are: (i) the orientation of the CAD geometry
across which the part is sliced into layers to build the part, (ii) processing param-
eters like scan velocity, power density, etc. Parameters like powder properties and
processing environmental influence the melt pool size in the powder bed. After a
layer is deposited, a new powder layer with a predefined thickness is placed on the
powder bed. For successful deposition, the melt pool must be large enough to fuse
and connect adjacent tracks in each layer and deep enough to fuse and bond with the
previous layers. Incomplete fusion may occur if the energy density is insufficient,
while excessive energy may lead to defects in the fabricated part. An increase in the
energy density increases track overlap and improves fusion.
Among different powder bed techniques, selective laser melting (SLM) and
electron-beam melting (EBM) are mainly used for the rapid production of net-shaped
or near-net-shaped components by a high-power density laser or electron-beam. The
powder bed fusion method directly produces highly dense metal parts from metal
powder with characteristics close to the bulk material. Choi et al. [78] have reported
SLM made Alloy 718 with 99.8% density.
Selective laser melting, also known as direct metal laser melting or laser powder
bed fusion, uses a high power-density laser to melt and fuse metallic powders. The
high-energy laser melts the powder to create a fully dense metal layer with mechan-
ical properties similar to conventionally manufactured metals. The scan patterns are
rotated from layer to layer to obtain a more uniform layer-to-layer and stripe-to-stripe
fusion. Two types of layering strategies, based on the rotation of the scan patterns with
respect to the previous layer, either by 90° (i.e., scan patterns alternated in orthogonal
directions) or by about 67° from layer to layer, are adopted (Fig. 6.17). Ozel et al.
[79] have shown that the rotation of the scan orientation by 67° results in wider fused
tracks with larger overlaps for a given energy density. Dinda et al. [80] have shown a
significant effect of the scanning pattern on the solidification morphology during the
deposition of a multiple layer Alloy 718 component. Unidirectional laser scanning
results in the formation of primary dendrites at an angle of 60° with the substrate
in all layers. In contrast, the primary dendrites in a bidirectional scanning change
by 90° in each layer with respect to their growth direction in the previous layer
[80]. This effect of laser scanning on the solidification pattern may result in printing
components of precisely the same geometry with strikingly different solidification
Fig. 6.17 Schematic depicting 90° and 67° rotation of the stripe patterns, with respect to the
previous layer, during 3-D printing of an alloy by selective laser melting
patterns [80, 81]. Trosch et al. [82] have shown the SLM process can produce Alloy
718 components with mechanical properties better than forged and cast material at
room temperature and similar to forged products at elevated temperatures.
The microstructure of additively manufactured superalloys may be quite different
from their wrought or cast counterparts. A textured microstructure characterizes the
microstructure of an additively manufactured alloy built by an SLM process due
to the growth of columnar grains across multiple layers parallel to the building (Z-
axis) direction. The columnar grains are separated by high-angle boundaries and are
characterized by substructures of packets of parallelly arranged dendrite cells with
low-angle boundaries. As a result, the AM alloy exhibit a variation in mechanical
properties of the alloy in the scan and built directions. A heat treatment at high temper-
atures may not entirely change the elongated shape and crystallographic orientations
of the grains. Still, it may eliminate the dendritic substructure and bring the properties
close to the wrought alloys.
Although AM results in a near-net shape geometry of the component, post-
manufacturing treatments and finish machining are often required to relieve high
residual stresses and undesired porosity to achieve the final desired geometry, dimen-
sional tolerances, and surface quality [83]. The technique has been used to additively
manufacture parts of materials like stainless steel [84], Alloy 625 [85, 86] and Alloy
718 [65, 87], Ti6Al4V alloy [88, 89], etc.
Electron-beam additive manufacturing of metals produces similar columnar archi-
tecture parallel to the build direction. EBM utilizes an electron beam to selectively
melt the powder bed layer by layer in a high vacuum. Unlike metal sintering tech-
niques that operate below the melting point, EBM parts are void-free [86, 90]. The
process occurs under a vacuum, making it suitable to manufacture parts of reac-
tive materials, like titanium, with a high oxygen affinity. The process is carried
out at high temperatures (up to 1000 °C) to allow partial sintering of the powder
bed and minimize residual stresses during the build, leading to differences in phase
228 6 Fabrication
formation through solidification and solid-state phase transformation. The high-

temperature processing of the powder results in microstructural differences between
the component made by an EBM technique compared to that produced by SLM.
In a powder-fed directed energy deposition, a high-power laser melts the metal
powder before it is supplied to the focus of the laser beam. A hermetically sealed
chamber filled with inert gas or a local inert shroud gas is often used to shield
the melt pool from atmospheric oxygen to better control material properties. The
technique offers a high degree of control and freedom because multiple powders
can be fed simultaneously through the nozzle [65]. With this technique, desired
chemical composition and microstructural features can be obtained by adjusting
the feed rate [91]. The technique is best suitable for manufacturing near-net shape
components and repairing high-value parts with little wastage [92–94]. The process
supports various metallic materials, including titanium, stainless steel, aluminum,
speciality materials, composites, and functionally graded material. However, a post-
manufacturing operation like machining is often required to obtain tight tolerances
because of poor resolution and rough surface finish [95].
Additive manufacturing has the potential to reduce scrap generation, saves the
cost of machining, has high material utilization, reduce the manufacturing time and
can fabricate complex shapes that are otherwise impossible via conventional routes
[65]. Due to these advantages, AM has a significant impact on the manufacturing of
advanced components of Jet engines, urbine blades, rocket engines and many other
applications. However, controlling the fabricated components’ mechanical texture
and chemical properties is crucial for obtaining target properties in AM parts that
cannot be made by any other means.
6.5.2 Additive Manufacturing of Alloy 625
Alloy 625 is an attractive material for 3D printing by selective layer melting and
electron-beam melting techniques. The two techniques give good metallurgical
bonding of the powder with minimal defects and fine dendritic microstructure. Both
methods produce similar columnar microstructures of the alloy. However, a signif-
icant difference is reported in the size and shape of the γ phase particles and the
spacing, width, and texture of the columnar grains [86] due to the difference in the
cooling rates of the melt pools in the two processes. The scheme of rastering does
not appear to have any significant effect on tensile properties of the alloy [96]. Table
6.11 shows mechanical properties of the 3D printed alloy produced by selective laser
melting and electron-beam melting.
Figure 6.18 shows typical optical microstructure of Alloy 625 3D printed
by an SLM technique adopting a 67° layer rotation scheme. The microstruc-
ture revealed laser fused stripes in the surface layer (XY plane) and overlapped
fusion zones in the XZ plane. Inverse pole figure (IPF) maps of three orthogonal
XY, XZ and YZ planes in as-built revealed a columnar architecture of the grains
in the build direction, wherein individual columnar grains of solid solution γ phase
Table 6.11 Tensile properties of some 3-D printed Alloy 625 additively manufactured by selective
laser melting and electron-beam melting
AM sample Rastering YS (MPa) UTS (MPa) Ductility (%) Charpy energy Reference
(J)
SLM1 0° 572 920 48 104 [96]
SLM2 90° 568 925 46 102 [96]
SLM3 Mixed 571 915 49 103 [96]
SLM4 – 540 690 36 – [85]
SLM5 – 477–518 744–797 31–48 – [97]
SLM + anneal – 395 824 51 110 [96]
SLM + HIP1 – 360 880 58 – [86]
EBM – 410 750 44 – [86]
EBM + HIP2 – 330 770 69 – [86]
YS Yield strength; UTS Ultimate tensile strength; Ductility Elongation; HIP Hot isostatic pressed
were separated by high-angle boundaries (Fig. 6.19). This microstructure is consis-

tent with most as-built SLM microstructure (see, e.g., see [96].). The deflection of
the columnar grains away from the build direction is attributed to the moving laser
source. The YZ plane is characterized by columns of grains, separated mainly by
low-angle boundaries, oriented in a slightly zigzag fashion with respect to the build
direction.
The melt pool morphology on the top (XY plane) of the deposited layers and
the XZ plane shows a typical Gaussian morphology, oriented in the direction of
scanning/building, with a structure containing fine columnar grains of small dendritic
arm spacing (Fig. 6.20). This melt pool morphology is due to the multi-pass melting
with significant overlapping in horizontal and vertical planes. A schematic of the
overlapping of the melt pools in the two planes is shown in Fig. 6.21. The horizontal
interactions are usually governed by the laser beam overlapping in the XY plane. In
Fig. 6.18 Typical optical microstructure of the as-printed alloy showing the laser fused stripes on
the surface layer (horizontal plane) and the overlapped fusion zones in an orthogonal vertical plane
230 6 Fabrication
Fig. 6.19 Inverse pole figure (IPF) maps of the three orthogonal surfaces generated by electron-
backscattered diffraction revealing columnar architecture of the grains in the building direction: a
XY plane; b XZ plane; c YZ plane; d IPF triangle for the orientation labels of grains in (a–c)
Fig. 6.20 Scanning electron micrographs delineating the melt pool morphology, marked by arrows,
in the three orthogonal planes: a XY plane; b XZ plane; c YZ plane
6.5 Additive Manufacturing
Fig. 6.21 Schematic drawings showing overlapping of the melt pools during selective laser melting: a horizontal overlapping; b vertical overlapping
231
232 6 Fabrication
contrast, the vertical overlapping is governed by the layer thickness and the hatch
angle.
The 3D printed microstructure is characterized by chemical inhomogeneities
between dendritic cells and overlapping regions of adjacent racks and layers.
These inhomogeneities are due to the segregation of niobium and molybdenum
(Fig. 6.22). This microstructure is different from the typical solidification microstruc-
tures because the rapid melt solidification during SLM prevents macro-segregation.
Fig. 6.22 Segregation of niobium, molybdenum and carbon at interdendritic regions of the solid-
ified melt in a selective laser melted Alloy 625 sample. The lower panel shows maps of different
elements of a segregated region
However, the microsegregation of niobium and molybdenum in SLM is also suscep-

tible to forming the non-equilibrium Laves phases at interdendritic regions, grain
boundaries and layer interfaces due to the eutectic formation noted earlier. Chlebus
et al. [98] have shown the occurrence of tiny particles of the eutectic mixture (γ
+ Lave phase) or its divorced form and fine MC type carbides in the interdendritic
regions of SLM printed Alloy 718. Dinda et al. [99] have shown that the columnar
dendritic structure is stable up to 1000 °C and have demonstrated the formation of a
fully recrystallized equiaxed structure at around 1200 °C.
Ganesh et al. [85] have studied the mechanical and fatigue behavior of a laser-
printed Alloy 625. They have reported yield strength and tensile strengths of the
laser-printed Alloy 625 to be about 540 and 690 MPa with ductility of about 36%.
These properties were consistent with those reported by Xue et al. [97]. The yield
strength of the laser-printed alloy is higher compared to a wrought alloy, but the
ultimate tensile strength and ductility are lower (Sect. 4.5.1). The laser printed alloy
exhibited stable crack growth during the J-integral test and fracture toughness values
(J0.2 ) in the range of about 200–255 kJ/m2 . The crack propagated along the growth
direction of the specimens, which was predominantly along the {111} plane. Under
fatigue conditions, the laser-printed alloy showed a consistently steady-state fatigue
crack growth rate within the Paris’ Law regime
√ (Sect. 4.6) when examined in the
stress intensity (K) range of 14–38 MPa m. The fatigue crack growth rate within
this K range is lower than that for a wrought Alloy 625. However, the difference in
fatigue crack growth rate of the laser printed and wrought Alloy 625 diminishes with
an increase in K. Table 6.12 compares empirical constants of the Paris’ equation
(Eq. 4.18) for the laser-printed Alloy 625 with those for the wrought Alloy 625
[100]. Authors have attributed the improved fatigue crack growth resistance of the
laser-printed Alloy 625 in the low-stress intensity range to its higher yield strength
and residual stresses.
Additive manufacturing technologies have opened up new vistas of industrial
production processes to create components of complex materials with complex
shapes at promisingly low costs. However, to obtain good quality final compo-
nents, high-quality control of the additive printing processes and the raw material,
starting from the production of the powder itself, is necessary.
Table 6.12 A comparison of fatigue crack growth rate constants in the laser-printed and wrought
Alloy 625 samples within the Paris’ law regime
√
Alloy sample K (MPa m) Stress ratio C m Reference
SLM1 14–25 0.3 3.23 × 10−12 5.21 [85]
SLM1 21–31.1 0.1 1.48 × 10−12 5.42 [85]
SLM1 27.6–36.1 0.1 1.95 × 10−12 5.33 [85]
Wrought1 21.1–54.4 0.05 8.55 × 10−10 3.73 [100]
Wrought2 23–41 0.05 4.48 × 10−10 3.8 [100]
234 6 Fabrication
6.6 Summary
Ease of fabrication is an integral part of an alloy’s importance. The success of Alloy

625 is its ease of fabrication, apart from its excellent combination of strength and
corrosion behavior. The excellent deformability and welding of the alloy allow to
fabricate various shapes and structures for different applications, ranging from pres-
sure vessels to vacuum bellows for exploiting different alloy’s properties. Conven-
tional welding processes and procedures can readily join it with itself and to other
materials. The alloy usually requires no post-weld heat treatments to maintain its high
strength and ductility. However, machining of the alloy may be somewhat tricky. The
alloy is also finding excellent acceptance for 3D printing of components by additive
manufacturing techniques.
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Chapter 7
Corrosion Behavior of Alloy 625
Alloy 625 belongs to the Ni–Cr–Mo series of nickel alloys known for their excel-
lent resistance against uniform corrosion, localized corrosion and stress-corrosion
cracking in both oxidizing and reducing media. Ni–Cr–Mo alloys also provide
exceptional resistance to chloride-induced localized corrosion and stress-corrosion
cracking. The chromium content in these alloys may vary from about 15 to 25
wt% and molybdenum from about 8 to 17 wt%. The high concentration of molyb-
denum imparts excellent corrosion resistance in non-oxidizing (or reducing) media
like hydrochloric and sulfuric acids, and chromium imparts corrosion resistance in
oxidizing aqueous environments like nitric acid. Alloys with such a combination of
alloying additions find their application in chemical and metal processing industries.
Alloy 625 contains 20 to 23 wt% chromium and 8 to 10 wt% molybdenum along
with about 3 to 4 wt% niobium. These elements give Alloy 625 excellent corro-
sion properties over a broad spectrum of corrosive chemical and gaseous environ-
ments. For instance, the alloy can be used for fabricating storage tanks for chemical
wastes, including hydrochloric and nitric acids. The two acids represent reducing and
oxidizing types of corrosion behavior, respectively, and material with good corro-
sion resistance against one usually corrodes severely against the other. This chapter
describes, in brief, the corrosion behavior of Alloy 625 in different types of environ-
ments and compares it with other alloys. In the last section, a brief account of the
corrosion behavior of Alloy 625 PLUS, a precipitation-hardened variant of Alloy
625 (Chap. 5), has also been included to give an idea that the precipitation of γ
does not affect its corrosion behavior. However, the precipitation of the Ni2 (Cr, Mo)
phase may affect the corrosion behavior, though no reports supporting such a claim
are available.
Throughout the chapter, the compositions of various environments are mentioned
in weight per cent (wt%) for liquids and volume per cent (vol%) for gases, unless
specified otherwise.
https://doi.org/10.1007/978-981-19-1562-8_7
242 7 Corrosion Behavior of Alloy 625
7.1 The Basic Concepts of Corrosion
7.1.1 The Electrochemical Principle
The chemical and electrochemical destruction of metals and alloys in the presence
of reactive environments is termed corrosion. Corrosion of metals transforms them
into “rust”, a term commonly used for iron corrosion products that predominantly
contain oxides, hydroxides, and aqueous salts. During corrosion, an electrolytic cell
sets up comprising [1]:
(i) an anode that ionizes the metal to metal ions (cations) as per the oxidation
reaction
M → Mn+ + ne− (7.1)
which pass the ions into the solution, leaving their electrons within the original
metal surface.
(ii) a cathode that consumes the free electrons within the metal by reducing O2
and H2 O as per following reduction reactions
O2 + 4H+ + 4e− → 2H2 O (acidic solutions) (7.2)
O2 + 2H2 O + 4e− → 4OH− (neutral or basic solutions) (7.3)
2H+ + 2e− → H2 (in absence of dissolved oxygen) (7.4)
(iii) a conductive liquid that acts as an electrolyte through which positively charged
cations are transferred to the cathode and negatively charged anions (OH− ) to
anode simultaneously,
(iv) a metallic path, which completes the electrical circuit between the two
electrodes to migrate electrons from anode to cathode.
Figure 7.1 shows a schematic diagram of a typical electrochemical cell depicting
the corrosion of a metal M immersed in water. The anodic and cathodic reactions
proceed in balance to maintain the overall electrical neutrality of the system. For
instance, in an iron alloy, two hydrogen ions are reduced for oxidation (corrosion) of
every iron atom (Fe → Fe+2 + 2e− , 2H+ + 2e− → H2 ). In the presence of dissolved
oxygen in water, the cathodic reaction reduces oxygen to produce hydroxide ions as
per Eq. 7.3. This reaction corrodes more rapidly as it only involves oxygen diffusion
to cathodic areas. Therefore, an increase in dissolved oxygen increases the corrosion
rate.
Metallic materials have varying tendencies to oxidize depending upon their
oxidizing potential. An electrochemical series rank the relative corroding tendencies
7.1 The Basic Concepts of Corrosion 243
Fig. 7.1 A schematic diagram of a typical electrochemical cell formed during the corrosion of a
metal M immersed in water
of metals and alloys based on their oxidation potentials [1]. Metals/alloys with more
positive potential placed higher on the noble side, gold being the noblest. The driving
force for the corrosion reaction is the difference between the oxidation potentials of
anode and cathode, and the cathodic reaction controls the rate of corrosion. Anode
and cathode are set up based on relative oxidation potential of regions—a region
with more positive oxidation potential becomes the cathode. In a bi-metallic joint,
the inherent difference between the two metals decides the anode and cathode. In
contrast, within a single piece of metal, local variation in the oxidation potential due
to inherent factors like inclusions, chemistry, microscopic surface imperfections, or
even exposure of different crystallographic planes create a potential difference within
adjacent regions.
The corrosive medium is the most crucial factor that influences the rate of corro-
sion attack. The aggressiveness of a corrosive media is governed by factors like
acidity, temperature, concentration, motion relative to the metal surface, degree of
oxidizing power and aeration, and the presence of inhibitors or accelerators.
The corrosion media can be categorized as oxidizing or reducing in nature. The
aqueous environments are usually oxidizing due to dissolved oxygen unless specif-
ically treated for its removal. The cathodic reactions mainly reduce water to form
hydroxyl ions (Eq. 7.3). On the other hand, acidic environments containing most
dilute acids are reducing in nature and liberate hydrogen gas at the cathode as
per Eq. 7.4 [1]. Likewise, chemical environments can be broadly categorized as
oxidizing and reducing. A solution containing compounds like chromic acid, nitric
acid, concentrated sulfuric acid and oxidizing salts such as ferric or cupric salts,
nitrites, chromates, etc. form the oxidizing media. The cathodic reactions in oxidizing
media reduce anions or high valence cations (e.g., ferric to ferrous). On the other
hand, lowering chemicals like dilute halogen or other mineral acids and alkalis form
the reducing media. In reducing environments, the cathodic reaction usually reduces
hydrogen ions to generate the atomic hydrogen or gas.
When the corrosion occurs uniformly over a metal surface, it is termed general
or uniform corrosion. On the other hand, corrosion attacks can be very local or on
specific features like the grain boundaries of the structure.
7.1.2 Polarization and Passivity
Nobel metals like gold and platinum have little susceptibility to oxidation due to their
sizable positive oxidation potential. That is why they are found in nature in their pure
metallic state. On the other hand, metals like zinc and iron are very active due to
their negative oxidation potential and oxidize readily [1]. An increase in dissolved
oxygen in a corrosive solution further increases the corrosion rate of an active metal
(Eq. 7.3). However, at very high concentrations of dissolved oxygen, the corrosion
rate may drop to a very low value because of the chemisorption of oxygen at the
metal surface, which prevents it from further coming in contact with the electrolyte.
This stabilizes the corrosion and reduces its rate to a very low value. Such a loss in
chemical reactivity of metals and alloys under a particular environment is referred
to as “Passivity”. Polarization refers to a shift in the potential away from the free
corroding potential (termed as open circuit potential). A potential change in the
“positive” direction is called “anodic polarization”. On the other hand, a potential
change in the “negative” direction is termed “cathodic polarization”.
An S-shaped curve depicts the polarization behavior of a metal exhibiting a typical
active–passive behavior (Fig. 7.2). The behavior of an alloy can be divided into three
regions: active, passive and transpassive. As the oxidation potential of the anode (or
the oxidizing power of the solution) increases toward noble, the current per unit area
(or the corrosion rate) increases as the metal behaves identically to that of a normal
metal until a critical current density is reached at which the maximum corrosion rate
Fig. 7.2 A schematic

depicting the typical
polarization behaviour of an
active–passive metal
7.1 The Basic Concepts of Corrosion 245
is observed. This region is termed as “active”. An increase in the potential further

(i.e., oxidizing power of the solution) causes a corresponding fall in the corrosion rate
by orders of magnitude as the protective passive film forms. This corresponds to the
“passive” region, and the phenomenon is called passivation. Further increase in the
oxidizing potential (power) produces little change in the corrosion rate of the material.
But at very high values of the potential (concentrations of the oxidizers), the corrosion
rate may again start increasing with an increase in the potential. This region is termed
the “transpassive” region. Nickel, chromium, titanium, and zirconium spontaneously
passivate in air. Alloying iron with chromium above 11 wt% Cr produces famously
known passive stainless steel [1]. In nickel–chromium alloys, passivity arises due to
the formation of a thin invisible protective film of a metal oxide or an insoluble salt.
7.1.3 Corrosion Rate Expression
The corrosion rate can be expressed in several ways. The most common is based on
the rate of penetration inside the surface or the thinning of the structure, which is
used to predict the life of corroding components assuming uniform corrosion. The
most common expression is “mils per year (mpy)”, which can be measured as mass
loss per unit area and time, as [1].
534W
mpy = (7.5)
D AT
where W is the weight loss (in mg), D is the density of the metal/alloy (in g/cm3 ), A
is the area of the surface exposed to the environment (in square inch), and T is the
time of exposure (in hours). Another similar expression is millimeters per annum
(mm/a). Forty mpy equals about one mm/a. Throughout this chapter, the corrosion
rate is expressed in mpy unless specified.
7.2 Role of Alloying Elements
Nickel-based alloys are designed to deal with the aggressive nature of the chemical
industry. Nickel has a much higher tolerance for alloying additions in solid solution
than iron or other Iron-based alloys with excellent metallurgical stability of its face-
centered structure. These properties allow large amounts of alloying addition to tailor
properties of alloys for a wide range of corrosive environments with little compromise
in microstructure or mechanical properties required. Inherently, pure nickel is more
stable and noble than iron in the electrochemical series [1]. It resists the corrosive
nature of reducing acids, hydrofluoric acid and stress-corrosion cracking, particu-
larly in chlorides and caustic environments. It forms a stable oxide in weak alkaline
solutions even at high anodic potentials but fails in acidic solutions. Other elements
are added to form protective, stable oxides under acidic and oxidizing environments.
From the corrosion perspective, the major alloying additions are chromium, copper,
molybdenum, tungsten, niobium, and iron. Each element imparts resistance against a
specific form of corrosion or media, in addition to their role in improving mechanical
properties. The following gives a brief description of the role of alloying addition
that contributes to the corrosion resistance of Alloy 625.
Chromium—Chromium provides resistance to the alloy in oxidizing environ-
ments and high-temperature oxidation and sulfidation by forming a layer of passive
Cr2 O3 film. However, this film cannot protect the alloy from pitting and crevice
corrosion under harsh conditions and protects only in the presence of molybdenum.
In oxidizing environments, a higher chromium content imparts a higher corrosion
resistance, particularly at concentrations above 20 wt%. At high temperatures, the
protective nature of the oxide film decreases due to an increase in its crystallinity.
Molybdenum—Chemically, molybdenum behaves similar to chromium but is
less resistant against oxidizing solutions. It dissolves quickly by converting to its
hexavalent species. However, its addition improves the resistance of the alloy in
reducing media like hydrochloric acid and pitting and crevice corrosion in aqueous
chloride-containing environments. In combination with chromium, it provides resis-
tance in extremely versatile environments of both oxidizing and reducing chemicals.
It improves the stability of the Cr2 O3 film by protecting it by forming a Mo-rich outer
layer of molybdate ions. Molybdate ions protect the film by inhibiting the initiation
and propagation of localized corrosion and promoting re-passivation.
Iron—Iron does not play any significant role in the corrosion resistance of Alloy
625, except for its small contribution to the resistance to certain concentrated sulfuric
and nitric acids and high-temperature carburizing environments.
Niobium—Niobium forms a stable pentavalent oxide, but its maximum concen-
tration in Alloy 625 is too low to form a complete oxide layer. However, its addition
helps in reducing the susceptibility of the alloy to intergranular corrosion as carbon
prefers to combine with niobium to form more stable carbide particles. Likewise, it
also improves the resistance to pitting and crevice corrosion.
Aluminum–Aluminum addition improves the resistance to oxidation at elevated
temperatures.
Titanium—Titanium plays a role similar to niobium in enhancing corrosion resis-
tance by combining with carbon to reduce the alloy’s susceptibility to intergran-
ular corrosion due to the precipitation of chromium carbide particles during heat
treatments.
Nitrogen—Nitrogen improves pitting and crevice corrosion resistance, but it is
usually restricted to a very low level of about less than 50 ppm due to its other
attended effects.
Rare Earth elements—Sometimes, rare earth elements like yttrium, lanthanum
and cerium are also added in very small quantities to improve high temperature and
hot corrosion resistance.
7.3 General Corrosion 247
7.3 General Corrosion
Several solution-dependent and material-dependent factors determine general or

uniform corrosion in aqueous media. Solution-depending factors like density, temper-
ature, pH value, and electrochemical potential of the solution govern the aggres-
siveness of the corrosive media as they influence the solubility and dissociation
of attacking anions and corrosion products. High values of both parameters favor
ionic reactions and thus, accelerate the corrosion process. Material-dependent factors
include parameters like alloy composition, surface condition, material purity, heat
treatment, etc. which primarily influence corrosion initiation.
7.3.1 Hydrochloric Acid
Hydrochloric acid is a reducing acid across its entire concentration range. Its strongly
acidic character and the harmful effect of chloride ions make it a severe corrosive
medium. The presence of oxidizing contaminants (e.g., ferric or cupric ions) can
drastically change the corrosive characteristics of hydrochloric acid. Alloy 625 has
good resistance to dilute hydrochloric acid due to its 9 wt% molybdenum content.
The general corrosion resistance of the alloy in hydrochloric acid is summarized
in the iso-corrosion chart (Fig. 7.3) as a function of acid concentration at different
temperatures [2]. Figure 7.4 compares 20 mpy iso-corrosion lines of Alloy 625
with other Ni–Cr–Mo alloys in the hydrochloric acid [2]. Alloys C-276 and 686
Fig. 7.3 Iso-corrosion lines

depict the corrosion
behaviour of Alloy 625 in
hydrochloric acid as a
function of temperature and
acid concentration [2]

the corrosion behaviour of
nickel–chromium alloys in
hydrochloric acid as a
function of temperature and
acid concentration. The
figure shows iso-corrosion
lines corresponding to a
corrosion rate of 20 mpy [2]
exhibit nearly similar resistance in hydrochloric acid due to similar molybdenum

and tungsten contents. The two alloys exhibit corrosion resistance better than Alloy
625 due to higher molybdenum content and extra addition of tungsten, which also
behaves in the same manner as molybdenum in improving corrosion resistance in
reducing chemical solutions. Alloys like 825 and 25-6MO, on the other hand, exhibit
low corrosion resistance. Adding the oxidizing species like Fe3+ ions may decrease
the corrosion rate of the Alloy 625 [3].
7.3.2 Sulfuric Acid
Sulfuric acid has a dual nature. It behaves as reducing acid in dilute and interme-
diate concentrations, up to about 25 wt% [2]. At higher concentrations, it starts
acting as oxidizing in nature. At concentrations above 87 wt%, a concentration most
commonly encountered in a commercial product is strongly oxidizing in nature at
room temperature [2]. The nature of the sulfuric acid may further vary depending
upon aeration, temperature and nature of impurities present. With an increase in
temperature, it becomes more oxidizing. Therefore, materials resistant to reducing
media are preferred for sulfuric acid in dilute and intermediate concentrations, while
materials resistant to oxidizing conditions are preferred for higher concentrations of
sulfuric acid. Ni–Cr–Mo alloys like C-22, 625 and 686 show excellent resistance to
sulfuric acid, particularly in a hot environment, due to their high molybdenum and
chromium contents. Alloy 625 offers even better resistance due to the presence of
Fig. 7.5 Iso-corrosion lines depict the corrosion behaviour of Alloy 625 in sulphuric acid as a
function of temperature and concentration [3]
niobium. Figure 7.5 shows the general corrosion behavior of Alloy 625 as a function
of acid concentration and temperature [3]. Its corrosion resistance deteriorates at
higher concentrations of the acid.
Figure 7.6 compares the 20 mpy iso-corrosion plots of C-276, 625, G-3, 825
and SS 316 alloys in sulfuric acid [2–4]. At lower concentrations, Alloy 625 shows
resistance similar to that of Alloy C-276.
7.3.3 Nitric Acid
Nitric acid is strongly oxidizing in nature. Since the resistance to nitric acid is essen-
tially due to the formation of a passive film on the surface, alloys with high chromium
offer the best resistance in a nitric acid environment as they quickly form the passive
Cr2 O3 film. Among nickel-based superalloys, Alloy 690 exhibits the least corrosion
rate of about 0.03 mpy (Fig. 7.7) [2] as it contains the highest chromium content
(~30 wt%). The performance of Ni–Cr–Mo alloys in nitric acid is strongly related
to their chromium content only. Therefore, Alloy 625 offers much better corrosion
resistance than Alloy C-276 by virtue of the higher chromium concentration in Alloy
625. Therefore, alloys with higher chromium concentrations provide better resistance
than those with lesser content. Iron addition in nickel alloys improves their resistance
in the nitric acid, as demonstrated by the reduced corrosion rate of Alloy 825, which
Fig. 7.6 Comparative corrosion behaviours of Alloy 625, C-276, 825, G-3 and 316 stainless steel
corresponding to 20 mpy corrosion rate in sulphuric acid solutions as a function of concentration
and temperature [3]
Fig. 7.7 Average corrosion

rates of some nickel alloys in
boiling 10% nitric acid
solution [2]
Fig. 7.8 A comparison of the corrosion rates of different high-performance alloys in 10 M HNO3 —
0.01 M HF and 10 M HNO3 —0.1 M HF solutions [2]
contained nearly identical chromium content as that in Alloy 625 (Fig. 7.7). In boiling
65% nitric acid, Alloy 625 exhibits a corrosion rate of about 30 mpy [2].
In general, stainless steels perform better than most nickel-base alloys in nitric
acid. Nickel alloys are more effective in resisting corrosion in mixed acid media. The
nickel alloys are typically used in nitric acid solutions that contain small amounts of
chlorides or fluorides from other sources like hydrofluoric acid, chlorinated water,
etc. For example, in a boiling 15% nitric acid solution containing 3% hydrofluoric
acid solution, AISI 316 stainless steel corrodes at a rate of about 236 mpy, Alloy
625 corrodes at a rate of about 34 mpy [2]. Figure 7.8 shows a comparison of the
corrosion behavior of Alloy 625 with other alloys in 10 M HNO3 – 0.01 M HF and
10 M HNO3 – 0.1 M HF solutions [2]. Alloy 625 exhibits much better corrosion
resistance than iron-chromium and other Ni–Cr–Mo alloys.
7.3.4 Hydrofluoric Acid
Hydrofluoric acid is considered a reducing acid and chemically weaker than sulfuric
or hydrochloric acid [5]. However, it is extremely corrosive and toxic in nature and
hazardous to health than most acids. Further, unlike other acids, the hydrofluoric acid
usually attacks in a non-uniform manner and mainly penetrates the metal surface in
the form of thin cracks, pits, voids, trenches and sometimes on grain boundaries
[5] as it readily dissolves the passive oxide films that protect against corrosion.
Figure 7.9 schematically illustrates this behavior of the hydrofluoric acid. Standard
Fig. 7.9 The schematic

illustrates the non-uniform
attack and penetration of the
hydrofluoric acid into the
metal surface
acid-resistant materials, like titanium, zirconium, reactive metals, etc. or glass, are not
suitable for resistance against hydrofluoric acid solutions. Non-metallic materials like
polythene are the best. Among metals, only gold and platinum are entirely resistant
to attack in aqueous hydrofluoric acid solutions.
Nickel alloys offer moderate corrosion resistance to hydrofluoric acid over many
wet acid concentrations and temperatures. Chromium and copper additions in nickel
alloys are beneficial for vapor phase applications, while the iron is detrimental.
Monel 400 is among the few alloys that offer good corrosion resistance to aqueous
hydrofluoric acid [2]. A comparison of the corrosion resistance of Alloy 625 with
Monel 400 and some other nickel alloys in non-deaerated hydrofluoric acid is shown
in Fig. 7.10 [6].
7.3.5 Phosphoric Acid
Pure phosphoric acid has no adequate oxidizing power and is not very aggressive.
Industrial phosphoric acid, also known as wet-process acid, is made by reacting
the phosphate rock with sulfuric acid and is quite oxidizing in nature and corrosive
due to the presence of impurities like various metallic ions, unreacted sulfuric acid,
fluorides and chlorides. The corrosivity of the wet process acid is not directly related
to the concentration of the P2 O5 compound because an increase in the concentration
of the P2 O5 compound decreases the concentration of impurities. The corrosivity of
the wet process acid is maximum at a concentration between about 42 and 54 wt% of
P2 O5 [5]. The most commonly used nickel alloys for aggressive and hot phosphoric
acid environments are G-30, 625, C-22, C-276 and 686 alloys. Figure 7.11 shows
the corrosion rate of Alloy 625 as a function of temperature in 42 wt% wet-process
phosphoric acids compared to some other nickel alloys [5]. These alloys owe their
excellent corrosion resistance in the phosphoric acid to their high chromium and

the 20 mpy iso-corrosion
curves for different
nickel-based superalloys and
316L stainless steel in
hydrofluoric acid solution [6]

corrosion rate with
temperature in 42%
wet-process phosphoric acid
[5]
molybdenum contents and the small amounts of niobium or tungsten additions. In a

solution of 25 wt% phosphoric and 2 wt% hydrofluoric acids, at boiling temperature,
Alloy 625 corroded at a rate of about 2 mpy in a 48 h test [2]. More extended tests
in different concentrations of evaporating wet-process phosphoric acid, containing
various acid impurities, showed very low rates and no localized attack [2]. Alloy 625
is generally used for 70 wt% wet phosphoric acids [5].
7.3.6 Organic Acids
Organic acids are less corrosive than inorganic acids because they do not ionize easily
[7] though aeration and temperature may increase their corrosivity. Acetic, formic,
propionic, butyric, and sulphonic acids are among the important organic acids. With
a few exceptions, organic acids are weak and non-oxidizing. Alloy 625 has excellent
resistance to organic acids. In boiling acid solutions, Alloy 625 exhibits corrosion
rates of < 1 mpy in glacial acetic, ~ 4 mpy in 1:1 acetic-acetic anhydride solution, ~
1 mpy in 10% acetic + 2% formic solution, 3 mpy in 5% formic acid solution [2].
The relative corrosion behavior of Alloy 625 in 40% and 88% formic acid solutions,
compared to some other similar alloy, is shown in Fig. 7.12 [5]. It exhibits the highest
corrosion rate of about 9.1 mpy in 40% boiling methane sulphonic acid. However,
the corrosion rate of Alloy 625 is much lower than the corrosion rates of other similar
alloys (Table 7.1) [4].
Fig. 7.12 Corrosion

behaviour of alloys 625,
C-276 and 825 in 40 and 88
wt% boiling formic acid [5]
Table 7.1 Corrosion rates of different Ni–Cr–Mo alloys in methane sulphonic acid environments
(all concentrations are in wt%) [4]
Acid condition Corrosion rate of alloys (mpy)
Alloy 625 Alloy C-22 Alloy C-2000 Alloy G-30
20% boiling 5.5 36 23 30
40% at 93 °C 4.0 < 0.4 < 0.4 < 0.4
40% boiling 9.1 80.4 32 33
70% at 79 °C 0.4 < 0.4 < 0.4 < 0.4
7.3.7 Salts
Corrosion in salt solutions is more pronounced than in pure water because the salt’s
dissolution in water increases its conductivity. Salts can be broadly categorized into
two categories, namely, halides and non-halides, each of which is further classified
into different categories based on the nature of their solutions (Table 7.2). Halide salts
are very damaging because of their insidious and unpredictable nature, leading to
premature failure of components. Chlorides are most common among the halide salts
and promote stress-corrosion cracking, pitting and crevice attack. Fluoride salts are
less common but more harmful to reactive metals like titanium, zirconium, niobium,
etc. Figure 7.13 shows the effect of different sodium halides at 50 °C on the re-
passivation potential of Alloy 625 and other Ni–Cr–Mo alloys [5]. The re-passivation
potential directly measures the localized corrosion resistance, and a higher value
of the re-passivation potential means more resistance. The strong effect of sodium
chloride on the resistance of Ni–Cr–Mo alloys to localized corrosion is reflected in a
significant change in their re-passivation potential with a change in the alloy compo-
sition. In contrast, minimal change in the re-passivation potential occurs in sodium
iodide or fluoride solutions (Fig. 7.13). Higher values of the re-passivation poten-
tial for alloys containing higher chromium and molybdenum signify their benefits
against localized corrosion in sodium chloride solutions.
High contents of molybdenum and chromium in Alloy 625 makes it very resistant
to pitting and crevice corrosion in all classes of salts. The addition of niobium along
with chromium and molybdenum in the alloy gives it an excellent resistance to
stress-corrosion cracking and intergranular corrosion in aqueous salt solutions at
high temperatures. For example, a U-bent Alloy 625 specimen, subjected to 45%
magnesium chloride solution for various exposure periods, does not show evidence
of cracking [2]. Alloy 625 exhibits corrosion rates less than 4 mpy across multiple
salt environments at temperatures up to 235 °C for durations up to 200 h [2].
Table 7.2 Classification of salts based on the corrosive nature of their solutions [2]
Nature Halide Non-halide
Neutral Sodium-chloride Sodium-sulfate
Potassium-chloride Potassium-sulfate
Neutral and Sodium-hypochlorite Sodium-nitrate
Alkaline-oxidizing Calcium-hypochlorite Sodium-nitrite
Potassium-permanganate
Acid Magnesium-chloride Potassium-bisulphate
Ammonium-sulphate
Aluminum-sulfate
Acid-oxidizing Cupric-, ferric-, mercuric-, Cupric-, ferric-, mercuric-nitrate
stannic-chloride or sulfate
Alkaline Potassium fluoride Sodium- and potassium-
phosphates and carbonates
Nature Halide Non-halide
Neutral Sodium-chloride Sodium-sulfate
Potassium-chloride Potassium-sulfate
Neutral and Sodium-hypochlorite Sodium-nitrate
Alkaline-oxidizing Calcium-hypochlorite Sodium-nitrite
Potassium-permanganate
Acid Magnesium-chloride Potassium-bisulphate
Ammonium-sulphate
Aluminum-sulfate
Acid-oxidizing Cupric-, ferric-, mercuric-, Cupric-, ferric-, mercuric-nitrate
stannic-chloride or sulfate
Alkaline Potassium fluoride Sodium- and potassium-
phosphates and carbonates
7.3.8 Seawater
Seawater contains a vast amount of chlorine which makes passive metals prone to
general and localized corrosion. Alloy 625 is one of the best alloys for applications in
seawater or marine environments owing again to its high chromium and molybdenum
contents. It is placed very close to noble metals compared to most other alloys in the
seawater galvanic series (Fig. 7.14) [2, 8, 9]. It behaves mainly as a cathode when
in contact with other materials in seawater. Under stagnant and flowing conditions,
it shows extremely low (negligible) weight loss in seawater [2]. Its high chromium
and molybdenum content also give it excellent resistance against pitting corrosion,
crevice corrosion and stress corrosion cracking. Figure 7.15 compares the corrosion
fatigue strength of Alloy 625 with other alloys in seawater. Alloy 625 and its low
cycle fatigue (LCF) variant (Alloy 625LCF) both exhibit excellent corrosion fatigue
strength in seawater (Fig. 7.15) [10]. The two variants have the same chemical compo-
sition and mechanical properties. Still, the LCF variant has better cyclic and thermal
fatigue properties due to a tighter control of the trace elements like carbon, silicon,
Fig. 7.13 Re-passivation potentials for different Ni–Cr–Mo alloys in 1 M solution each of NaF,
NaI, NaCl and NaBr (Cyclic potential at 50 °C and 0.5 mV/s) [4]
and nitrogen during manufacturing of the alloy. The corrosion fatigue strength is an
essential parameter for metals subjected to cyclic stress in corrosive environments
as the joint action of corrosion and fatigue greatly intensifies the damage.
7.3.9 Alkaline Solutions
Alkaline environments refer to environments with a pH > 7.0. These environments

are basic in nature due to the presence of alkali components and are less corrosive
than acidic environments. However, alkaline environments can be very corrosive in
the presence of dissolved oxygen. A higher amount of chromium in alloys for alkaline
solutions is always beneficial. In alkaline environments, corrosion may often cause
pitting and other localized attacks when the attack is concentrated at susceptible
anodic areas. Increasing the nickel amount generally improves the resistance to attack
in alkaline solutions. The most commonly used nickel alloys for alkaline solutions are
Nickel 200, Alloy 400, Alloy 600 and Alloy 625. All these alloys show corrosion rates
of < 1 mpy in boiling 50% caustic (NaOH) solution when tested at 720 h [2]. However,
oxidizing species may cause preferential de-alloying of molybdenum in Ni–Cr–Mo
alloys [11, 12]. Figure 7.16 shows the general corrosion rates of some nickel-alloys
in electrolyte solutions of pure sodium hydroxide (NaOH) and 50% caustic soda
contaminated with 500 ppm ferric ions (Fe3+ ), 1% sodium hypochlorite (NaOCl)
and 1% sodium chlorate (NaClO3 ) [13] oxidizing species. Nickel 200 exhibited
Fig. 7.14 Galvanic series of

high-performance alloys in
seawater [2]

corrosion fatigue strength
with ultimate tensile
strengths of alloys in
seawater [2]
Fig. 7.16 a General corrosion and b internal damage as crack or dealloying in some Ni-alloys
in electrolyte solutions of pure NaOH and 50% caustic soda contaminated with oxidizing species
such as 500 ppm ferric ions (Fe3+ ), 1% sodium hypochlorite (NaOCl) and 1% sodium chlorate
(NaClO3 ) [13]. The alloys containing high Mo exhibited the highest corrosion rate in contaminated
electrolytes
the lowest corrosion rate among the tested alloys, and the B-3 alloy exhibited the
highest. In general, alloys containing a high amount of molybdenum suffered high
corrosion rates due to its de-alloying [12, 14]. The corrosion damage was due to
internal penetration of the media. For the Nickel 200 alloy, the internal penetration
was restricted mainly to surface roughening, while in molybdenum-containing alloys
(C-276, 22, B-3), it caused de-alloying and some intergranular attacks [13]. In Alloy
600, the internal penetration resulted in surface roughening, cracks, fissures and
intergranular attack. The depth of internal attack increased with the temperature
[13]. The sub-surface microstructure of molybdenum de-alloyed alloys typically
shows a spongy nickel layer of the leftover de-alloyed alloy matrix, covered by an
outer layer of pure nickel formed as a result of the re-precipitation of the previously
dissolved nickel [13]. Potassium hydroxide is reportedly less aggressive than sodium
hydroxide concerning de-alloying [11].
7.4 Localized Corrosion
Localized corrosion is an accelerated attack at discrete sites when the anodic areas on
a metal surface remain stationary, rather than mobile, under certain conditions. The
metal at the localized sites corrodes much faster than the rest of the metal surface.
Once initiated, the attack is stabilized by the development of localized aggressive
conditions resulting from metal cation hydrolysis and chloride migration. The local-
ized attack is insidious as it may fail the component prematurely without any warning.
Typical forms of localized corrosion include pitting on an exposed non-corroding
surface and corrosion in a creviced region shielded from the bulk environment. An
exciting form of localized corrosion is microbially induced corrosion (MIC), of both
pitting and crevice type. MIC is caused by bacteria of various types that live and
multiply in standing water at places like pits, grain boundaries, weld undercuts,
inside walls of pipes and tubing and other metallic structures. Ni–Cr–Mo alloys are
generally immune to the microbially induced corrosion attack.
Alloys containing chromium and molybdenum are usually more resistant to local-
ized corrosion. The relative resistance of an alloy against localized corrosion can be
measured based on parameters like pitting resistance equivalency number (PREN),
critical pitting temperature (CPT) and critical crevice temperature (CCT). PRENs
for nickel- and iron-based superalloys are empirically calculated based on their
molybdenum, chromium, tungsten, niobium and nitrogen concentrations (in wt%)
as [2]:
PREN = %Cr + 1.5 (%Mo + %W + %Nb) + 30 (%N) (7.6)
A higher value of PREN is indicative of superior resistance of the alloy to localized

corrosion, though alloys having similar values may differ considerably in actual
service. Table 7.3 compares the PREN of Alloy 625 with some similar corrosion-
7.4 Localized Corrosion 261
Table 7.3 Pitting resistance equivalency number (PREN), critical pitting temperature (CPT) and
critical crevice temperature (CCT) of Alloy 625 and some other corrosion-resistant alloys
Alloy Composition (wt%) PREN CPT (°C) CCT (°C)
Ni Cr Mo W Nb N
316 stainless steel 12 17 2.2 – – – 20.4 20 <0
Alloy 825 42 21.5 3 – – – 26.0 30 5
Alloy 25-6MO 25 20 6.5 – – 0.20 35.8 70 30
Alloy 625 62 22 9 – 3.5 – 40.8 > 85 35
Alloy C-276 58 16 16 3.5 – – 45.2 > 85 45
Alloy C-22 60 20.5 14 3.5 – – 46.8 > 85 > 85
Alloy 686 58 20.5 16.3 3.5 – – 50.8 > 85 > 85
PRENs are estimated using Eq. 7.6. CPT and CCT were determined by ASTM G-48 standard tests,
methods C and D, respectively [2]
resistant superalloys. All nickel alloys with a PREN greater than 40 are resistant to
crevice corrosion in seawater. Alloy 625 has a PREN value of about 40.8.
The critical pitting/crevice temperature refers to the temperature above which
pitting/crevice for an alloy occurs in a specific environment. The higher the CPT or
CCT, the more resistant the alloy is to pitting or crevice corrosion.
7.4.1 Pitting Corrosion
Pitting corrosion occurs when the passive film breaks down locally in corrosive
environments, making the localized sites anodic. The locally exposed metal corrodes
much faster than the rest of the surface. When this occurs, corrosion takes the form
of pits rather than uniform thinning. Although pitting can occur for various reasons,
like a local variation in concentration or defects, certain chemicals such as chloride
salts are known to promote pitting. The passive metals are particularly susceptible
to pitting in chloride environments. The accumulation of chloride ions dissolves the
passive film locally, resulting in pit formation. The pit initiation events are relatively
scarce and stochastic in nature. The exact time and location of the passive film
breakdown cannot be predicted. Once pits are initiated, they grow very fast because
of the continuous change in the local chemistry that moves the interface rapidly.
The pitting corrosion occurs at temperatures above a critical pitting temperature,
which depends on material factors like alloy composition, impurities concentrations,
surface condition, and solution chemistry, such as chloride ion concentration, pH
value, and electrochemical potential. The oxidizing chlorides (e.g., FeCl3 , CuCl3,
etc.) are the most aggressive pitting agents. The non-oxidizing chlorides (e.g., NaCl)
reduces oxygen at the cathode.
Pitting is an autocatalytic process in which the corrosion products promote further
corrosion reactions [1]. Figure 7.17 illustrates the autocatalytic nature of a pit in an
Fig. 7.17 The autocatalytic mechanism of pitting corrosion
oxygenated NaCl electrolyte. The pit is the anode, and the metal surface is the
cathode. The production of positive metal ions in the pit gives a local excess of
positive charge, which attracts the negative chlorine ions from the electrolyte to
maintain neutrality and produce neutral MCl molecules resulting in increased MCl
concentration. “M” refers to metal in MCl. MCl hydrolyzes in water and forms
insoluble MOH and free acid (H+ and Cl− ). Both H+ and Cl− ions accelerate metal
dissolution. Increased dissolution increases Cl− ion migration making the process
self-stimulating and self-propagating (Fig. 7.17).
Alloy 625 possesses excellent resistance against localized corrosion in sulfur
dioxide scrubbing environments containing ppm levels of chloride ions. Figure 7.18
shows the resistance of Alloy 625 to localized corrosion as a function of the pH
level of the sulfur dioxide containing part-per-million (ppm) levels of chloride ions
[15]. The areas below the line for each alloy represent the combination of pH and
chloride ion content below which severe pitting is not observed. Alloy 625 possesses
the pitting corrosion resistance much superior to many other alloys.
The critical pitting temperature (CPT) of an alloy depends upon the service envi-
ronment and conditions. It can be determined experimentally using ASTM Standard
Test Method G-48, Method C. In this method, the alloy is immersed in a standard
Fig. 7.18 The resistance of

Alloy 625 to localized
corrosion as a function of the
pH level of the sulphur
dioxide containing ppm
levels of chloride ions [15]
acidic 6 wt% ferric chloride solution at a set temperature for test durations from 24 to
72 h. The test temperature is raised incrementally until the onset of pitting. New and
unexposed samples are exposed in new test solutions at each test temperature. Table
7.3 compares the CPT of Alloy 625 with some other alloys. A significantly improved
CPT of nickel alloys compared to iron-base alloys, stainless steels, and nickel alloys
containing higher molybdenum can be noticed. Thus, Alloy 625 is more resistant to
pitting than Alloy 825 or AISI 316 stainless steel.
7.4.2 Crevice Corrosion
Crevice corrosion is another form of localized attack and, as the name implies, occurs
within crevices formed in between overlapping sections of metallic or non-metallic
structures. Like pitting corrosion, it is also hard to detect by exterior examination. It
occurs due to the formation of differential ion concentration or oxygen cells. Halide
salts promote both mechanisms. Initially, corrosion reaction occurs uniformly over
the entire surface, including the interior of a crevice. Every electron generated during
the formation of metal ions is consumed by the oxygen reduction reaction (Eq. 7.3)
and produces one hydroxyl ion in the solution to maintain charge neutrality. However,
the oxygen in the crevice is depleted after some time because of restricted convec-
tion, which becomes more pronounced with time. No further oxygen is available
after finishing oxygen, although the metal dissolution continues as Eq. 7.1 [1]. The
continued dissolution produces an excess of positive charge, balanced by the migra-
tion of chloride ions into the crevice. This results in an increased concentration
Fig. 7.19 A schematic drawing illustrating the autocatalytic nature of crevice corrosion [1]
of chloride ions within the crevice. Hydroxyl ions also migrate, but they are less
mobile than chloride ions and migrate slowly. Metal salts hydrolyze in water to form
insoluble hydroxide and free acid, according to the reaction
M+ Cl− + H2 O = MOH + H+ Cl− (7.7)
Both chloride and hydrogen ions increase the metal dissolution rate within the
crevice. This makes the crevice corrosion an autocatalytic reaction. A schematic
representation of the crevice corrosion is shown in Fig. 7.19.
Molybdenum plays a vital role in resistance against crevice corrosion. Even highly
corrosion-resistant alloys without molybdenum may incur crevice corrosion. For
example, Alloy 690 containing about 29% chromium has an excellent resistance
against chloride stress-corrosion cracking owing to its high chromium contents. Still,
it exhibits crevice corrosion in coastal zones over prolonged periods [16]. Alloy
625 containing molybdenum provides a better resistance against crevice despite its
chromium concentration being less than Alloy 690. Nonetheless, Alloy 625 is not
entirely immune to the crevice attack. For example, Alloy 625 tubes suffered crevice
corrosion under vinyl hoses secured with serrated nylon hose clamps as part of a
flow loop containing chlorinated seawater [17]. This behavior has been attributed to
adding extra chlorine to the seawater, which raised the alloy’s potential to the point
that crevice corrosion initiated.
Like, CPT for pitting corrosion, critical crevice temperature (CCT) for an alloy is
determined by conducting a test as per ASTM Standard Test Method G-48, Method
D. This test is similar to the Method G-48, Method C test for the CPT. It uses a
multiple crevice device (TFE-fluorocarbon washer) attached to the surface of the

specimen. Table 7.3 also gives the CCT of Alloy 625 with other alloys.
7.4.3 Intergranular Corrosion
Intergranular corrosion (IGC) is a localized attack along the grain boundaries of

a metal or alloy. Corrosion can proceed to the point where whole metal grains fall
away, and the metal loses its strength and metallic characteristics. A schematic repre-
senting the IGC attack is shown in Fig. 7.20. Intergranular corrosion is usually
caused by improper heat treatment or in the heat-affected welding zones when
chromium carbide particles precipitate along grain boundaries. The precipitation
of grain boundary carbides creates chromium depleted zones in the vicinity of
boundaries (Fig. 7.20a). This phenomenon is commonly known as sensitization.
For instance, heating of an 18–8 stainless steel (AISI 304 grade) at temperatures
between about 425 and 750 °C causes the precipitation of chromium carbide at the
grain boundaries, which depletes chromium from the matrix in the vicinity of grain
boundaries [1]. This makes the chromium depleted area anodic with respect to the
rest of the grain. Sensitization of an alloy makes it susceptible to intergranular attack
and may cause failure along grain boundaries (Fig. 7.20b).
Alloy 625 is stabilized against intergranular attack by tying up the carbon with
niobium as niobium carbide, making it less available to precipitate as chromium
carbides at grain boundaries. However, the alloy may become susceptible to inter-
granular attack due to improper annealing treatments that inhibit the formation of
niobium carbides, leaving carbon available for precipitation as chromium carbides
Fig. 7.20 Schematic drawings depict inter-granular corrosion of a metal. a Sensitization of the
metal due to the formation of chromium depleted zone along grain boundaries. b Intergranular
failure of the metal along weakened grain boundaries
Fig. 7.21 The corrosion

behaviour of sensitized
Alloy 625 in boiling 65%
nitric acid after 1 h. Alloy
samples were first subjected
to annealing treatments at a
temperature between 925
and 1050 °C, followed by
sensitization treatments at
temperatures between 700
and 875 °C [18]
by a subsequent heat treatment in the temperature range over 650–816 °C. Solu-
tion annealing increases the alloy’s susceptibility to sensitization in this temperature
range. Figure 7.21 shows the intergranular corrosion behavior of Alloy 625 due
to sensitized grain boundaries [18]. Alloy samples were annealed at temperatures
between 925 and 1205 °C for 1 h and water quenched. Samples were then subjected
to sensitizing heat treatments at temperatures 704, 760, 816 and 871 °C for 1 h to
precipitate out chromium carbides precipitates along grain boundaries, followed by
air cooling. Annealed and sensitized samples were subjected to boiling 65% nitric
acid as per the standard ASTM A262 test. The alloy exhibited the maximum sensi-
tization at 760 °C for all the samples annealed in the range 1093–1204 °C as they
displayed the highest corrosion rate. Samples annealed at 982 °C showed the lowest
corrosion rate, followed by sample annealed at 927 °C. Low corrosion rates at temper-
atures less than 1050 °C were due to the precipitation of MC and M6 C carbides that
contain niobium and molybdenum predominantly. During annealing at 927 and 982
°C temperatures, the MC and M6 C carbides bound the free carbon with niobium and
molybdenum, leaving little carbon for chromium to interact during the subsequent
sensitizing heat treatment at temperatures in the range 704–871 °C. As a result, little
or no precipitation of chromium carbides occurred at grain boundaries during the
sensitization treatment. A comparatively higher corrosion rate of the alloy annealed at
927 °C compared to that annealed at 982 °C could be attributed to the precipitation of
higher volume fractions of the MC and M6 C carbides in the latter owing to the faster
precipitation kinetics at this temperature (see, Fig. 3.20 in Chap. 3). When the alloy is
annealed at temperatures above the solution annealing temperature, carbides particles
dispersed throughout the matrix dissolve leaving free carbon in the matrix. When such
solutions are exposed to sensitization temperatures, chromium-containing carbide

precipitates preferentially along grain boundaries. Formation of the grain carbides
results in continuous chromium depleted zones along grain boundaries which are
susceptible to attack by oxidizing media.
7.5 Corrosion in High Temperature Pressurized Waters
The high-temperature water is described as (i) steam, when T < T c (sometimes may
be above T c also) and p < pSaturation ; (ii) subcritical water, when T < T c and p >
pSaturation (sometimes may be above pc also) (iii) supercritical water, when T > T c ;
p > pc , where T c (= 374 °C) and pc (= 22.05 MPa) are critical temperature and
pressure of the water above which it becomes supercritical [19–21]. Supercritical
water is also described as a dense gas. Its density is between the liquid and gaseous
states of the water and is characterized by high diffusivity and good heat-transporting
properties.
The physical properties of pressurized high-temperature water vary significantly
with temperature and pressure [22]. The density and ionic product of the high-
temperature water drop drastically in the vicinity of T c (Fig. 7.22). With increased
pressure, this drop shifts toward a higher temperature with a reduced magnitude.
The solvent character of the high-temperature water may vary from highly polar at
high densities to nearly non-polar at low densities. The low-density water suppresses
Fig. 7.22 Variation in density and ionic product of water as a function of temperature at different
pressures. The two properties drop drastically in the vicinity of the critical temperature, T c . The
drop shifts towards higher temperatures at higher pressures [22]
ionic reactions and favors radical reactions. Steam and low-density supercritical water
thus behave like non-polar solvents with low solvency for ionic compounds. On the
other hand, high densities favor the solubility and the dissociation of ionic species like
salts, acids, and bases. The supercritical high-density water thus possesses complete
solvency for most gases and organic compounds [23]. As a result, organic and inor-
ganic materials containing corrosive agents like chlorine, sulfur, phosphorous, etc.
react and dissolve immediately to form one single phase.
Aqueous corrosion in ambient conditions is due to ionic reactions. In acidic solu-
tions at ambient conditions, the corrosion resistance of nickel–chromium alloys is
generally due to the formation of thermodynamically stable protective Cr2 O3 film
(Cr3+ compound). At a temperature > ~ 100 °C, the solubility of oxygen in water,
and consequently the oxidizing power of the solution, increases with temperature
(Fig. 7.23) [22] At the same time, the resistance of Cr3+ oxide against oxidation
decreases by the formation of soluble Cr4+ compounds [24], which makes the film
unstable above a specific temperature and result in its transpassive dissolution. This
instability is different from the local attack on Cr2 O3 film by halide ions at low
temperatures. Alloy 625 exhibits a similar tendency to change from pitting corrosion
to uniform corrosion in subcritical water [22].
Figure 7.24 illustrates the electrochemical and chemical dissolution behavior of
nickel–chromium alloys in high-temperature solutions. Chromium is more stable
against the acidic solution, while nickel tolerates better oxidizing conditions. When
the solution density is high, the concentration of H+ ions is high (low pH values) as
Fig. 7.23 A schematic representation of the variation in the electrochemical potential as a function
of temperature for the formation of soluble chromate in acidic and alkaline solutions [22]
7.5 Corrosion in High Temperature Pressurized Waters 269
Fig. 7.24 Schematic electrochemical potential and pH value map of the stability of chromium and
nickel oxide films on nickel–chromium alloys in high-temperature water solutions. Increasing the
electrochemical potential at low pH values dissolves chromium electrochemically as chromate.
At the same time, it makes nickel chemically unstable, which dissolves as soluble Ni2+ aqueous
complexes. On the other hand, a subsequent increase of the pH value at high potentials NiO becomes
stable above a specific pH value. Therefore, at high electrochemical potentials and high pH values,
NiO provides the protective film [22]
essentially acids dissociate in the high-temperature dense water. An increase in the

electrochemical potentials results in the electrochemical dissolution of chromium
as chromates while nickel dissolves as soluble Ni2+ aqueous complexes [22]. On
the other hand, high pH values at high potentials stabilize the NiO phase, forming
a protective layer. A situation with a high pH value may arise when OH– ions are
added to the solution from an external source or the dissociation of acid reduces.
When the water passes from subcritical to supercritical water conditions, a drop in
the solution density reduces the dissociation of acid. No oxide is stable when the
pH is low, and the potential is high, and, in such situations, the alloy will undergo
general corrosion.
The high temperature also affects the pitting corrosion behavior of the alloy. With
increasing temperature, the pitting potential decreases due to decreasing protective
character of the oxide film [25, 26]. Still, it reaches a level at which it stays constant
above a specific temperature, and the alloy is no more susceptible to pitting. This
temperature is called the inversion temperature [27]. The inversion temperature may
vary significantly with the chloride media. For instance, the inversion of the Alloy 625
in a sodium chloride solution containing 0.1 mol/kg of NaCl is 150 °C [26], while in
a hydrochloric acid solution containing 0.05 to 0.2 mol/kg of the acid is above 250 °C
[28]. The morphology of corrosion pits at low temperatures is typically hemispherical
[22]. At the inversion temperature, corrosion morphologies change from isolated
hemispherical pits at low temperatures to shallow interconnected pits covering the
entire surface at higher temperatures [22], similar to the general corrosion. Some
authors attributed this transition to a change in the characteristics of the oxide film,
while others attributed it to its transpassive dissolution [22].
7.5.1 Acidic High-Temperature Waters
Kritzer et al. [22] have done an exhaustive review of Alloy 625 corrosion behavior in
strongly oxidizing and pressurized high-temperature solutions of many acids. These
solutions comprised solutions of hydrofluoric acid (HF), hydrochloric acid (HCl),
hydrobromic acid (HBr), sulfuric acid (H2 SO4 ), nitric acid (HNO3 ) and phosphoric
acid (H3 PO4 ) in the concentration range over 0.05 mol/kg to 1.0 mol/kg, and oxygen
concentrations from 0.5 mol/kg to 3.6 mol/kg.
At temperatures up to about 100 °C, no severe corrosion is observed in any acid
solution. In the temperature range of about 100–150 °C, the only slight intergranular
attack may be observed due to impurities like phosphorus, sulfur, and silicon present
in concentrations higher than 10–100 ppm [22]. Prior precipitation of chromium
carbides along grain boundaries may also cause some dissolution of the chromium
depleted regions adjacent to carbides [29–31].
At temperatures above about 150 °C, severe pitting may occur in HCl and HBr
solutions [32–34] (see, e.g., Fig. 7.25a [23]) as the critical pitting temperatures for
the two acid solutions is about 150 °C, though the lowest temperature for the bromide
solution is higher than that of the chloride solution. Typical pit penetration rates of
about 600 to 1000 μm in 100 h have been reported for Alloy 625 [28]. Other acid
solutions show only minor corrosion in this temperature range. Observation of pits
in HCl and HBr solutions is consistent with the aggressive natures of the two halide
ions. Mitton et al. [35] have reported stress-corrosion cracking at temperatures less
than 200 °C after several hundreds of hours.
At temperatures above 250 °C, the alloy may exhibit severe general corrosion in
HCl, HBr, H2 SO4 , and HNO3 solutions, independent of pressures above 22 MPa [28,
32, 33, 36–38]. This behavior is attributed to the increased solubility of the oxygen
in the water, which makes it highly oxidizing [22]. At the same time, the oxidation
resistance of passive film decreases due to decreasing stability of the Cr3+ oxide film
[24]. The morphology of the general attack has the shape of interconnected shallow
pits (Fig. 7.25b [23]). The HF and H3 PO4 solutions cause low levels of corrosion at
Fig. 7.25 Change in the corrosion behaviour of Alloy 625 in hydrochloric acid solutions containing
0.05 mol/kg hydrochloric acid and 0.48 mol/kg of oxygen at 24 MPa pressure. The alloy exhibited
pitting during corrosion at lower temperatures, which tend to change to a general form of corrosion at
high temperatures due to reduced stability of the Cr3+ oxide film. a A scanning electron micrograph
of a pit formed at160 °C; b Typical wave-like appearance of corrosion product due to the formation
of interconnected shallow pits at 350 °C. Reprinted from [23], Copyright (2004), with permission
from Elsevier
these temperatures [28, 32], which can be attributed to (i) extremely low degree of
dissociation of the two acids even at these high temperatures; (ii) the formation of
insoluble phosphates or fluorides that provide secondary protection.
The typical corrosion parameters of Alloys 625 in pressurized oxidizing solutions
of different acids at subcritical temperatures are summarized in Table 7.4 [22]. Based
on corrosion rates, the corrosivity of acids in these environments can be arranged in
the following order: HNO3 > HBr > HCl > H2 SO4 > H3 PO4 ≈ HF.
Stress-corrosion cracking (SCC) is a common phenomenon in oxidizing high-
temperature solutions [22, 23]. Figure 7.26 shows the failure of an Alloy 625 tube
by SCC in a solution containing 0.10 mol/kg HCl and 0.48 mol/kg oxygen at 220
°C and 38 MPa pressure. This condition corresponds to a temperature transition
region between passive and transpassive states. The SCC started at the bottom of
a shallow pit, and the tube failed in about 25 h [23]. This cracking is due to the
breaking of the protective layer under high-temperature water’s highly chemically
aggressive environment, rather than high mechanical stresses generally responsible
for local destruction of the protective film in SCC. Kritzer et al. [22] have contested
for chemical destruction of the film under such an aggressive environment because
Table 7.4 Typical minimum corrosion temperatures and corrosion rates of intergranular corrosion,
pitting and transpassive dissolution of Alloy 625 in oxidizing aqueous solutions of different acids
containing 0.05–0.2 mol/kg acid and 0.5 mol/kg of oxygen at 24 MPa pressure [22]
HF HBr HCl HCla H2 SO4 H3 PO4 HNO3
Intergranular corrosion (°C) 170 150 110 110 145 50 10
Pitting (°C) – 170 140 215 – – –
Pitting rate (μm/100 h) – 1000 1000 1000 – – –
Transpassive dissolution (°C) – 320 300 290 300 – 270
Corrosion rate (μm/100 h) < 30 800 400 400 300 < 10 1800
a Polished inner surface
Fig. 7.26 Failure of an

Alloy 625 tube by SCC in a
solution containing 0.10
mol/kg HCl and 0.48 mol/kg
oxygen at 220 °C and 38
MPa pressure. Reprinted
from [23], Copyright (2004),
with permission from
Elsevier
the applied load is too low to break the oxide film. On the other hand, the observation
of the stress-corrosion cracking by Mitton et al. [35] at temperatures less than 200
°C, mentioned above, is attributed to the high penetration rates of pitting leading to a
severe thinning of the wall that increased mechanical stresses. Hydrogen appears to
play no role in stress-corrosion cracking of the alloy in these conditions. Its evolution
is significant only at high anodic potentials in strongly oxidizing high-temperature
waters [22].
Surprisingly, increasing the temperature to supercritical values reduces the corro-
sion rates by at least two orders of magnitude. Kritzer et al. [22] have attributed the
behavior to the low density of the supercritical water, which makes it a non-polar
solvent with very low solvency for inorganic compounds, leading to low corro-
sion rates. Nonetheless, an increase in the density of the supercritical solution still
increases the corrosion rate. For example, the alloy exhibits an increase in the corro-
sion rate by a factor of 50 in oxidizing supercritical HCl or H2 SO4 solutions when the
density of the solution is increased from about 150 kg/m3 (at 24 MPa pressure and
400 °C temperature) to about 510 kg/m3 (38 MPa pressure) [22, 28, 38]. In general,
the severe corrosion of the alloy ceases when the density of the solution decreases
to values less than 200 kg/m3 due to the protective nature of the nickel oxide layer
at low densities (Fig. 7.22).
The melting of corrosion products in high-temperature pressurized water solutions
unexpectedly increases corrosion rates due to the formation of corrosive two-phase
environments. For example, Alloy 625 in an oxidizing solution containing 0.1 mol/kg
phosphoric acid (at T = 430–470 °C; p = 24 MPa) exhibits negligible corrosion.
However, the corrosion rate increased tremendously to about 850 μm/h when the
acid concentration is increased to 0.2 mol/kg [37]. This unexpected increase in the
corrosion rate is attributed to the formation of a two-phase environment when nickel
(III) phosphate corrosion product, which has a melting point lower than the process
temperature, melted in the pressurized high-temperature water [38].
7.5.2 Neutral High-Temperature Waters
Neutral high-temperature water containing only oxygen is not very corrosive. It does
not corrode even after relatively prolonged exposure. For example, the alloy exhibits
a corrosion rate < 10 μm in 100 h, though some pitting was observed in supercritical
low-density solutions after 800 h [22]. The low corrosion rate is attributed to the
protection by the NiO film. NiO is the most stable oxide film in neutral supercritical
water. On the other hand, chromium and molybdenum oxides dissolve by forming
their hexavalent acids H2 CrO4 and H2 MoO4, respectively. Likewise, the alloy may
exhibit a low corrosion rate in oxidizing salt solutions of chlorides and sulfates due
to the low solubility of the NiO film. However, the alloy may exhibit severe pitting
in oxidizing sodium chloride solutions at temperatures higher than 200 °C because
it is higher than the critical pitting temperature in HCl solutions [22].
7.5.3 Alkaline High-Temperature Waters
In oxygenated dilute sodium hydroxide (NaOH) solutions, the alloy is protected by

the formation of NiO layer at subcritical temperatures (Fig. 7.24) since the nickel
oxide has the lowest solubility in the weak alkaline pH range compared to chromium
and molybdenum oxides [39]. At high pH values, the alkaline solutions also inhibit
chloride-induced pitting corrosion as the alkaline solutions quickly neutralize the H+
ions formed during pit initiation suppressing the pit’s possible growth [22]. Alloy 625,
therefore, exhibit very low corrosion in oxygenated alkaline solutions at subcritical
temperatures. The alloy is non-corrosive in oxygenated sodium hydroxide water
solutions at subcritical temperatures [39].
However, at supercritical temperatures and low densities, the alloy exhibit severe
corrosion in oxidizing solutions of NaOH [40]. The severe corrosion is due to the
melting point of NaOH (320 °C) lower than the temperature of the supercritical water
and its poor miscibility in low-density supercritical water. As a result, a condition of
two phases exists in low-density supercritical temperatures containing high NaOH
concentrations. This two-phase contains an oxidizing NaOH melt as an additional
phase with enhanced solvency for salts, which can dissolve even the nickel oxide
[40, 41]. In oxygen-free NaOH solutions, no severe corrosion is observed even at
supercritical temperatures because of the absence of metal oxide-producing reduction
reaction.
Chromium does not protect nickel–chromium alloys in subcritical and supercrit-
ical water solutions. At subcritical temperatures, chromium dissolves by forming
hydrogen chromate [HCrO4– ] or chromate [CrO2− 4 ] in the aqueous phase [22]. In
contrast, at supercritical temperatures, it dissolves by forming chromic acid [H2 CrO4 ]
or salts in the melt phase.
7.6 High-Temperature Corrosion
High-temperature corrosion is the degradation of materials due to chemical attacks

from solids, liquids (molten metals or salts) or gases at elevated temperatures, typi-
cally above 0.4T m . The modes of high-temperature corrosion include oxidation,
carburization, sulfidation, metal dusting, corrosion by halogens, etc.
7.6.1 Oxidation
Nickel-based alloys are superior to Iron-based or cobalt-based alloys for high-

temperature applications because of their excellent oxidation resistance. These alloys
gain their high-temperature resistance primarily due to the formation of the protec-
tive Cr2 O3 oxide film, and the extent of resistance is directly related to the chromium
concentration. However, the Cr2 O3 film becomes volatile at temperatures above 980
°C [5], which reduces the protection of the alloy. At higher temperatures, alloys
containing a small amount of aluminum (e.g., Alloy 214) exhibit better resistance
to oxidation due to the formation of a more protective Al2 O3 film. Sometimes rare
earth elements like lanthanum and yttrium are also added to enhance the resistance
of the oxide scales to spallation [42].
The damage of metal during oxidation is due to its conversion into an external
oxide scale. In addition, oxidation may cause an internal attack and the formation of
isolated internal voids. The degree of oxidation generally increases with an increase
in temperature. During exposure in the air, the internal attack may also result in the
formation of internal nitrides along with internal oxides when significant spallation
of Cr2 O3 film occurs in alloys with insufficient aluminum. Thermal cycling has a
marked effect on oxidation attacks due to the spallation of the oxide scales, with a
higher frequency of causing more significant damage.
Alloy 625 has good resistance to oxidation and scaling at high temperatures. The
primary protective oxide layer is Cr2 O3 . The oxide layer becomes enriched with
Cr2 O3 as the temperature increases from 600 °C [43]. Between 800 and 1050 °C, the
oxide scale is almost exclusively of Cr2 O3 . At temperatures above about 1050 °C, the
oxide layer gets enriched with niobium and titanium [43]. The oxidation resistance
of the alloy is comparable to that of alloys 600 and 800 and better than Alloy C-276
[8]. Figure 7.27a compares the oxidation behavior of Alloy 625 with some other
alloy based on the mass change in air containing 5% water vapor at 1000 °C for
up to 1000 h. Alloy 625 is among the best materials for oxidation resistance in air
containing about 5% water vapor. Figure 7.27b shows the results of cyclic oxidation
tests of Alloy 625 and other nickel-base alloys at 982 °C, subjected to 2880 cycles
(over 40 days) of 15 min heating cycles up to 982 °C, followed by cooling in the air
Fig. 7.27 a Oxidation behaviour of Alloy 625 and some other nickel alloys exposed to air containing
5% water vapour at 1000 °C. b Scale adherence of oxide films during cycling oxidation of Alloy
625 and other alloys at 982 °C [8]
7.6 High-Temperature Corrosion 275
for 5 min [8]. Alloy 625 shows excellent adherence to its oxide scale. It exhibited an
outstanding ability to retain the protective oxide coating under this cyclic condition.
7.6.2 Carburization
Carburization occurs in environments that contain carbonaceous gases like CO, CO2 ,
CH4 and other hydrocarbons when the carbon diffuses into the metal surface and
combines with alloying elements to form various carbides. The formation of internal
carbides may lead to metal degradation and embrittlement, which result in a reduction
in tensile and Charpy impact properties [44]. The corrosion damage is directly related
to the magnitude of carburization. Carburization can be quantified in terms of the
mass of the carbon gained (mg/cm2 ) and the depth of carburization. Often, the gaseous
carburization environments are also oxidizing in nature. In such environments, the
dominant character of the damage is governed by the partial pressure of carbon and its
activity at a given temperature [45]. In general, carburization occurs at temperatures
above 800 °C and carbon activity < 1 [44].
The low solubility of carbon in nickel alloys and the formation of a protec-
tive, stable oxide scale make them inherently resistant to carburization. However,
these alloys contain many carbide-forming elements that may form their carbides.
Figure 7.28 compares the mass of carbon gained in Alloy 625 and other alloys after
carburization for about 1000 h in a mixture of H2 -l% CH4 at 1000 °C [8]. The Alloy
625 exhibited a carburization resistance better than that of Alloy 800. Its mass change
in a slightly oxidizing carburizing environment of H2 -5.5% CH4 -4.5% CO2 gaseous
mixture (oxygen partial pressure ~ 10−20 atm) at 1000 °C for about 1000 h was
comparable to Alloys 600 and better than Alloy 800 and 601 [8].
Fig. 7.28 Carburization behaviour of Alloy 625 at 1000 °C compared to other alloys in a H2 -1%
CH4 and b H2 -5.5% CH4 -4.5%CO2 environments [8]
Table 7.5 Carburization

Alloy Carbon mass gain per unit area (mg/cm2 )
behavior of alloys in 5% H2
+ 5% CO + 5% CH4 argon 871 °C for 215 927 °C for 215 982 °C for 55 h
gas [46] h h
Alloy 214 0.14 0.3 0.6
Alloy 617 0.26 2.4 5.0
Alloy 625 0.31 1.1 5.3
Alloy S 0.32 1.6 2.1
Alloy 600 0.40 1.3 2.8
Alloy 230 0.40 2.0 2.5
Table 7.5 compares carburization behavior of Alloy 625 in an atmosphere

containing 5% H2 + 5% CO + 5% CH4 (by volume) in argon gas at 871, 927 and 982
°C temperatures [46]. The partial pressure of oxygen at different test temperatures
corresponded to 8.13 × 10−23 , 2.47 ×10−22 and 6.78 ×10−22 atm, respectively. The
magnitude of the carbon pick-up increased significantly at 982 °C despite a shorter
duration of exposure.
7.6.3 Sulfidation
Sulfidation corrosion occurs when a metal is exposed to sulfur compounds in high-

temperature environments. Unlike oxide scales, sulfide scales are not protected as
they contain many defects, which allows a faster diffusion of metal ions through the
scale. Nickel alloys form a low-temperature Ni3 S2 eutectic compound at 635 °C when
exposed to an environment comprising only H2 and H2 S [5]. As a result, the liquid
Ni3 S2 sulfide accelerates corrosion significantly. The formation of the low-melting
eutectic restricts the use of nickel alloys in such environments at temperatures up to
about 600 °C only.
Nickel alloys owe their resistance to sulfidation to the protective Cr2 O3 film as the
Cr2 O3 film is impervious to sulfur diffusion. A small addition of aluminum or silicon
further enhances the sulfidation resistance by forming an Al2 O3 - or SiO2 -rich sub-
layer. The destructive sulfidation attack occurs mainly at sites where the protective
oxide breaks down. Once sulfide phases include, they oxidize preferentially and
form new sulfides deeper inside the alloy, often at grain boundaries or at the sites
of other chromium- or aluminum-rich phases. Most sulfur-bearing high-temperature
environments also contain gases like SO2 , CO, CO2 and H2 O. In such sulfidizing-
oxidizing environments, relative partial pressures of oxygen and sulfur govern the
formation of oxide or sulfide scales. Table 7.6 compares the sulfidation of Alloy 625
with some other heat-resistant alloys in an argon gas environment comprising 5%
H2 , 5% CO, 1% CO2 , 0.15% H2 S at 871 °C for 215 h. The alloy exhibits a maximum
metal loss of more than 24 mils. This corrosion rate had consumed more than half the
Table 7.6 Metal loss of

Alloy Metal loss (mils) Maximum metal affected b
Alloy 625 and some other
(mils)
heat-resistant alloys at 871 °C
after 215 h in argon gas Alloy 230 Consumed a > 19.5
containing 5% H2 , 5% CO, Alloy 625 Consumed a > 24.0
1% CO2 , 0.15% H2 S [5]
Alloy 800 H 7.6 > 30.0
Alloy 617 3.8 21.3
Alloy HR 160 0.8 6.2
a Consumed refers to the state of the sample when the maximum
metal affected is greater than one-half of the sample thickness
b Maximum metal affected = metal loss + maximum internal
attack
thickness of the coupon kept for testing [5]. Cuevas-Arteaga et al. [47] have shown
that cobalt addition significantly reduces the sulfidation rate.
7.6.4 Halide Corrosion
High-temperature halide corrosion is common in fossil fuel boilers, coal gasifica-

tion equipment, gas turbines, and municipal and chemical waste incinerators. Halide
corrosion refers to corrosion by gaseous Cl2 /HCl. It can be more harmful than oxida-
tion. It proceeds by the formation and volatilization of chloride scales due to lower
melting points of metal chlorides (e.g., 696 °C for FeCl2 ) and higher vapor pres-
sures of corresponding oxides. For environments dominated by gaseous chlorine,
chromium bearing nickel alloys are preferred due to relatively high melting points
of NiCl2 (1030 °C) and CrCl3 (1150 °C) [5]. In the presence of oxygen, corrosion
involves the formation of oxides and volatile oxychlorides (e.g., chromium oxychlo-
rides and molybdenum oxychlorides) depending upon relative partial pressures of
oxygen and chlorine. In such environments, high nickel contents in the alloys are
beneficial because nickel forms one of the least volatile chlorides [5].
The use of a nickel alloy for environments containing chlorine may depend upon
the relative concentration of the chlorine. For instance, Alloy 625 exhibits an inter-
mediate resisstance level in air containing 2% chlorine. Table 7.7 compares the
corrosion behavior of Alloy 625 with some other nickel superalloys in air containing
2% chlorine after exposure for 50 h at 900 °C [48]. In this environment, Alloy 214
exhibits the best resistance to halide corrosion due to the presence of aluminum in
the alloy, which forms the impervious protective Al2 O3 scale. However, Alloy 600,
which contains chromium lesser than Alloy 625, exhibits better resistance. The low
resistance of Alloy 625 than that of Alloy 600 could be due to molybdenum (9 wt%)
in the former. Molybdenum and tungsten are known to be detrimental against the
halide atmosphere [5]. This does not mean that Alloy 625 always performs poorly
in all halide environments. In gaseous environments containing a mixture of HCl,
Table 7.7 Metal loss of

Alloy Metal loss (mils) Total depth (mils)
Alloy 625 and some other
heat-resistant alloys after 50 h Alloy 214 0.6 1.6
of exposure at 900 °C in air Alloy 800 H 1.0 4.3
containing 2% chlorine [48]
Alloy 600 2.0 5.0
Alloy 601 0.2 5.2
Alloy 625 4.0 7.0
Alloy C-276 6.1 8.1
Alloy 230 1.3 8.2
Alloy 617 3.8 11.8
Table 7.8 Mass change in alloys exposed to a nitrogen gas environment containing 10% CO2 , 9%
O2 , 4% HCl, 130 ppm HBr and 100 ppm SO2 after 300 h [8]
Alloy Mass change (mg/cm2 )
593 °C 704 °C 816 °C 927 °C
SS 309 − 2.62 − 117.89 − − 77.70
SS 316 − 5.48 − 152.08 − 32.75 − 45.74
SS 347 − 1.61 − 327.80 − 221.65 − 68.36
Alloy 600 − 0.32 − 0.98 − 6.93 − 10.18
Alloy 601 − 0.50 − 2.19 − 7.24 − 29.53
Alloy 617 − 0.51 − 8.38 − 10.81 − 44.64
Alloy 625 − 0.52 − 2.06 − 5.86 − 5.91
Alloy 690 − 0.13 − 1.12 − 14.27 − 24.21
Alloy 800 − 0.53 − 245.22 − 6.63 − 18.98
Alloy 825 − 1.53 − 127.34 − 8.52 − 25.89
HBr and SO2 , Alloy 625 is one of the best materials, especially at high temperatures.
Table 7.8 compares the metal loss of Alloy 625 with other alloys tested in a gaseous
mixture of N2 -l0% CO2 -9% O2 -4% HCI-130 ppm HBr-100 ppm SO2 environment at
593, 704, 816, and 927 °C for 300 h. All the alloys exhibited metal loss (expressed as
negative mass change) suggesting of their spalling or vaporisation loss or both. The
rate of metal loss in most alloys increased with increasing temperature. The high-iron
alloys show higher mass losses at 704 °C than at 927 °C [8] due to extensive internal
oxidation triggered by the molten FeCl2 (melting p oint = 696 °C). The morphology
of the corrosion scale at high temperatures (e.g., 927 °C) is distinctly different from
that at low temperatures. At higher temperatures, voids are frequently seen that are
more pronounced in iron-rich alloys. Figure 7.29 shows these effects in 316-grade
stainless steel and Alloy 625 after exposures at 704 and 927 °C. Evidently, for the
test temperature regime of 593–927 °C, the nickel-base alloys are better for avoiding
704 °C liquid phase corrosion.
Fig. 7.29 Typical scanning electron subsurface micrographs of 316 stainless steel and Alloy 625
alloys exposed to a gaseous mixture of N2 -l0% CO2 -9% O2 -4% HCI-130 ppm HBr-100 ppm SO2
environment at 704 and 927 °C. a 316 stainless steel exposed at 704 °C; b 316 stainless steel exposed
at 927 °C; c Alloy 625 exposed at 704 °C; d Alloy 625 exposed at 927 °C. Reprinted from [8].
Copyright 1991 by The Minerals, Metals & Materials Society. Used with permission
7.6.5 Molten Salt Corrosion
Molten salt corrosion at high temperatures is often encountered in heat-transfer and

energy-storage media used in solar energy and nuclear systems, fuel cells, high-
temperature batteries, metallurgical extraction processes and heat-treating industry.
Molten salts dissolve the protective oxide scales from the metal surface, exposing
the surface for a further oxidation cycle, followed by the dissolution of the oxide
film in the molten salt. Oxygen and water vapor in the molten salts accelerate the
kinetics of molten salt corrosion. Metals react with molten sodium hydroxide to form
metal oxides, sodium oxide, and hydrogen. The attack mechanism is predominantly
intergranular corrosion by the salt components, especially chlorine [49]. Table 7.9
compare the corrosion damage of Alloy 625 with other nickel alloys after their
exposure in a sodium chloride bath at 840 °C after 100 h [49]. A fresh salt bath was
used for each run, and the air was used as the cover gas. Alloy 625 exhibited an
intermediate level of corrosion resistance in the molten NaCl salt bath.
Table 7.9 Depth of the salt

Alloy Total depth
penetration in Alloy 625 and
some other alloys when tested mm mils
in a sodium chloride bath at Alloy 601 0.066 2.6
840 °C for 100 h [49]
Alloy 214 0.079 3.1
Alloy 800 H 0.109 4.3
Alloy 625 0.112 4.4
Alloy 617 0.122 4.8
Alloy 230 0.140 5.5
Alloy 600 0.196 7.7
7.7 Environmentally Assisted Cracking
Environmentally assisted cracking refers to the phenomenon by which an ordinarily

ductile material loses its toughness and ductility when subjected to mechanical
loading in the presence of specific corrosion environments. Three factors, namely, (i)
a specific aggressive environment, (ii) mechanical tensile stress, and (iii) a susceptible
microstructure, are simultaneously needed for an alloy to exhibit environmentally
assisted cracking (Fig. 7.30). Alteration or elimination of any one of the three miti-
gates the occurrence of environmentally assisted cracking. Of these, alteration of the
environment or the change of the alloy is the best solution as the complete elimina-
tion of stresses is somewhat tricky due to geometrical considerations of components.
When neither the alloy nor the environment can be changed, environmentally assisted
Fig. 7.30 A schematic

diagram depicting factors
essential for the occurrence
of environmental assisted
cracking
7.7 Environmentally Assisted Cracking 281
cracking can be mitigated by eliminating tensile stresses on the exposed surface by

introducing compressive stresses using techniques like shot peening.
Environmentally assisted cracking generally includes phenomena like stress-
corrosion cracking, hydrogen embrittlement and sulfide stress cracking.
7.7.1 Stress-Corrosion Cracking
Nickel-base alloys are, in general, not prone to stress-corrosion cracking in chlo-

ride environments compared to stainless steels. They are also preferred in caustic,
polythionic acid, and some deep sour gas well environments. Figure 7.31 shows
the effect of nickel on the susceptibility to chloride ion stress-corrosion cracking in
boiling 42% magnesium chloride test solution [15]. Figure 7.31 shows that all alloys
containing more than 45% nickel are immune to chloride stress cracking. Alloy
625 has a minimum of 58% nickel and will not crack in a chloride environment.
However, it suffers stress-corrosion cracking in conditions associated with supercrit-
ical water oxidation, as discussed in Sect. 7.5.1. It undergoes intergranular cracking
when exposed to supercritical water and chlorides at high temperatures. Kim et al.
[50] have shown that subcritical and supercritical pressurized hydrochloric acid water
solutions of pH two cause stress-corrosion cracking of Alloy 625 along grain bound-
aries. In subcritical solution conditions, the stress-corrosion cracking occurs under
the combined influence of stresses and the defective de-alloyed oxide layer formed
due to de-alloying of nickel and iron and the oxidation of chromium and molyb-
denum. In such conditions, the stress-corrosion cracking may occur at stresses as
low as 30% of the yield strength. In supercritical conditions, no de-alloying occurs,
and the stress-corrosion cracking is a direct consequence of the chemical attack of
hydrochloride molecules at grain boundaries under the influence of stress. Table 7.10
Fig. 7.31 The classic

indicator of the susceptibility
to chloride-ion
stress-corrosion cracking of
nickel-containing alloys in
the boiling 42% magnesium
chloride test. The threshold
represents the minimum time
beyond which cracking starts
for a given amount of nickel
present in the alloy. Alloys
containing more than 45%
nickel are immune to
chloride stress cracking [15]
Table 7.10 Environments in which Alloy 625 exhibited stress-corrosion cracking [51]
Thermal history Environment for SCC
Annealed High-temperature water, degassed
Annealed Polythionic acid
Annealed Oxygenated water plus lead
Annealed Water containing 21 ppm O2 at 316 °C
Annealed Steam, cycled between 318 and 385 °C, 10 ppm Cl− , 8 ppm
O2
Cold worked Water containing 100 ppm O2 at 288 °C
Cold worked and aged at 204 °C Water saturated with H2 S + 5% NaCl + 0.5% acetic acid
(NACE solution) at room temperature
Cold worked and aged at 500 °C Water with 5% NaCl and 0.5% acetic acid at room
temperature
As produced tube Hydrochloric acid solutions of pH 2, 300 to 426 °C, 24.1
MPa
lists environments in which stress-corrosion cracking has been observed in Alloy 625
[51].
7.7.2 Hydrogen Embrittlement
Hydrogen embrittlement refers to the loss of ductility caused by hydrogen ingress

into the metal. It may cause intergranular, transgranular, or quasi-cleavage cracking.
The degree of susceptibility to hydrogen embrittlement can be measured as a function
of the ductility loss. Like ferrous alloys, nickel alloys are also susceptible to hydrogen
damage in both aqueous and gaseous hydrogen environments, but to a lesser extent
owing to greater ease of slip and reduced solute diffusivities in their face-centered
cubic lattice.
Variables that affect hydrogen embrittlement the most are [52]: (i) the surface
hydrogen fugacity for gaseous hydrogen and cathodic charging current density for
the electrolytically charged hydrogen; (ii) impurities like sulfur, phosphorus, arsenic,
antimony and tin; (iii) temperature. Under the gaseous atmosphere, hydrogen pres-
sure has a steep dependence on the embrittlement at low pressures, followed by a
region of cracking that is independent of pressure [52]. For electrolytically charged
hydrogen, the time to failure decreases monotonically with charging current density
[52]. Presence of alloying impurities such as sulfur, phosphorus, antimony and
tin aid the entry of adsorbed hydrogen into the metal by inhibiting the recombi-
nation of hydrogen adatoms (adsorbed atoms) from forming hydrogen gas which
can then escape. Besides, these impurities increase the embrittlement of alloys by
forming low-melting eutectic compounds at grain boundaries that cause decohe-
sion of grains. Hydrogen embrittlement decreases with an increase in temperature
[52]. The maximum embrittlement temperature depends on the composition and

microstructure of the alloy. This hydrogen embrittlement behavior contrasts to stress-
corrosion cracking in chloride environments, in which it increases with an increase
in temperature [52, 53].
Nickel-base superalloys show a reduction in tensile ductility when charged with
hydrogen, depending on the thermo-mechanical history of the alloy. They are
generally more resistant to hydrogen stress cracking in as-cold-worked conditions
compared to cold-worked and aged states [54]. Age-hardenable alloys age-hardened
to peak or near-peak strength show the least hydrogen embrittlement resistance.
Stabilization treatments, followed by aging, reduce the resistance of these alloys
compared to direct aging. Hydrogen stress cracking of nickel alloys may also occur
without losing tensile ductility when alloys possess high yield strengths or are under
high hydrogen fugacity [54].
Alloy 625 possesses an intermediate level of resistance against hydrogen embrit-
tlement induced by both gaseous hydrogen and internal hydrogen. Hydrogen embrit-
tlement has little effect on the yield strength of the alloy. In contrast, it reduces
alloy’s notch tensile strength, ductility and threshold stress intensity for subcritical
crack growth. The severity of internal hydrogen embrittlement increases with the
dissolved hydrogen, up to 50 part-per-million (ppm) hydrogen by weight. Increasing
dissolved hydrogen contents causes a change in the fracture mode from ductile to
brittle, which manifests itself in fractographic changes from dimpled features at low
dissolved hydrogen contents to {111} planar facets at higher dissolved hydrogen
contents (up to 50 wt. ppm hydrogen) [55]. The alloy is resistant to hydrogen-stress
cracking when cold worked to a yield strength above 1240 MPa [54]. However, when
the cold-worked alloys are aged at low temperatures, their resistance to hydrogen
cracking reduces considerably. This behavior is attributed to the segregation of phos-
phorus and sulfur to grain boundaries, which provide low-energy fracture paths or
an ordering reaction of the form Ni2 (Cr, Mo). Figure 7.32 relates the ductility loss
(reduction in area) with hydrogen charged to the precipitation of the ordered Ni2 (Cr,
Mo) phase in the alloy [56].
7.7.3 Sulfide Stress Cracking
Sulfide stress cracking is another form of hydrogen embrittlement prevalent

commonly in the oil and gas industry or environments containing water and hydrogen
sulfide. Sulfide stress cracking usually results in a brittle failure of the alloy under
tensile loading above a threshold stress. Atomic hydrogen diffuses into the metal at
cathodic sites in hydrogen sulfide environments and causes embrittlement in the local-
ized hard zones or weldment of sensitive materials. Table 7.11 gives the minimum
stress (threshold stress) required for Alloy 625 and some other alloys to initiate
cracking in a sulfide environment at room temperature under constant load [57]. The
atmosphere contained a mixture of oxygen-free water containing 3000 ppm dissolved
H2 S, 5% NaCl and 0.5% acetic acid (NACE solution). Alloy 625 exhibited threshold
Fig. 7.32 Effect of the degree of order on the hydrogen embrittlement susceptibility due to the
precipitation of Ni2 (Cr, Mo) [56]
Table 7.11 The threshold stress required for Alloy 625 and other alloys to initiate cracking at room
temperature under constant load in a mixture of oxygen-free water containing 3000 ppm dissolved
H2 S, 5% NaCl and 0.5% acetic acid (NACE solution) [57]
Alloy Thermal history Yield strength Ultimate tensile Threshold stress
(MPa) strength (MPa) (MPa)
MP35N Cold rolled and 2005 2046 1965
annealed
C-276 Cold rolled 1503 1631 1473
G Cold rolled 1496 1617 1470
K-500 Cold rolled and 1124 1317 1101
annealed
625 Annealed 558 979 546
625 Cold rolled 1327 1355 1301
718 Solution annealed 986 1172 960
and aged
X-750 Solution annealed 1304 1318 1013
and aged
Nitronic 50 Cold rolled 880 1076 862
stress close to its yield strength in both annealed and cold rolled conditions (Table
7.11). Alloys with a higher yield strength cracked at a higher threshold stress value.
7.8 Corrosion Behavior of Alloy 625 PLUS
As noted in Chap. 5, Alloy 625 PLUS is a precipitation-hardened variant of Alloy 625

in which a higher amount of titanium (~1.4%) is added to accelerate the precipitation
of the γ phase particles. Since titanium plays only a limited role in enhancing the
resistance against intergranular corrosion in Alloy 625, the corrosion behavior of
the age-hardened Alloy 625 PLUS against all other forms of corrosion is similar
to that of Alloy 625. Cozar et al. [58] have studied the effect of titanium on the
intergranular corrosion resistance of age-hardened Alloy 625. These studies were
carried out using the standard ASTM G 28 A procedure in a boiling aqueous solution
of 50% sulfuric acid and ferric sulfate. They have shown that age-hardening of an
Alloy 625 containing 1.2% titanium decreases its corrosion resistance slightly. The
corrosion rate increases with time and temperature of aging at temperatures above
600 °C (Fig. 7.33). The aging of the alloy at 550 and 580 °C does not sensitize this
alloy. On the other hand, its resistance to pitting corrosion is less affected by aging
[58].
The corrosion resistance of the age-hardened Alloy 625 PLUS is compared with
age-hardened Alloy 718 that has identical strength but inadequate corrosion resis-
tance. On the other hand, Alloy 625 has similar corrosion resistance but requires
warm or cold working to increase its strength, which is not always feasible, partic-
ularly for larger cross-section components. The following compares the corrosion
behavior of age-hardened Alloy 625 PLUS (1040 °C/2 h/AC + 732 °C/8 h/FC to
621 °C/8 h/AC) with those of age-hardened Alloy 718 and cold-worked Alloy 625.
Fig. 7.33 The effect of

ageing time and temperature
on the corrosion rate of
Alloy 625 containing 1.2%
titanium, tested as per the
ASTM G 28 A standard.
Before the ageing
treatments, the alloy was
annealed at 1050 °C for one
hour, followed by water
quenching [58]
In general, age-hardened Alloy 625 PLUS exhibits corrosion resistance superior

to that of aged Alloy 718 and similar or superior to cold worked Alloy 625 [59-
62]. Besides, Alloy 625 PLUS is resistant to stress-corrosion cracking in chloride
and sulfide environments. The aged alloy also exhibits excellent stress-corrosion
resistance in slow strain rate conditions. Slow strain rate tests conducted on double-
aged Alloy 625 PLUS in a severe oil field environment at 177 °C containing sour
brine (16.5% NaCl + 1 MPa H2 S and 1 MPa CO2 , added at room temperature)
with 10 g/l elemental sulfur exhibited excellent resistance to cracking with a ratio of
time-to-failure in the corrosive environment versus the inert atmosphere exceeding
0.9 with no secondary cracking [60]. The mechanical and fatigue properties of the
age-hardened Alloy 625 PLUS are better than that of 718 and K-500 alloys [61].
The aged alloy can resist sulfide stress-corrosion cracking for over 1000 h during
tests conducted in the NACE TM0177 environment at room temperature [59]. The
NACE TM0177 environment comprises a room temperature solution of 5% sodium
chloride and 0.5% acetic acid, continuously purged with hydrogen sulfide. The alloy
exhibits excellent resistance to sulfide stress-cracking/hydrogen embrittlement at
ambient temperature. Samples of age-hardened Alloy 625 PLUS tested at 100%
yield strength resisted cracking at 204 °C for 28 days showed no crack growth in any
of the fatigue pre-cracked samples with stress intensities of 58 to 75 MPa m1/2 , while
one of the nine Alloy 625 samples, in cold-worked condition, cracked and three of
the four aged Alloy 718 samples cracked [59]. The yield strength of different aged
Alloy 625 PLUS samples varied from 827 to 958 MPa.
Age-hardened Alloy 625 PLUS has excellent resistance against pitting and
crevice corrosions by chlorides. Its pitting resistance, evaluated in a ferric chlo-
ride/hydrochloric acid solution and a “modified green death” solution, is similar
to that of cold-worked Alloy 625 and superior to that of age-hardened Alloy 718
(Table 7.12) [59]. Resistance at higher temperatures indicates excellent resistance
of the alloy. The crevice corrosion resistance of Alloy 625 PLUS, evaluated using
Table 7.12 Pitting temperature test results for 625 PLUS, 625 and 718 alloys pitting temperature
(°C) [59]
Alloy Condition Pitting temperature (°C)
6 wt% FeCl3 + 1wt% Modified green death a
HCl (24 h exposure) (96 h exposure)
Alloy 625 PLUS 1040 °C/2 h/AC + 732 > 98, > 98 75, 80
°C/8 h/FC to 621 °C/8
h/AC
Alloy 625 25% cold rolled > 98, > 98 80, 90
Alloy 718 1025 °C/2 h/WQ + 788 56, 62 45, 45
°C/8 h/AC
aModified green death = 7 vol% H2 S04 + 3 vol% HCl + 5 wt% CuCl2 ·2 H2 O + 5 wt% FeCl3 ·6
H2 O
7.8 Corrosion Behavior of Alloy 625 PLUS 287
Table 7.13 Crevice corrosion test results for 625 PLUS, 625, and 718 alloys (°C) [59]
Alloy Condition Crevice corrosion weight Crevice temperature
loss (mg/cm2 ) (°C)
6 wt% FeCl3 + 1wt% HCl Yellow death a (96 h
(40 °C/72 h) (55 °C/72 h) exposure)
Alloy 625 PLUS 1040 °C/2 h/AC + 732 1.2 6.0 40, 40
°C/8 h/FC to 621 °C/8
h/AC
Alloy 625 25% Cold Rolled 3.7 13.7 35, 40
Alloy 718 1025 °C/2 h/WQ + 788 35.0 47.2 < 25, < 25
°C/8 h/AC
a Yellow death = 4 wt% NaCl + 0.1 wt% Fe2 (SO4 )3 + 0.01 M HCl
constant-temperature weight-loss tests in the ferric chloride (FeCl3 )/hydrochloric

acid (HCl) solution and “yellow death” solution, was also similar to that of Alloy
625 and superior to that of Alloy 718. Table 7.13 compares the crevice corrosion
behavior of alloys 625 PLUS and 718 in aged conditions and Alloy 625 in cold-
worked condition [59]. The temperature at which the crevice corrosion initiated on
Alloy 625 PLUS is significantly higher than the Alloy 718 in "yellow death" solution.
Similar trends were observed in the weight loss tests in 6 wt% FeCl3 + 1 wt% HC1
at higher temperatures of 40 °C and 55 °C. The higher level of corrosion resistance of
the Alloy 625 PLUS is attributed to its higher chromium and molybdenum contents
compared to Alloy 718.
7.9 Summary
Alloy 625, in general, offers good resistance to uniform and localized corrosion
in various kinds of environments, e.g., inorganic and organic acids, molten slats,
pressurized waters, gaseous environments etc. due to its high Chromium and Molyb-
denum contents. Chromium provides resistance to oxidizing chemicals, while the
molybdenum and high nickel improve the alloy’s resistance to non-oxidizing envi-
ronments. The presence of niobium prevents it from sensitization and thus, stabilizes
against intergranular attack. Under the pressurized water conditions, Alloy 625 under-
goes severe pitting corrosion in acidic water at subcritical temperatures, which leads
to stress-corrosion cracking on prolonged exposure. While at supercritical tempera-
tures, the corrosion rate reduces. On the other hand, the alloy exhibits a low corrosion
rate in neutral water at supercritical temperatures and in alkaline water at subcritical
temperatures, owing to the protection provided by the NiO film. At high tempera-
tures, Alloy 625 exhibits good resistance to oxidation, carburization and sulfidation
while exhibiting an intermediate level of resistance to gaseous halides and molten salt
environments. This combination of corrosion resistance properties against a broad
range of environment makes Alloy 625 one of the most acceptable materials in the
chemical and petrochemical industries.
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Chapter 8
Life Management of Alloy 625
Components
Alloy 625 is being used for various applications in the chemical, marine, nuclear,
power generation, and aerospace industries [1–9]. These applications range from
process tubing, feedstock superheaters, bubble caps, distillation columns for the
petrochemical industry [9, 10], heat exchangers and reactor core in pressurized
water reactors in the nuclear industry [7], and for marine application [5], owing
to its outstanding and versatile corrosion resistance over a wide range of tempera-
tures and pressures. Alloy 625 is also used as turbine shrouds, spray bars, hydraulic
tubing, thrust reverser systems, etc. in the aerospace industry. Most of these applica-
tions remain at temperatures in the intermediate range of about 0.45–0.63 T m (where
T m is the melting temperature in Kelvin). The alloy undergoes significant service
degradation during service exposure due to microstructure modifications and, conse-
quently, mechanical properties changes [11–13]. Many critical components of Alloy
625 in various plants are likely to have operated for long durations and even may have
outlived their design life. Such components need to be replaced beyond their stipu-
lated life. Since the economy of an industrial plant or machinery is directly linked
to the service life of its components, efforts are always made to maximize the life
of components with their safe operations. A logical and economical decision is to
extend the life of a component before its retirement. Life extension of service-spent
components is common in thermal power plants based on their operating history,
inspections, material testing, and remaining life assessment.
As Alloy 625 is used for applications at temperatures in the intermediate range,
slight corrosion or no loss of thickness is envisaged during its thermal exposure in
most industrial applications. The alloy, however, undergoes significant microstruc-
tural modifications during long-term thermal exposure at intermediate temperatures.
It develops complex microstructures by precipitating out several competing phases,
namely, γ , δ, Ni2 (Cr, Mo) and various carbide phases in the disordered matrix. It
has been noted in Chaps. 3 and 4 that the precipitation of γ and Ni2 (Cr, Mo) phase
particles hardens the austenitic matrix while that of the δ and carbide phases impairs
tensile ductility and impact strength of Alloy 625. Available experience with the
service exposure of Alloy 625 has demonstrated that it is possible to reverse the
https://doi.org/10.1007/978-981-19-1562-8_8
294 8 Management of Alloy 625 Components
degraded microstructure and rejuvenate the lost properties, at least for the compo-
nents that have experienced negligible creep deformation [11, 12]. Since the alloy
is costly, there are strong economic reasons to delay the retirement of Alloy 625
components merely based on the design life and utilize the alloys to the maximum
by extending its life by rejuvenating the lost properties. This chapter aims to assess
the performance of Alloy 625 and evaluate its damage and failure mechanisms during
industrial application. These mechanisms can be used to devise strategies for the life
extension of Alloy 625 components. A few case studies illustrate the successful life
extension of Alloy 625 tubes and specific circumstances that led to their failure during
service.
8.1 Definitions of Damage, Failure, and Life
Any progressive and cumulative change in the alloy due to service exposure that
causes deviations in its properties away from the initial properties and has the poten-
tial to affect its current and future performance adversely can be termed as “damage”.
The performance in the present context refers to the structural performance of load-
bearing components of a plant. Any damage, unless reversed, may lead to the failure
of a component.
Failure of a component may be defined as its inability to perform its intended
function in a safe, reliable, and economical manner. This inability may be caused
by cracking, breaking away, or degradation in the component’s properties below
the codal requirement, forcing its premature retirement to avoid unforeseen and
catastrophic failure.
The life of a component may be defined as the “period during which the component
can perform its intended function safely, reliably, and economically” [14] and is a
function of operating conditions. The life of a component is considered expended
when one or more of the following criteria is satisfied [14].
• The component has spent more time in the service than the life, based on the
design life.
• There is a high probability of its failure based on previous failure statistics.
• The frequency of the repair renders its continued operation uneconomical.
• Observing cracks during a non-destructive examination, which can propagate
catastrophically under operating conditions.
• Excessive surface degradation by corrosion or erosion, including the degradation
of coatings.
• Excessive grain boundary attack and pitting by oxidation or hot corrosion.
• Severe structural damage by a foreign object.
• Life exhaustion as indicated by destructive sampling and testing.
• Excessive deformation due to creep resulting distortions and unfavorable changes.
• Sudden and complete fracture.
8.2 Basic Philosophy of Life Management 295
8.2 Basic Philosophy of Life Management
Life assessment and life extension of critical components are essential for the
economy and the safety of plants. The basic philosophy of the life management of
structural components stems from their damage-tolerance philosophy used for main-
taining the structural integrity of commercial transport vehicles, military aircraft,
structures, and pressure vessels. The damage tolerance philosophy has evolved on
fracture mechanics principles, which envisages the presence of a crack of length, a,
in a material and its resistance against the growth of crack under stress (Fig. 8.1a).
Under tensile conditions, all structures fail by catastrophic propagation of the crack
in the material when its size reaches a critical size (length) ac , even though the gross
stress may be much below the yield or failure stress. The critical crack size depends
on factors like fracture toughness, ligament size, loading conditions, etc. The mate-
rial degradation during service exposure embrittles the alloy and reduces its fracture
toughness and resistance against catastrophic growth of the crack, as illustrated in
Fig. 8.1b. In a virgin (unexposed) material, the nucleation and growth of a crack
follows a two-step sequence as depicted by Curve A. The first step, Region I, corre-
spond to an embryonic, microscopic damage event that may lead to the nucleation
of a microscopic crack. The microcrack may even be inherently present in the virgin
material or may have nucleated due to events like dislocation rearrangements, coars-
ening of precipitates, formation of cavities, and microcracks during deformations like
creep, fatigue, etc. The second step, Region II, depicts the growth and propagation
of the nucleated microcrack with time (Curve A), till it reaches the critical size ac in
a period of t 1 , beyond which the material may fail by the rapid growth of the crack.
Reduction in the fracture toughness due to service degradation significantly reduces
the critical size, depicted by curve B. In the service degraded alloy, the structure fails
Fig. 8.1 a Schematic depicting a crack of size a under a tensile stress σ. b Variation in the crack
size during service exposure in virgin and service degraded material
at a critical size, ac1 , which reduces its time to failure to t 2 (t 2 < t 1 ). Dynamic loading
conditions, like fatigue, vibrations, etc. accelerate the stage II growth behavior of
cracks, resulting in the shift of the failure point toward the left (depicted by the A
curve) to a shorter failure period t 3 .
Conventional non-destructive examination (NDE) techniques like dye-penetrant
inspection, ultrasonic measurements, radiography, eddy-current testing, etc. may be
used to monitor the stage II size and growth of cracks during periodic inspection
of components. However, these techniques are based on the premise that cracks of
size larger than their detectable limits exist and will grow slow enough to permit
their periodic examination during the regular in-service inspection (ISI). Regular
inspections help retire a component before its catastrophic failure. However, there
are many instances when these techniques failed to detect cracks before the failure.
In such cases, the material degradation during the service has either reduced the
crack’s critical size below the detectable limit or accelerated its growth too fast to
be detected by the NDE technique employed. In such instances, the initiation of the
crack alone may lead to the component’s failure.
8.3 Damage Mechanisms in Alloy 625 During Service

Exposure
Damage mechanisms in Alloy 625 components may change depending upon

their operating history. For instance, at “low temperatures”, failure may occur by
microstructural modifications, resulting in the degradation of properties below the
codal requirement. At “high temperatures”, failure may be dominated by cracking and
fracture, which may or may not be promoted by microstructural modifications. The
two temperature regimes can be defined based on the rupture ductility of Alloy 625,
which depends upon its relative strength compared to the loading stress at operating
conditions. As noted in Chap. 4, service age-hardening of the alloy by intermetallic
phase precipitates dominate the strength of the alloy up to about 750 °C. Above
750 °C, most intermetallic precipitates coarsen or dissolve, and phenomenon like
creep starts dominating. However, the precipitation of intermetallic phases hardens
the alloy and reduces its rupture ductility significantly (Sect. 4.5). Service age-
hardening may force the retirement of the component or may cause its failure in
a brittle manner. On the other hand, above 800 °C, the failure modes may differ
due to creep rupture, thermal or mechanical fatigue, tensile properties modified by
environmental interactions, or a combination of such processes. Accordingly, the
service damage in Alloy 625 can be broadly classified into two categories. First,
the microstructural damage, which involves a significant change in the microstruc-
ture due to the precipitation of intermetallic and carbide phases that may embrittle
the alloy. Second, the structural or mechanical damage, which involves the forma-
tion of microcracks and cavities due to deformation of the alloy because of fatigue,
8.3 Damage Mechanisms in Alloy 625 During Service Exposure 297
creep, etc. Microscopic studies and mechanical properties evaluation of the service-
exposed components can estimate both the damages. Besides, several surface crack
detection NDE techniques, like liquid-penetrant tests, ultrasonic inspection, eddy-
current inspection, and internal crack detection techniques such as ultrasonic and
radiography, can also identify the two damages.
8.3.1 Microstructural Damage
The microstructure of an alloy may change significantly depending upon the oper-
ating temperature, exposure time, and loading conditions. In addition, corrosion and
oxidation of exposed surfaces may also occur at intermediate to high temperatures
depending on ambient conditions. This section primarily summarizes the types of
microstructural changes the Alloy 625 undergoes as a function of temperature and
time. Detailed descriptions of these changes have been given in Chap. 3. Under
deforming conditions, the applied stress may accelerate these changes. At tempera-
tures up to about 450 °C, practically, there may not be any change in the microstruc-
ture. However, microstructural defects, like dislocations present due to cold working
steps in the fabrication process, may be relieved during exposure at around 400 °C
or above.
When the alloy is exposed to temperatures in between about 540–750 °C, fine
precipitates of the Ni2 (Cr, Mo) and γ phases forms, though the Ni2 (Cr, Mo) phase
may not remain stable at temperatures above about 628 °C (Fig. 3.20). During
prolonged thermal exposure at temperatures above 650 °C, the δ phase may nucleate
at grain boundaries, and the γ phase may also transform to its stable δ phase structure
(Fig. 8.2).
In the temperature range of about 750 to 950 °C, microstructural changes occur
readily due to faster diffusion kinetics. This temperature range is characterized by the
Fig. 8.2 Optical

microstructure of a service
exposed Alloy 625
tube sample showing the
predominant formation of δ
phase particles in the vicinity
of grain boundaries during
prolonged exposure of the
alloy at temperatures above
650 °C
precipitation of M23 C6 secondary carbides and the δ phase particles at temperatures

up to about 900 °C (Fig. 3.20). The two processes extend the precipitation sequences
at temperatures < 750 °C but their mechanisms may change due to enhanced kinetics.
At temperatures > 950 °C, the molybdenum-rich M6 C carbides may form. Precipi-
tation of secondary carbides (both M23 C6 and M6 C) is a consequence of the degen-
eration of the primary carbides (Sect. 3.2.5). Alloy 625 shows less tendency to form
topologically close-packed phases, compared to other Ni–Cr–Mo-based alloys like
Hastelloy X, in this temperature range.
At temperatures >1100 °C, the alloy may experience a high oxidation rate and even
incipient melting at about 1288 °C (Fig. 8.3) (Sect. 1.1). The alloy may reach such
high temperatures due to overheating or temperature excursions. Although the highest
operating temperature of an alloy for structural applications is determined based on
its strength and oxidation resistance under operating conditions, the risk of incipient
melting during overheating restricts its usage to temperatures up to about 150 °C
less than its liquidus temperature. Overheating may cause the failure of components
due to local melting (Fig. 8.4) or dissolution of the hardening phases that causes a
sudden drop in the strength. Overheating may also deplete alloying elements that
provide oxidation resistance and may, therefore, accelerate the oxidation process of
the alloy even when it returns to the normal operating temperature. Further, even if
the prolonged exposure to over temperature does not result in the mechanical failure,
it may cause excessive surface corrosion damage, particularly under hot corrosion
conditions, which can reduce the strength of the alloy.
Microstructural modifications may embrittle Alloy 625. Embrittlement of the
alloy may nucleate microcracks when the movement of dislocations is impeded by
the interfaces between second phase particles, like carbides or δ-phase particles,
and the matrix or grain boundaries. Accumulation of dislocations at these interfaces
builds up stress at the intersection of slip bands and particles that nucleates crack
when the stress concentration is large enough.
Fig. 8.3 An optical

micrograph showing
incipient melting of grain
boundaries in Alloy 625
8.3 Damage Mechanisms in Alloy 625 During Service Exposure 299
Fig. 8.4 Failure of an Alloy

625 tube due to local melting
of the alloy
8.3.2 Structural Damage
Structural damage is due to the accumulation of strain over a long period. The prin-
cipal types of damages at elevated temperatures may be creep, low- or high-cycle
fatigue, thermal fatigue, and even degradation in the coatings of coated surface
components like gas turbines. Most of the damages caused by these mechanisms
may be localized. However, high-temperature creep may also cause bulk damage in
the form of dimensional changes or distortions, which can be easily detected and
measured with an accuracy of 0.1% of the strain. This strain can give an idea of
the extent of damage compared to the expected failure strain. The localized damage
may be in the form of cavitation, which can be evaluated by metallographic or other
techniques like radiography and ultrasonic measurements. Standard relationships
developed for steels can be used to correlate the degree of creep cavitation with the
life expended [15].
8.4 Damage Assessment in Alloy 625
The principal objective of the damage assessment is to extend the life of critical
components. This assessment is based on regular monitoring of their health at appro-
priate intervals for parameters like dimensional change, distortions, microstruc-
ture, cavitation, hardness, etc. using non-destructive examination techniques, and
repairing and maintaining their health at regular intervals. The challenge is to iden-
tify the time of intervals for inspection and life assessment such that it ascertains the
uninterrupted performance of components without failures in between such inter-
vals. These intervals are chosen based on conservative estimates of the degrada-
tions in the microstructure and the design limiting properties in previous compo-
nents under typical plant conditions during the period of interval. Under normal
circumstances, the remaining life is estimated based on NDE results during such
inspection considering the available data. However, when the access of NDE equip-
ment is limited, a similar analysis of post-service samples extracted from components
may be used to estimate the expended life. Any life-limiting defect or flaw observed
during inspections makes the basis of its removal.
Alloy 625, in general, offers excellent resistance to uniform and localized corro-
sion in various kinds of oxidizing and reducing environments (Chap. 7), in most
industrial environmental conditions. At high temperatures, the alloy exhibits good
resistance to oxidation, carburization, and intermediate resistance levels in molten
salt and gaseous environments containing sulfur and halides. However, the alloy
is susceptible to hydrogen embrittlement to a certain extent. It reduces the alloy’s
notch tensile strength, ductility, and threshold stress intensity for subcritical crack
growth with little effect on the yield strength. Hydrogen embrittlement may cause
the brittle failure of the alloy under tensile loading above a threshold stress. Under
pressurized water conditions, the alloy may undergo severe pitting corrosion in
acidic waters at subcritical temperatures, which leads to stress corrosion cracking on
prolonged exposure. Therefore, in most of its forms, corrosion does not fail Alloy 625
but may adversely affect in exceptional cases like hydrogen embrittlement. There-
fore, unfavorable environments of halides, sulfides, and acidic waters at subcritical
temperatures may reduce the life expectancy of components. However, estimating
the remaining life of components damaged by localized corrosion is somewhat tricky.
Nonetheless, localized corrosion mechanisms need to be monitored carefully. Identi-
fying the presence of such life-limiting corrosion mechanisms would provide guide-
lines to avoid such corrosions, which, in turn, would be effective in the component’s
life management.
The assessment of the damage in Alloy 625 at intermediate temperatures is mainly
reported as a loss in mechanical properties due to microstructural modifications.
Traditionally, microstructure-based and hardness-based techniques have been used
to assess the condition of blades and tubular components of power plants. Similar
approaches can be utilized for the assessment of Alloy 625 components, based on the
precipitation behavior of Ni2 (Cr, Mo), γ , δ, M23 C6 and M6 C phases in conjunction
with creep rupture data of the alloy at elevated temperatures. If the damage is by creep,
standard models [15] correlating microstructural features like cavities can be used
to predict life. The expenditure of creep and fatigue life can sometimes be estimated
by removing samples from the component and conducting accelerated tests in the
laboratory. However, temperatures of the accelerated tests on Alloy 625 are limited
up to about 750 °C because tests above it modify the microstructure significantly
(Chap. 3). Impact or fracture-toughness tests can determine service degradation in
the toughness. However, continuous monitoring of the toughness degradation is rather
difficult due to difficulties involved with the extraction of samples on a regular basis.
The remaining life-assessment methodologies depend upon the nature of the
dominant damage. Over the years, several techniques have evolved for assessing
the service damage, particularly for the life management of power plants [15], based
on service degraded properties of the material (microstructural and mechanical prop-
erties). The analyzed damage is then utilized to assess the remaining life using stan-
dard analytical models based on the operating history, component geometry, and
8.4 Damage Assessment in Alloy 625 301
the nature of the damage. The life assessment of Alloy 625 components can adapt
some standard life-assessment procedures of power plants. The following gives a
brief description of such life-assessment procedures. These procedures are based on
extrapolating past failures and the measurements of hardness, microstructural and
ultrasonic data during in-service inspections. In addition, the life-assessment methods
based on fracture mechanics analysis of the localized damage can be adopted. All the
life-assessment procedures contain inherent deficiencies and uncertainties, leading
to inaccuracies in the assessment results. However, a good combination of multiple
procedures may evaluate the remaining life with better accuracy.
8.4.1 Assessment Based on Extrapolation of Statistics of Past

Failures
History of past failures can provide valuable details about a potential future failure.
Historical data provides a limit for the uninterrupted operation of a component with
no significant failure. This information can be utilized to determine the time for neces-
sary corrective actions for the good health of a component. This method, however,
has limitations as the necessary details about microstructural, thermal, and operating
histories of failed components and their failure mechanisms are often difficult to
obtain. Further, Alloy 625 with similar life history may have different microstructures
or equal strength and hardness with varying life histories because the microstructure
of the alloy is susceptible to change at temperatures in the range of 600 – 725 °C
(Chap. 3). Variations in the microstructures and histories may bring a significant
error in assessing the predicted life.
8.4.2 Assessment Based on Hardness
Strength of the alloy changes during service exposure depending on the time and
temperature of the exposure. Change in the strength parameters, like hardness and
tensile strength, may be used to estimate an average temperature the alloy has experi-
enced during its service exposure, based on the previous history database. Figure 8.5
shows variation in the hardness with time when Alloy 625 tubes were exposed to
service at temperatures about 650 °C. The variation in the hardness can be fitted to a
parabolic relation H = H 0 + At + Bt 2 , where t is the exposure time in hours, H 0 is the
initial hardness (of virgin alloy), and A and B are hardness constants. A and B could
be fitted to 2.9 × 10–2 and −1.4 × 10–8 , respectively. When the hardness changes
as a function of the service temperature (T ) as well as the exposure time (t), the
hardness change can be correlated to a Larson-Miller parameter (LMP) relationship
given by LMP = T (20.7 + log t) (Sect. 4.7), where, T is temperature (in Kelvin) and
t is the exposure time in hours. However, the hardness-based analysis requires good
Fig. 8.5 Variation in the hardness of Alloy 625 as a function of time during prolonged thermal
exposure at temperatures around 650 °C
statistics of independent measurements because of the poor reproducibility and large

scatter in the data due to sensitivity of the hardness to local microstructure. A similar
correlation may be established using the tensile strength data, but obtaining a large
number of tensile data with varying service histories is rather tricky.
8.4.3 Assessment Based on Microstructure Cataloging
Microstructural modifications can also assess the damage at elevated tempera-

tures. Microstructure-based and hardness-based damage assessments are commonly
used to monitor the conditions of blades and tubular components of power plants.
Viswanathan [15] has used semi-quantitative and qualitative approaches involving
microstructural “cataloging” as a function of temperature to assess the remaining
life. He has shown a reasonably good correlation of microstructure with a “weighted
average” service temperature for ferritic steels [16]. Similar cataloging of microstruc-
tures as a function of an LMP-type parameter, incorporating time and temperature,
can be created for Alloy 625. This catalogue can be used as a guide to predict the
temperature and the life spent based on the microstructure of the service-exposed
samples. However, care would be required in using such catalogues as the microstruc-
tural damage up to about 725 °C is primarily due to the precipitation of Ni2 (Cr,Mo)
and γ phase particles and the two phases impart similar nature of hardening effects.
Above this temperature, dissolution and coarsening of particles, or the both, of the
two phases, precipitation of the δ phase and carbide particles start dominating during
prolonged exposure. This decreases the alloy’s creep strength, which is reflected in
the change in the slope of the LMP plot (Fig. 4.38). Nonetheless, the precipitation of
the Ni2 (Cr, Mo), γ , δ, M23 C6 and M6 C phase in Alloy 625 can be utilized to iden-
tify the typical temperature range within which the alloy has been exposed during
most of the service life [11]. However, this procedure may suffer from the limited
microstructure catalog data of Alloy 625. The qualitative microstructural analysis
can be coupled with hardness, impact energy, and fracture-toughness data to make
semi-quantitative life assessments.
8.4.4 Assessment of Damage by Ultrasonic Measurements
Ultrasonic measurements can be used as an excellent in-situ non-destructive tech-

nique to assess the progress of in-service degradation in Alloy 625 based on the ultra-
sonic measurement parameters in conjunction with hardness. Ultrasonic measure-
ments exploit the reflection of sound waves of high frequency, transmitted through
metals, from discontinuities like cracks, cavities, pores, grain boundaries, etc. Kumar
et al. [17] have extensively studied the effect of the thermal history of Alloy 625 on
ultrasonic parameters. They have correlated variations in the ultrasonic measure-
ments to hardness change with the progress of microstructural degradations [18].
The hardness variation can be due to the precipitation of γ , δ and Ni2 (Cr, Mo)
phases. Kumar et al. [17] have examined many ammonia cracker tubes service
exposed at 650 to 680 °C for different periods and compared them with virgin tubes
to understand the effect of the progress of microstructural degradation on the ultra-
sonic parameters. These tubes were divided into six categories, namely: (1) virgin
tubes; (2) virgin tubes after a short period of exposure of 747 h in service; (3) virgin
tubes after an intermediate period of exposure of 57,194 h in service; (4) virgin tubes
after a long period of exposure of 120,000 h in service; (5) re-solution annealed (RSA)
tubes; (6) RSA tubes after their second service exposure of 23,000 h. The resolution
annealed (RSA) tubes refer to those tubes which had already been exposed for a
service of 120,000 h in the ammonia cracker plant, removed from the plant, and
subjected to a solution annealing treatment of 1150 °C/0.5 h [19] to restore their
mechanical properties to the codal requirements.
Figure 8.6 shows the variation in Poisson’s ratio and the attenuation measured
in many ammonia cracker tubes in the categories mentioned above. The scatter in
the data observed in different types of tubes is listed in Table 8.1. The Poisson’s
ratio decreases with the progress of microstructural degradation, as reflected in its
decrease with an increase in the hardness (Fig. 8.6a). During the initial stages of
precipitation, the hardness does not change appreciably and remains within the virgin
alloy’s scatter band (Table 8.1). However, a noticeable change in Poisson’s ratio
can be observed. The values of hardness and Poisson’s ratio of the virgin tubes
lie in the ranges of 140–174 VHN and 0.314–0.318, respectively. In contrast, the
Poisson’s ratio decreases to between 0.309–0.313 during age-hardening within 747 h,
Fig. 8.6 Variation in a Poisson’s ratio of Alloy 625 and b attenuation of longitudinal ultrasonic
waves with an increase in the alloy’s hardness with the progress of service degradation (after [17])
though the hardness does not change much (140–200 VHN) compared to the virgin
tubes, except for a slight increase in the upper bound. This behavior is attributed
to the depletion of alloying elements from the matrix, which increases the alloy’s
modulus and decreases the Poisson’s ratio. The hardness/yield strength does not
change much because the particles at the initial stages of precipitation are very small
to impede dislocations effectively. However, the maximum change in the Poisson’s
ratio is observed after short exposure times during service, while the shift remains
insignificant during the prolonged exposures.
On the other hand, appreciable variation in both hardness and Poisson’s ratio
is observed during service degradation at intermediate and later stages, though the
hardness increase is more prominent. The hardness at intermediate and later stages
are in the range of 250–300 and 230–360 VHN, respectively, while the Poisson’s
ratio at the two stages is in the range 0.309–0.312 and 0.295–0.308, respectively. This
data shows that the Poisson’s ratio does not change appreciably during prolonged
aging. However, a significant increase in the hardness is due to enhanced nucleation
and growth of hardening precipitates. A substantial scattering in the hardness and
Poisson’s ratio values is due to varying extents of damage/degradation upon service
exposure for the same duration.
Interestingly, the RSA tubes exhibit lower hardness (126–135 VHN) and slightly
higher Poisson’s ratio (0.317–0.319) than the virgin tube. The RSA treatment
involved solution annealing of the service-exposed tubes, while the virgin tubes are
usually supplied in as-annealed condition. The annealing temperature is below the
solution annealing temperature, and the alloy’s microstructure in the two conditions
may vary differently (Sect. 6.3). The annealed alloy may contain some fine precip-
itates of a second phase. This sensitivity of the Poisson’s ratio on microstructure
indicates that the Poisson’s ratio is a better parameter for monitoring the degradation
during the initial period, while hardness is a better parameter for the intermediate
and later stages. This is consistent with the response of the ultrasonic velocity on
precipitation-hardened aluminum alloys [20, 21] and nickel-base superalloy PE16
Table 8.1 Variations in the Poisson’s ratio and the attenuation of ultrasonic longitudinal waves with the hardness of ammonia cracker tubes of Alloy 625 service
exposed at temperatures in the range 650–680 °C [17]
Thermal history of tubes Hardness (HVN) Poisson’s ratio Attenuation (dB/mm)
Range Mean Range Mean Range Mean
8.4 Damage Assessment in Alloy 625
Virgin tubes 140–174 155.0 ± 14.0 0.314–0.318 0.3159 ± 0.0017 0.18–0.34 0.281 ± 0.067
RSA tubesa 126–135 135.3 ± 3.9 0.317–0.319 0.3171 ± 0.0019 0.35–0.50 0.405 ± 0.054
Virgin + SE (747 h)b 140–200 169.2 ± 16.8 0.309–0.313 0.3114 ± 0.0012 0.25–0.34 0.288 ± 0.031
Virgin + SE (57,194 h) 250–300 269.5 ± 18.3 0.309–0.312 0.3104 ± 0.0011 0.27–0.36 0.320 ± 0.026
Virgin + SE (120,000 h) 230–360 293.4 ± 30.8 0.295–0.308 0.3017 ± 0.0044 0.15–0.28 0.216 ± 0.032
RSA + SE (23,000 h) 220–240 236 ± 1.4 0.314–0.315 0.3146 ± 0.0009 0.43–0.60 0.510 ± 0.124
a RSA: Re-solution annealed. RSA tubes refer to rejuvenated service degraded tubes after a solution annealing treatment of 1150 °C/0.5 h. The tubes were service
exposed for 120,000 h [17, 19]

b SE:Service Exposed. Numbers in the parenthesis refer to the period of exposure. RSA + SE tubes refer to the RSA tubes that were put in the service for the
second time
305
[22]. The ultrasonic velocity and Poisson’s ratio in these alloys decrease with their
hardness increase. A decrease in the Poisson’s ratio with an increase in the precip-
itation is due to a larger influence of the precipitates on the ultrasonic shear wave
velocity than the longitudinal wave velocity. The larger influence of the microstruc-
tural change on the shear wave velocity is attributed to its association to two perpen-
dicular planes (propagation and vibration) than the one plane in the case of longitu-
dinal waves [23]. Kumar et al. [17] have also noticed that the nature of precipitates in
Alloy 625 affect the ultrasonic velocity and the yield strength/hardness differently.
The dissolution of the Ni2 (Cr, Mo) phase and the precipitation of the δ phase influ-
ence the ultrasonic velocity more than the yield strength. In contrast, dissolution and
precipitation of the γ phase influence the yield strength more than the ultrasonic
velocity.
The attenuation of ultrasonic waves may help identify the abnormal microstruc-
ture during in-service inspections. Figure 8.6b shows the variation in attenuation of
ultrasonic longitudinal waves with microstructural conditions. All the virgin tubes
and the service-exposed virgin tubes exhibited lower attenuation (<0.36 dB/mm).
In contrast, the RSA tubes and the service-exposed RSA tubes showed a higher
attenuation (>0.36 dB/mm). Even though the starting microstructure and hardness
of the RSA and virgin tubes were similar, high attenuation for the RSA tubes has
been attributed to the microcracks/voids that formed during service exposure and
to the grain growth during their resolution annealing treatment [10]. The effect of
microcracks/voids on increasing the attenuation value is consistent with an indepen-
dent study on a failed tube, which exhibited very high attenuation (0.51 dB/mm)
despite low hardness (233 VHN) and high value of Poisson’s ratio (0.315) [17]. In
addition to Poisson’s ratio and hardness, the periodic attenuation measurements may
help identify an abnormal change in the microstructure, such as an increase in the
grain size or the formation of creep cracks due to abnormal service conditions or an
accidental increase in the temperature or load. The limitations of ultrasonic measure-
ments are that it needs extensive technical expertise and knowledge for meaningful
results. They cannot be done on parts/sections that are rough, irregular in shape, or
very small or thin. Reference standards are needed to calibrate the equipment and
characterize flaws.
8.4.5 Assessment Based on Bulk Creep Damage
The bulk creep-damage of components can be assessed by two approaches based

on: (1) plant operation data on the time–temperature history of the component in
conjunction with standard material-property and plant in-plant inspection (ISI) data
[15]; (2) post-service evaluation of the actual component. The damage rules are based
on the time spent or the strain accrued at a given time t i , which can be related to
corresponding rupture time or strain [15].
The remaining fraction of the life during service can be calculated as a ratio of the
time to rupture of the service-exposed specimen to the expected time to rupture for
the virgin alloy tested under the same conditions. The expended life fraction can be
calculated using the life-fraction rule (LFR) by subtracting
the remaining life fraction
from unity. According to LFR, a failure occurs when t i /t r = 1, where t i is the time
spent at given stress and temperature, and t r is the rupture life of the material for the
same test conditions. For many materials like steel, the LFR may utilize different
temperatures for a given stress value when the material’s microstructure remains
unchanged. Therefore, this rule must be applied to Alloy 625 keeping in mind the
microstructural changes that occur at about 725 °C.
A similar rule can be followed for the accumulated strain, which can be measured
with an accuracy of 0.1%. This strain can be compared with the expected failure
strain for the material under service conditions to estimate the remaining lives. A
sudden increase in the creep rate may indicate its entry into the tertiary creep stage
and hence provide a forewarning to failure. The limitation of this damage rule is
that it gives a gross estimate of the creep damage due to errors associated with creep
test data. Besides, the assumed history based on the material properties may itself
bring in significant error due to similar effects of the hardening phases.
The post-service evaluation of actual components involve conventional NDE tech-
niques, dimensional measurements, and creep-life evaluation by accelerated creep-
rupture testing. Each of them may also have its source of errors. For instance, dimen-
sional measurements may fail to detect the local creep damage caused by localized
strains in the heat-affected zones and regions of stress concentrations in the base
metal, which may even cause accelerated failure. Estimating the remaining creep
life based on accelerated creep-rupture tests at temperatures well above the service
temperature requires the stress value as close to the service stress value as possible
because of the compliance of only iso-stress creep conditions with the life-fraction
rule employed. Despite these limitations, the post-service evaluation techniques make
better estimations based on actual properties developed during ISI intervals. However,
this technique is relatively expensive and time-consuming as it involves destruc-
tive tests requiring the removal of samples from operating components. Removal of
samples limits their number and locations and requires plant shutdown for extended
periods.
The best strategy can be to combine the two approaches. The plant operation data
can be utilized to identify critical locations and the extent of detailed evaluations
required, followed by a reasonable selection of samples and test conditions of post-
service assessment.
8.4.6 Assessment Based on Fracture Mechanics Analysis
The remaining life of thick-wall components can be estimated by combining damage

initiation criteria with crack-growth data using fracture-mechanics analysis under
different loading conditions. The driving force for the crack growth is a function of the
stress and the strain rate far from the crack tip, depth of the crack, and the microstruc-
tural state of the alloy. Correlations between the crack growth rate in the material
as a function of the service life and the microstructure can be established based on
prior data or testing of the samples harvested from service-exposed components. As
noted earlier, the precipitation of various intermetallic phases during service expo-
sure of Alloy 625 manifests itself in reducing its fracture toughness, while grain
boundary carbides and embrittling phases like δ-phase enhance the crack growth
rate along their interfaces. The effect of such microstructural modifications on the
component’s life can be estimated using finite-element analysis or standard analyt-
ical models to calculate the crack growth rate as a function of the loading stress,
crack size (a), material constants, and geometry of the component.
Fracture mechanics analysis-based assessment is illustrated considering an
example of the growth of a longitudinal crack on the outer surface of an Alloy
625 tube of an outer diameter of 89 mm and thickness 9 mm under fatigue loading
at about 650 °C. The internal pressure of the tube would tend to open up the crack
along axial direction under the influence of the hoop stress, which may lead to its
failure when the crack reaches a critical size, ac , beyond which it may rupture the
tube by catastrophic propagation of the crack. The value of the ac would be governed
by factors like K1C , J1C , wall thickness, and remaining ligament thickness. For the
virgin alloy (KIC = 140 MPa m1/2 [24]), the critical crack size ac can be calculated
using widely accepted analytical or numerical approaches. The critical size can be
calculated using the following relationship [25]
Kcπ
ac = (8.1)
π Mσh
8σf ln sec 2σf
where K c is the fracture toughness, σ f is the flow stress, σ h is the hoop stress given
by pd , p is the internal pressure, d and t are inner diameter and thickness of the tube,
2t
2
and M is the “Folias factor” expressed as 1 + (rai ∗t) , where r i is the inner radius
of the tube. The flow strength σ f was taken as (σ y + σ u )/2, where σ y and σ u are
yield strength and ultimate tensile strength of the virgin alloy, taken from the Special
Metals data sheet [26]. Equation 8.1 gives a critical crack length of 65 mm for the
catastrophic propagation of the crack in the virgin tube.
Assuming the crack growth in the Paris Law regime under fatigue loading
conditions, the fatigue crack growth rate per cycle, da/dN, can be given by the
following.
da
= C(K )m (8.2)
dN
where C and m are material constants. The life of the tube is estimated as a function
of initial crack size (i.e., 4, 6, 8, 10 mm) and a width (depth) up to half-thickness
(i.e., 4.5 mm) using the three-dimensional Finite Element Method (FEM) analysis. A
cyclic load of the amplitude of 14 MPa with zero stress ratio (σ min /σ max ) was applied
on the inner surface of the tube till its failure. The tube was assumed to have failed
when the axial size of the crack reached a critical value beyond which it may rupture
by catastrophic propagation of the crack or its size along the radial direction reaches
through-thickness where it would develop a leak before catastrophic rupture. The
fatigue life estimation analysis was carried out for the virgin and service-exposed
materials.
Virgin Alloy For the virgin alloy, fracture toughness and fatigue parameters are KIC
= 140 MPa m1/2 and m and C as 2.798 and 5.7 × 10–12 N/m3/2 , respectively [24].
Figure 8.7 shows variation in the crack length in axial and radial tube directions. The
number of cycles to failure decreased with increasing the initial size of the crack.
This analysis shows that the virgin tube would fail by the through-thickness leak
of the tube for all the cases of initial crack length considered. The crack reached
through-thickness in the radial direction much before it reached the critical size of
63 mm in the axial direction. The tube would develop a leak after about 1.95 × 105
cycles of fatigue if the initial crack length were 4 mm and would fail after about 7.2
× 104 cycles if the initial crack length were 10 mm. The axial length of the crack in
both cases would be about 22 mm at the time of the leak, which was much below the
catastrophic failure of the tube under hoop stress conditions.
Service-Exposed Alloy Two types of service degradations, namely: (1) simply a

reduction in the toughness of the alloy by about 50%, as caused by the precipitation
of the hardening Ni2 (Cr, Mo) and γ phase particles; and (2) 50% reduction in the
toughness and 30% increase in crack propagation rate due to the precipitation of
embrittling phases, like the δ phase and grain boundary carbide films, were consid-
ered. The critical crack length along the axial direction for catastrophic failure in such
service-exposed alloys (50% toughness loss) would be reduced to about 38.5mm (by
about 40%), indicating that the tube would develop a leak much before its catas-
trophic failure. The toughness and fatigue parameters for the two service degraded
conditions were assumed as (1) KIC = 70 MPa m1/2 (50% decrease with respect to
that of the virgin alloy), and m = 2.798 and C = 5.7 × 10–12 N/m3/2 , and (2) KIC =
Fig. 8.7 Variation in a axial and b radial length of cracks as a function of 14 MPa of fatigue cycles
in a virgin 8.9 mm thick Alloy 625 tube. The horizontal broken line signifies the size at which the
tube would fail by developing a through-thickness leak
Fig. 8.8 Plots represent the effect of different types of service degradations on the fatigue life
of the tube. Service ‘degradation 1’ assumes a reduction in the alloy’s toughness by about 50%,
while ‘degradation 2’ assumes a 50% toughness reduction along with a 30% increase in crack
propagation rate. Plots show variation in the a axial length and b radial length of a 10 mm long
crack as a function of 14 MPa of fatigue cycles in virgin and service exposed Alloy 625 tubes.
The horizontal broken line signifies the size at which the tube would fail by catastrophic failure or
developing a through-thickness leak
70 MPa m1/2 (about 50% decrease), and m = 3.637 (30% increase in crack propaga-
tion rate with respect to that in virgin alloy) and C = 5.7 × 10–12 N/m3/2 . The fracture
analysis of such alloys indicates that the precipitation of grain boundary carbides and
embrittling δ phase significantly reduces the life of the tube. 30% increase in the crack
growth rate reduced the life by about 90% as the tube would develop leak after about
7.4 × 103 fatigue cycles compared to about 7.2 × 104 cycles when the crack growth
rate was increased by 30% (Fig. 8.8). Simply reducing the fracture toughness by
50% would reduce the fatigue cycles to about 6.7 × 104 for a crack with an initial
length of 10 mm size. The number of cycles can be translated into the period for the
remaining life based on the frequency of the load cycle.
A similar analysis can be performed for the damage caused by creep conditions.
The essential parameters required for life assessment of a component under creep
loading are creep rate constant (A), creep rate exponent (n), crack-growth rate coef-
ficients (b), and crack-growth rate exponents (m), crack size, a, and geometry of
the component. These parameters can be either assumed from the previous data or
generated by non-destructive examination during ISI and creep testing of samples.
A detailed description of this approach is given by Viswanathan [15].
This analysis demonstrates that the remaining life for failure can be predicted
as a function of defects and service degradation for a given loading condition and
can be utilized for life assessment of structures in which microcracks are observed
during routine in-service inspections. The crack growth period, t g , can be assumed
as the remaining life. The approach can be combined with the incubation time for
crack initiation in the service degraded material when no crack is observed. The
incubation time, t i , of the crack can be estimated using the reference stress and
samples representing the component’s microstructural state and service life. If the
incubation time t i is less than the desired service life, a crack-growth analysis can be
performed to calculate the crack growth life, t g . The safe operation of the component
for the remaining period can be decided if the total crack life, t i + t g , is less than the
desired service life. Inaccuracies in this technique may arise due to errors in selecting
proper values for the constants because of the large scatter in the crack-growth data.
However, better accuracy can be achieved by performing tests on actual samples.
8.4.7 Assessment Based on Microstructural Examination

of Cavitation Damage
Cavitation may be the principal damage mechanism at heat-affected zones, high-

stressed regions, and embrittled regions like grain boundary carbide films and δ
phase particles. The damage by creep cavitation can be assessed by microstructural
examination of the surface. The microstructural studies can be carried out by repli-
cating or in-situ examination of the surface and ex-situ investigation of the extracted
service-exposed samples during preventive maintenance. Neubauer and Wedel [27]
have classified the stage-wise creep damage in steels’ microstructures and classi-
fied the damage into four classes. These classes are (1) Class A damage when the
cavities are isolated; (2) Class B damage when cavities are oriented; (3) Class C
damage when cavities are linked, and microcracks appear; and (4) Class D damage
when macrocracks form. Figure 8.9 depicts different stages of creep and concomi-
tant microstructural damage. The four damage classes have been correlated to 0.46,
65, 0.81, and 1.0 fractions of the expended life [27]. This type of microstructural-
based damage analysis is often utilized to estimate the remaining life of thermal
power plants. Alloy 625 may also exhibit similar microstructural damage in creep
dominant service conditions (Fig. 8.10). The plant history data can establish similar
correlations between creep damage microstructures and operation history parameters
like tensile stress, temperature, and time through the Larson and Millar Parameter
(LMP). These correlations can be used to semi-quantify the creep damage in Alloy
625 components and estimate their remaining life.
8.5 Life-Limiting Damage Criteria for Alloy 625

Components
Life-limiting damage refers to the extent of the damage beyond which it is unsafe
to operate critical components due to catastrophic consequences. Such damages
call for immediate replacement of components. Several such damages have been
identified, which can be used to define the life-limiting damage criteria in Alloy
625. These criteria may make the basis for the acceptance of the service exposure
damage for the continued operation of Alloy 625 components. They may be employed
Fig. 8.9 Schematic illustration of different stages of creep cavitation and concomitant microstruc-
tural damage [27]
Fig. 8.10 An optical

micrograph exhibiting Class
D creep damage in an Alloy
625 tube
with pre-defined tolerances depending upon the criticality of the component and its
function.
8.5 Life-Limiting Damage Criteria for Alloy 625 Components 313
8.5.1 Maximum Hardness of 350 BHN
The hardness of Alloy 625 increases with service exposure at intermediate tempera-
tures (600 - 725 °C). Figure 8.5 shows the hardness variation of the alloy with time
when exposed at about 650 °C. The alloy tends to reach a plateau in hardness at a value
of about 350 BHN. The alloy with a hardness in this range is very brittle with little
ductility at room temperature. It exhibits very low impact energy (~10 J) and limited
flaw tolerance capability with K1C ≈ 40 MPa m1/2 [11]. The alloy’s microstructure
contains a high-volume fraction of embrittling intermetallic and carbide phase parti-
cles. The alloy may be susceptible to catastrophic failure for impact loading condi-
tions. A criterion limiting the maximum hardness of the service-exposed alloy to 350
BHN can be easily employed based on hardness measurements during routine main-
tenance. However, the hardness measurements are associated with significant errors,
particularly during ISI, as they are usually carried out using a portable rebound type
hardness tester, which is highly dependent on surface preparation and skills of the
person carrying out the test.
8.5.2 Minimum 10% Elongation at the Operating

Temperature
This criterion is developed considering the most conservative approach of nuclear

reactor pressure vessel design, which is one of the most critical engineering compo-
nents with respect to its operation and consequential damage. Neutron irradiation of
components in a nuclear reactor severely affects material’s yield strength, ductility,
and creep properties. In general, the yield strength increases, and ductility reduces
with neutron irradiation. Studies have shown that a minimum 10% elongation at oper-
ating temperatures is a safe limit with a minimum of 95% confidence (Fig. 8.11) [28]
for the safe operation of the reactor pressure vessel. The service exposure of Alloy 625
at intermediate temperatures exhibits embrittling behavior similar to that of neutron
irradiation, i.e., a reduction in ductility and an increase in the yield strength. A similar
acceptance criterion of a minimum of 10% elongation at operating conditions may
be adopted for the safe operation of Alloy 625 critical components. Multiple testing
of samples from a given location may be considered to take care of the scattering
associated with sample location, specimen preparation, and testing errors.
8.5.3 Maximum Microstructural Damage
In-situ metallography is commonly used to assess damage in carbon and

low alloy steels due to carbide coarsening and cracking by creep, fatigue,
high-temperature corrosion, hydrogen embrittlement, intergranular corrosion, etc.
Fig. 8.11 The figure depicts a minimum 10% elongation at operating temperature as a safe limit
with a minimum of 95% confidence for the safe operation of a nuclear pressure vessel. The data
shows variation in fracture elongation as a function of accumulated fast neutron radiation damage
(fluence) in SS304 steel irradiated at 550 °C [28]
Maximum microstructural damage is identified to limit the life of the component.

Establishing a similar microstructure-based criterion for Alloy 625 is rather chal-
lenging to define because of the limitation of the standard ISI techniques to resolve
its life-limiting microstructural features. As noted earlier, age-hardening of the alloy
is due to the precipitation of intermetallic phase particles of various types. These
particles can only be imaged by electron microscopy (Chap. 3). Even a criterion
based on the precipitation of grain boundary carbides, similar to that used for steel
structures in power plants, is rather difficult to adopt for Alloy 625 because grain
boundary carbides in nickel-base superalloys grow at very slow rates and remain very
fine. The thickness of grain boundary carbide films is often close to the resolution
limit of the optical microscope. Further, grain boundaries thickness measurement
may be associated with significant errors due to improper (deeper) surface etching
or the replication process. These limitations may result in a substantial error in quan-
tifying grain boundary carbides in any nickel-base superalloys. Such quantification
requires advanced metallography techniques, such as scanning and transmission
electron microscopy, capable of analyzing microstructures with higher resolution,
which are usually beyond the scope of regular ISI. However, precipitation of the
δ phase in Alloy 625 coincides with the precipitation of grain boundary carbides,
and profuse formation of the δ phase particles (as needle shape particles) can be
observed by optical microscopy unambiguously (see, Fig. 8.2). A criterion based on
the precipitation of the δ phase particles may be developed for defining the maximum
microstructural damage.
8.5 Life-Limiting Damage Criteria for Alloy 625 Components 315
8.5.4 Life Expenditure and Minimum Thickness Criteria

for the Creep Dominant Damage
When creep deformation is predominant, the fraction of the expended creep life can
be estimated based on creep-rupture tests of service-exposed samples. The fraction
of the life spent during service can be calculated using the ratio of the time to rupture
of the service-exposed specimen to the expected time to rupture for the virgin alloy
under the same conditions. A fixed percentage of the expended life can be defined
as the life-limiting damage criterion for self-loaded components depending upon
their criticality. However, for pressure-containing components, the criterion should
be based on the minimum thickness of the pressure-retaining boundary to keep the
hoop stress at the maximum operating pressure below the allowable design stress,
including the safety factor.
8.5.5 Class D Damage for Creep Cavitation
The Neubauer and Wedel [27] classification of creep cavitation damage mentioned
in Sect. 8.4.7 calls for different actions for the continuing service of the component.
While the Class A damage does not require immediate remedial action, the Class B
damage calls for their continuous monitoring and reinspection within a period of 1½
to 3 years. The Class C damage calls for limited service until repair, while the Class D
damage calls for an immediate repair or replacement [15]. These recommendations
are quite conservative, and a similar criterion of Class D damage for limiting the life
of creep damage in Alloy 625 components can be adopted.
8.6 Case Studies on the Performance of Alloy

625 Ammonia Cracker Tubes
Alloy 625 is being used for various applications ranging from tubing in the process
industry to thrust-reverser systems in the aerospace and exhaust manifolds of Formula
1 automobiles. Many researchers have reported service degradation of ammonia
cracker Alloy 625 tubes during prolonged exposure at about 650 °C [10–12, 29–
31]. Most of these studies have reported service degradation due to microstructural
modifications and little creep deformation. These tubes are designed for service in
annealed conditions with a maximum permissible creep of 1% in 105 h at 717 °C
and 15.7 MPa pressure [12]. A battery of ammonia cracker tubes are stacked in a
vertical rectangular furnace, which heats them from outside to maintain the process
temperature of the endothermic cracking reaction (Fig. 8.12). Each tube measures
approximately 90 mm in outer diameter, 8.9 mm in wall thickness, and 13 m in
length with an effective height of about 12 m inside the furnace. This section gives
Fig. 8.12 A schematic depicting the arrangement of Alloy 625 tubes in an ammonia cracker unit
a brief description of a few cases that illustrate the performance of Alloy 625 tubes,
including their failure in unusual conditions in ammonia cracker plants.
8.6 Case Studies on the Performance of Alloy 625 Ammonia Cracker Tubes 317
8.6.1 Service Degradation of Tubes and Rejuvenation of Lost

Properties
Chakravartty et al. [11] have carried out extensive studies on microstructural modi-
fications and concomitant mechanical properties’ degradation of an Alloy 625 tube
during service exposure of 100,000 h. They have shown that mechanical properties
degradation is a consequence of microstructure modifications, which are sensitive to
temperature. They have used the precipitation behavior of various phases as markers
to delineate the actual temperatures the tube had experienced at different tube loca-
tions during service (Fig. 3.20). They studied the microstructural degradation at
three areas designated as “top”, “middle”, and “bottom”, respectively at 1, 6, and
11 m distance from the top of the 12 m length inside the furnace. Chakravartty et al.
[11] have demonstrated that the examined ammonia cracker tube had experienced
increasing temperature from top to bottom in the range of about 600 - 800 °C. The
service-exposed alloy exhibited a mixture of fine Ni2 (Cr, Mo) and γ precipitates in
the top section, predominantly coarse γ phase particles in the middle section, and
the co-precipitation of very coarse γ and δ phase particles in the bottom section
of the tube (Fig. 8.13). In addition, the tube exhibited the precipitation of M23 C6
carbides at grain boundaries in the entire length of the tube. The thickness of the
carbide layer increased monotonically from top to bottom (Fig. 8.14).
The precipitation of the Ni2 (Cr, Mo) phase in Alloy 625 is known to occur during
prolonged aging at temperatures lower than 628 °C and that of the γ particles over
a temperature range of 600 to 750 °C, with its nose corresponding to the fastest
kinetics at around 650 °C (Fig. 3.15). The precipitation of the Ni2 (Cr, Mo) and γ
phases indicated that the temperature of the tube did not exceed beyond about 650 °C
in the top section and about 750 °C in its middle section, at least for a significant
period toward the end of its service life. Co-precipitation of carbide and the δ phases
occurs only at temperatures around 800 °C. The observation of M23 C6 carbide in the
entire tube length is consistent with its precipitation at temperatures in the range of
550–1000 °C. The size of the γ phase particles increased monotonically from top
to bottom. The precipitation of the δ phase occurred at the expense of γ phase, as
evidenced by the γ -precipitate free zones around δ particles (Fig. 6 of Ref. [11]).
An increase in the size of particles and the thickness of the grain boundary carbide
film from top to bottom also attested to the increasing tube temperature from top to
bottom as the exposure period was the same for the entire tube length.
Table 8.2 compares the mechanical properties data of the service-exposed tube
with that of the virgin tube material. From this table, it was clear that a significant loss
of properties had occurred throughout the cracker tube during service with a progres-
sive increase in microstructural degradation from top to bottom. After service expo-
sure, the room temperature yield strength along the tube length had almost doubled.
This increase in strength was accompanied by a massive reduction in the ductility
and impact properties, making the alloy vulnerable to catastrophic failure. While
the exposed tube was uniformly hardened due to the precipitation of γ particles,
the top section of the tube was hardened most due to the precipitation of additional
Fig. 8.13 Microstructural conditions of the alloy at the top, middle and bottom sections of an Alloy
625 ammonia cracker tube, as revealed by transmission electron microscopy. The ammonia cracker
tube was exposed for 100,000 h at about 650 ± 50 °C. Insets show electron diffraction patterns
from corresponding regions confirming the presence of different phases
Ni2 (Cr, Mo) particles, whose volume fraction was as high as that of γ particles.
However, these properties improved at elevated temperatures. Yield strengths of all
the sections showed a decreasing trend with increasing test temperatures, except in
the temperature range 300–550 °C where the yield strength showed either a plateau
or a slight increase within the temperature range [11]. The ultimate tensile strength
of both bottom and middle sections showed a slight increase with test temperature
up to 600 °C, whereas the ultimate tensile strength of the top area showed a slight
decrease up to about 450 °C. The UTS of all the sections dropped drastically with
Fig. 8.14 Precipitation of carbide films along grain boundaries at the a top, b middle and c bottom
sections of Alloy 625 ammonia cracker tube after a service exposure of 100,000 h at about 650 ±
50 °C. (a) is a transmission electron microscopy image, while (b) and (c) are optical images
Table 8.2 A comparison of room temperature tensile strength and ductility of virgin and service-
exposed wrought Alloy 625 ammonia cracker tubes [11]
Property Virgin Service-exposed alloy
Top Middle Bottom
Yield strength (MPa) 345 785 710 613
UTS (MPa) 758 1051 867 810
Elongation (%) 50 18 10 9
The virgin tube properties are averages of corresponding ranges given in the source
a further increase in the test temperature. However, the ductility improved initially,
followed by a rapid rise, with temperature for all the sections.
The presence of continuous and thick carbide precipitation at grain boundaries
reduced the toughness of the tube, as observed in middle and bottom specimens. The
specimens from the bottom section exhibited the maximum microstructural damage.
It showed a continuous carbide film at grain boundaries and the conspicuous acicular
δ precipitates in its vicinity and within the matrix. Similar degradation in mechanical
properties, particularly fracture properties, have been reported in other nickel-base
superalloys [32, 33]. The poor room-temperature ductility and low impact toughness
(10–40 J) of the bottom section even at 300 °C made the exposed tube vulnerable
to catastrophic failure. Fracture mechanics evaluation indicated that the√exposed
material had the minimal flaw tolerance capability at a KIC ≈ 40 MPa m [11],
consistent with another report by Thomas and Taits [9]. The severe loss of ductility
in the bottom section can be attributed to the profuse precipitation of δ particles,
which act as internal notches at grain boundaries, and the continuous carbide films
that block the transfer of the slip across grain boundaries. These factors promote
cracking locally, thereby limiting the attainment of the ultimate strength and lowering
of ductility and fracture toughness.
A solution annealing treatment at 1160 °C for 2 h reversed the damage due to
service exposure. The solution annealing treatment dissolved all the hardening phase
particles and carbides formed during service exposure and recovered all mechanical
properties to the codal requirements [11].
8.6.2 Failure of Tubes at a Temperature Less Than 550 °C
The top ends of cracker tubes are butt welded by stub ends (Fig. 8.12) that facilitate
lip-sealed and flange joints for leak tightness and strength. The stub ends remain
outside the furnace. The ammonia vapors from the inlet header enter the tubes at
527 °C below the stub ends outside the furnace. Stub ends, therefore, experience a
temperature not more than about 525 °C. However, in an incident, multiple stub ends
failed in a brittle manner (Fig. 8.15), at a location sufficiently away from the weld
joints, only after a service exposure of about 47,000 h [30]. Transmission electron
microscopy evidence confirmed that the failed stub end alloy always experienced a
temperature much below 600 °C as its hardness and microstructure remained similar
to that of the virgin, devoid of any precipitate like Ni2 (Cr, Mo), γ or δ phase parti-
cles which form at about 600°C and above. However, the microstructure exhibited
the formation of continuous layer of M23 C6 carbide film along grain boundaries,
which had caused its failure in a brittle manner (Fig. 8.15). The formation of grain
boundary carbides after 47,000 h of operation at a temperature less than about 550 °C
was somewhat surprising because the cracker tubes are known to easily survive a
full-service life of 100,000 h at a much higher average temperature of about 670 °C
[11]. The subsurface in the vicinity of the ruptured stub end revealed a homoge-
neous network of secondary and tertiary cracks around primary cracks, indicating
Fig. 8.15 A photograph of a

stub-end failed at a
temperature less than
550 °C. Reprinted from Ref.
[30], Copyright (2013), with
permission from Elsevier
Fig. 8.16 a Optical micrograph of an un-etched failed stub-end sample revealing thick carbide
layers along grain boundaries. b Secondary electron micrograph of the fractured surface of a failed
stub-end showing intergranular brittle nature of the fracture. Reprinted from Ref. [30], Copyright
(2013), with permission from Elsevier
a weakening of grain boundaries due to the formation of a thick M23 C6 film along
with them (Fig. 8.16a). The weak nature of grain boundaries was evident from the
brittle intergranular fracture mode (Fig. 8.16b). This unusual precipitation of the
M23 C6 carbide film at grain boundaries, at low temperatures, and in a shorter life
span was found to be due to the alloy’s chemistry, which contained much higher
nitrogen content than usually present nickel-base superalloys.
The stub end alloy contained about 250 ppm of nitrogen, which was about an
order higher than that Alloy 625 (Chap. 3), along with about 330 ppm of carbon.
The formation of the M23 C6 carbide film occurred in less than half the designed
life and at a temperature much below its formation temperature. Nitrogen levels in
superalloys are usually kept at less than 50 ppm. The carbon content is also kept
low to about 300 ppm. This carbon is further reduced to negligible levels in the
austenite matrix by scavenging out by strong carbide formers like titanium, niobium,
and hafnium that form MC carbides during solidification. The secondary M23 C6
carbide precipitates due to the degeneration of the primary MC carbides during
service exposure at temperatures between 550 and 1000 °C, which is a prolonged
process. Hence, the service exposure of even 100,000 h in Sect. 8.6.1 was insuffi-
cient to form enough grain boundary carbide film to cause the rupture. However,
when a high amount of nitrogen was present, primary carbide forming elements
(titanium, niobium, and hafnium) preferred to form nitrides, instead of carbides, due
to their stronger affinity to nitrogen [30]. The formation of the nitrides appeared to
consume titanium/niobium required to form primary MC carbides and, consequently,

left free carbon in the matrix for the formation of M23 C6 carbides, which otherwise
form after slow degeneration of the primary MC carbides at higher temperatures.
This free carbon easily formed carbide layers at grain boundary during service at
a lower temperature and comparatively in a shorter time period. The higher nitrogen
content in the alloy may have resulted from a poor quality of the raw material used
or a poor control of the melting conditions.
8.6.3 Fish Mouth Opening of a Tube by Temperature

Excursion
In an unusual incident, a cracker tube failed by creep rupture after an operation period
of about 5600 h. The ruptured tube showed a typical “Fish-Mouth Opening” of about
400 mm length and 150 mm width (Fig. 8.17). The tube’s “fish-mouth” opening in
the longitudinal direction is a classical failure mode when the hoop stress exceeds
the yield stress at high temperatures. The thickness of a middle portion of the “fish
mouth” had reduced by about 50% to 4.6 mm, from an initial thickness of 8.9 mm.
This heavy deformation indicated that the tube was subjected to creep deformation
for a considerable time. This type of rupture was rather unusual for ammonia cracker
tubes as it was the first such incident in about 75 years of the cumulative history of
ammonia cracker plants. However, such types of failures are quite common in tubular
boiler structures due to temperature excursion beyond their design temperature due
to (1) short-term overheating and (2) long-term overheating [15].
The short-term overheating failure occurs when the temperature excursion exceeds
870 °C, above which the harder ferrite phase in steels is completely converted into the
softer austenite phase. This transformation results in a drastic drop in the strength
causing failure of the tube. The short-term overheating failures are characterized
by considerable metal deformation, visible as elongation or thinning of the fractured
surface. Wall thinning and local bulging precede the fracture because of the material’s
loss of strength at high temperatures. The wide “fish-mouth” opening, often much
wider than the tube’s diameter, has thin-edge fractured surfaces due to considerable
swelling. Single or multiple short-term temperature excursions beyond 870 °C raise
tube’s temperature to an extent that it deforms under internal pressure. When the
thickness of the tube reaches a limit, it yields to the hoop stress to cause the failure.
On the other hand, long-term overheating occurs at temperatures below 870 °C
but above the normal operating temperature until the creep life is expended. During
long-term overheating, steel’s strength reduces gradually as it remains within the
ferritic-bainitic microstructure regime. The failed tube is characterized by minimal
swelling thickness reduction and a longitudinal split that is much narrow, compared
to that in a short-term overheating failure, often less than the diameter of the tube
itself.
Fig. 8.17 A photograph of

an Alloy 625 tube failed by a
characteristic fish-mouth
opening of the tube under the
influence of hoop stress
In the present case of fish-mouth failure of Alloy 625 tube, bulging and deforma-
tion of the metal before the fish-mouth opening and its width more than the diameter
of the tube points to be a characteristic “short-term overheating” type of failure.
Conservative estimates give hoop stress of about 63 MPa to 8.9 mm thick cracker
tubes of internal diameter about 71 mm and pressurized at 14 MPa. This hoop stress
would rupture the tube at a thickness of about 4.6 mm at uniaxial stress above
106 MPa [34]. This stress exceeds the yield stress of Alloy 625 at temperatures
above 1000 °C [26], indicating that the tube failed at a temperature above 1000 °C.
Microstructural analysis of the region around the fish mouth revealed the presence
of recrystallized grains. Recrystallization in this alloy occurs at temperatures over
1000 °C(Sect. 6.1). The microstructural analysis established temperature excursion of
the tube over 1000 °C, which was attributed to burners or some other external heating
source malfunctioning. At temperatures above 1000 °C and an internal pressure of
14 MPa, the tube would fail by creep rupture in about 2.8 h.
8.7 Summary
High-temperature creep and corrosion are the two most common life-limiting damage
mechanisms at elevated temperatures. Alloy 625 is inherently stable against these
two damages, at least in the intermediate range of its applications, because of its
chemistry. While the alloy embrittles significantly during service degradation due
to extensive microstructural modifications, it may not contribute towards the failure
of components. Still, the alloy may be vulnerable to catastrophic failure under
unfavorable conditions. This service damage can be reversed by appropriate solution
annealing treatments. Several standard life management techniques can be effectively
adapted to monitor service degradation and predict the remaining service life of Alloy
625 components.
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Appendix A
Superalloy Compositions
This appendix gives nominal compositions of commonly used iron-based, nickel-

based and cobalt-based superalloys. Some alloys, like Inconel 718, Incoloy 903,
etc., contain nickel and iron in comparable amounts. Such alloys are also classified
as iron-nickel alloys. However, this classification is ignored to restrict alloys to the
three major categories based on the highest elemental concentration in their nominal
compositions. These compositions are compiled based on the literature and the alloy’s
datasheets (Tables A.1, A.2, A.3, A.4).
© The Editor(s) (if applicable) and The Author(s), under exclusive license 327
to Springer Nature Singapore Pte Ltd. 2022
https://doi.org/10.1007/978-981-19-1562-8
328
Table A.1 Nominal compositions of selected wrought iron base superalloys

Alloy Ni Fe Co Cr Mo W Nb Al Ti C Others
Solid Solution hardened iron base superalloys
Alloy N-155 (Multimet) 20.0 32.2 20.0 21.0 3.0 2.5 1.0 – – 0.15 0.15 N, 0.2 La, 0.02 Zr
Haynes 556 21.0 29.0 20.0 22.0 3.0 2.5 0.1 0.3 – 0.10 0.50 Ta, 0.02 La, 0.002 Zr
I9-9 DL 9.0 66.8 – 19.0 1.25 1.25 0.4 – 0.3 0.30 1.10 Mn, 0.60 Si
Incoloy 800 32.5 45.7 – 21.0 – – – 0.38 0.38 0.05 –
Incoloy 800 H 33.0 45.8 – 21.0 – – – – – 0.08 –
Incoloy 800 HT 32.5 46.0 – 21.0 – – – 0.4 0.4 0.08 0.8 Mn, 0.5 Si, 0.4 Cu
Incoloy 801 32.0 46.3 – 20.5 – – – – 1.13 0.05 –
Incoloy 802 32.5 44.8 – 21.0 – – – 0.58 0.75 0.35 –
Alloy 25-6Mo 25.0 Bal – 20.0 6.5 – – – – – 2* Mn
RA 235MA 11.0 Bal – 21.0 – – – – – 0.1* 0.8* Mn, 2.0* Si, 0.2* N, 0.055 Ce
Precipitation hardened iron base superalloys
A-286 26.0 55.2 – 15.0 1.25 – – 0.2 2.0 0.04 0.005 B, 0.3 V
Discaloy 26.0 55.0 – 14.0 3.0 – – 0.25 1.7 0.06 –
Incoloy 903 38.0 41.0 15.0 0.1* 0.1 – 3.0 0.7 1.4 0.04 –
Incoloy 909 38.0 42.0 13.0 – 0.0 0.0 4.7 0.0 1.5 0.01 0.4 Si, 0.001 B
Pyromet CTX-1 37.7 39.0 16.0 0.1* 0.1 – 3.0 1.0 1.7 0.03 –
Incoloy 907 38.4 42.0 13.0 – – – 4.7 0.03 1.5 0.01 0.15 Si
Incoloy 909 38.0 42.0 13.0 – – – 4.7 0.03 1.5 0.01 0.4 Si
Appendix A: Superalloy Compositions
Table A.2 Nominal compositions of selected wrought cobalt base superalloys
Solid solution hardened cobalt base superalloys

Haynes 25 (L605) 10.0 3.0 50.0 20.0 – 15.0 – – – 0.1 1.5 Mn
Haynes 188 22.0 3.0* 37.0 22.0 – 14.5 – – – 0.1 0.90 La
Alloy S-816 20.0 4.0 42.0 20.0 4.0 4.0 4.0 – – 0.38 –
MP35-N 35.0 – 35.0 20.0 10.0 – – – – – –
MP159 25.0 9.0 36.0 19.0 7.0 – 0.6 0.2 3.0 – –
Stellite B 1.0 1.0 61.5 30.0 – 4.5 – – – 1.0 –
UMCo-50 – 1.0 49.0 28.0 – – – – – 0.12 –
329
Table A.3 Nominal compositions of selected wrought nickel base superalloys.
330
Solid solution hardened nickel base superalloys
Alloy 28 31 37.0 – 27 3.5 – – – – 0.02* 1.0 Cu, 2.0* Mn, 0.7* Si
Alloy 59 60 1.5* 0.3* 23 15.8 – – 0.25 – 0.01* 0.1* Si
Haynes 214 76.5 3.0 – 16.0 – – – 4.5 – 0.03 –
Haynes 230 55.0 3.0* 5.0* 22.0 2.0 14.0 – 0.35 – 0.10 0.015* B, 0.02 La
Monel 400 65.0 2.5* – – – – – – – 0.3* 31.0 Cu, 2.0* Mn, 0.5* Si,
Inconel 600 76.0 8.0 – 15.5 – – – – – 0.08 0.25 Cu
Inconel 601 60.5 14.1 – 23.0 – – – 1.35 – 0.05 0.5 Cu
Inconel 602 63.5 9.5 – 25.0 – – – 2.1 – 0.05 0.5 Zr, 0.5* Si
Inconel 617 55.0 – 12.5 22.0 9.0 – – 1.0 – 0.07 –
Alloy 622 Bal 4.0 2.5* 21.5 13.5 3.0 – – – 0.015* 0.35* V, 0.5* Mn, 0.08* Si
Inconel 625 61.0 2.5 – 21.5 9.0 – 3.6 0.2 0.2 0.05 –
Inconel 686 Bal 5.0* – 21.0 16.0 3.7 – – 0.14 0.01* 0.75* Mn
Inconel 690 58.0 9.0 – 29.0 – – – – – 0.05* 0.5* Si, 0.5* Mn, 0.015* S, 0.5* Cu
RA333 45.0 18.0 3.0 25.0 3.0 3.0 – – – 0.05 –
Hastelloy B 63.0 5.0 2.5* 1.0* 28.0 – – – – 0.05* 0.03 V
Hastelloy B3 65 1.5 3.0* 1.5 28.5 3.0* 0.2* 0.5* 0.2* 0.01* 3.0* Mn, 0.1* Si, 0.2* V, 0.2* Cu, 0.2* Ta,
0.01* Zr
Hastelloy C-4 65 3.0* 2.0* 16.0 16.0 – – – 0.7* 0.01* 1.0 Mn, 0.08 Si, 0.5 Cu
Hastelloy C-22 51.6 5.05 2.5 21.5 13.5 4.0 – – – 0.01* 1.0 Mn, 0.1 Si, 0.3 V
Hastelloy C-276 59.0 5.0 – 15.5 16.0 3.7 – – – 0.02* 1.0 Mn, 0.1 Si, 0.3 V
Hastelloy C-2000 59.0 3.0* 2.0* 23.0 16.0 – – 0.5* – 0.01* 1.6 Cu, 0.5 Mn, 0.08 Si
(continued)
Table A.3 (continued)
Hastelloy G 45.0 19.5 2.5* 22.3 6.0 1.0* 2.2 – – 0.05* 1.5 Cu, 1.0* Si
Hastelloy G3 45.0 19.5 5.0* 22.3 6.0 1.5* 0.5* – – 0.05* 2.0 Cu, 1.0* Si
Hastelloy G-30 43.0 15.0 5.0* 30.0 5.5 2.5 0.8 – – 0.03* 1.5* Mn, 0.8* Si, 2.0 Cu
Hastelloy N 72.0 5.0* – 7.0 16.0 – – – 0.5* 0.06 –
Hastelloy S 67.0 1.0 – 15.5 15.5 – – 0.2 – 0.02* 0.02 La
Hastelloy W 61.0 5.5 2.5* 5.0 24.5 – – – – 0.12* 0.6 V
Hastelloy X 49.0 15.8 1.5* 22.0 9.0 0.6 – 2.0 – 0.15 –
Haynes HR-120 37.0 33.0 3.0 25.0 2.5 2.5 0.7 0.1 – 0.05 0.7 Mn, 0.6 Si, 0.2 N, 0.004 B
Haynes HR-160 37.0 2.0 29.0 28.0 – – – – – 0.05 2.75 Si, 0.5 Mn
Nimonic 75 75.0 2.5 – 19.5 – – – 0.15 0.4 0.12 0.25* Cu
Nimonic 86 65.0 – – 25.0 10.0 – – – – 0.05 0.03 Ce, 0.015 Mg
Precipitation hardened Nickel base superalloys
Astroloy 56.5 < 0.3 15.0 15.0 5.25 – – 4.4 3.5 0.06 0.03 B, 0.06 Zr
Custom Age 625 PLUS 61.0 5.0 – 21.0 8.0 – 3.4 0.2 1.3 0.01 –
Haynes 242 62.5 2.0* 2.5* 8.0 25.0 – – 0.5* – 0.10* 0.006* B
Haynes 244 61.0 1.0* 2.0* 8.0 22.5 6.0 – 0.5* – 0.03* –
Haynes 263 52.0 0.7 11.0 20.0 6.0 – – 0.6 2.4 0.06 0.6 Mn, 0.4 Si, 0.2 Cu
Haynes R-41 52.0 5.0 15.0 19.0 10.0 – – 1.5 3.1 0.09 0.5 Si, 0.1 Mn, 0.006 B
Inconel 100 60.0 < 0.6 15.0 10.0 3.0 – – 5.5 4.7 0.15 1.0 V, 0.06 Zr, 0.015 B
Inconel 102 67.0 7.0 – 15.0 2.9 3.0 2.9 0.5 0.5 0.06 0.005 B, 0.02 Mg, 0.03 Zr
Alloy 901 42.5 36.2 – 12.5 6.0 – – – 2.7 0.10* –
(continued)
331
332
Inconel 702 79.5 1.0 – 15.5 – – – 3.2 0.6 0.05 0.5 Mn, 0.2 Cu, 0.4 Si
Inconel 706 41.5 37.5 – 16.0 – – – 0.2 1.75 0.03 2.9 (Nb + Ta), 0.15* Cu
Incoloy 825 42.0 30.0 – 21.5 3.0 – – – 0.9 0.01 1.8 Cu, 1* Mn
Incoloy 925 44.0 29.0 – 20.5 2.8 – – 0.2 2.1 0.01 1.8 Cu
Inconel 718 52.5 18.5 – 19.0 3.0 – 5.1 0.5 0.9 0.08* 0.15* Cu
Inconel 721 71.0 6.5 – 16.0 – – – – 3.0 0.4 2.2 Mn, 0.1 Cu
Inconel 722 75.0 7.0 – 15.5 – – – 0.7 2.4 0.04 0.5 Mn, 0.2 Cu, 0.4 Si
Inconel 725 57.0 9.0 – 21.0 8.0 – 3.5 0.35* 1.5 0.03* –
Inconel 751 72.5 7.0 – 15.5 – – 1.0 1.2 2.3 0.05 0.25* Cu
Inconel 693 Bal 4.25 – 29.0 – – 1.5 3.25 1.0* 0.15* 0.5* Si, 1.0* Mn, 0.01* S, 0.5* Cu
Inconel X-750 73.0 7.0 – 15.5 – – 1.0 0.7 2.5 0.04 0.25* Cu
M-252 56.5 < 0.75 10.0 19.0 10.0 – – 1.0 2.6 0.15 0.005 B
MERL-76 54.4 – 18.6 12.4 3.3 – 1.4 5.1 4.3 0.02 0.35 Hf, 0.06 Zr
Nimonic 80A 73.0 1.5 1.0 19.5 – – – 1.4 2.25 0.05 0.10* Cu
Nimonic 90 55.5 1.5 18.0 19.5 – – – 1.4 2.4 0.06 –
Nimonic 95 53.5 5.0* 18.0 19.5 – – – 2.0 2.9 0.15* + B, + Zr
Nimonic 100 56.0 2.0* 20.0 11.0 5.0 – – 5.0 1.5 0.30* + B, + Zr
Nimonic 105 54.0 – 20.0 15.0 5.0 – – 4.7 1.2 0.08 0.005 B
Nimonic 115 55.0 1.0 15.0 15.0 4.0 – – 5.0 4.0 0.20 0.04 Zr
C-263 51.0 0.7* 20.0 20.0 5.9 – – 0.45 2.1 0.06 –
Pyromet 860 44.0 28.9 4.0 13.0 6.0 – – 1.0 3.0 0.05 0.01 B
(continued)
Pyromet 31 55.5 14.5 – 22.7 2.0 – 1.1 1.5 2.5 0.04 0.005 B
Refractaloy 26 38.0 16.0 20.0 18.0 3.2 – – 0.2 2.6 0.03 0.015 B
Rene 41 55.0 < 0.3 11.0 19.0 10.0 – – 1.5 3.1 0.09 0.01 B
Rene 88 56.4 – 13.0 16.0 4.0 4.0 0.7 2.1 3.7 0.03 0.03 Zr
Rene 95 61.0 < 0.3 8.0 14.0 3.5 3.5 3.5 3.5 2.5 0.16 0.01 B, 0.05 Zr
Rene 100 61.0 1.0* 15.0 9.5 3.0 – – 5.5 4.2 0.16 0.015 B, 0.06 Zr, 1.0 V
Udimet 500 48.0 4.0* 19.0 19.0 4.0 – – 3.0 3.0 0.08 0.005 B
Udimet 520 57.0 – 12.0 19.0 6.0 1.0 – 2.0 3.0 0.08 0.005 B
Udimet 630 50.0 18.0 – 17.0 3.0 3.0 6.5 0.7 1.0 0.04 0.004 B
Udimet 700 53.0 < 1.0 18.5 15.0 5.0 – – 4.3 3.4 0.07 0.03 B
Udimet 710 55.0 – 14.8 18.0 3.0 1.5 – 2.5 5.0 0.07 0.01 B
Udimet 720 55.0 – 14.8 18.0 3.0 1.25 – 2.5 5.0 0.035 0.03 Zr
Udimet 720LI 57.0 – 15.0 16.0 3.0 1.25 – 2.5 5.0 0.025 0.03 Zr
Unitemp AF2-1DA 59.0 < 0.5 10.0 12.0 3.0 6.0 – 4.6 3.0 0.35 1.5 Ta. 0.015 B, 0.1 Zr
Waspaloy 57.0 2.0* 13.5 19.5 4.3 – – 1.4 3.0 0.07 0.006 B, 0.09 Zr
333
Table A.4 Nominal compositions of selected cast superalloys
334
Alloys Ni Fe Co Cr Mo W Ta Al Ti C Other
Nickel base superalloys
B-1900 64.0 – 10.0 8.0 6.0 – 4.0 6.0 1.0 0.1 0.015 B, 0.1 Zr
CMSX-2 66.2 – 4.6 8.0 0.6 8.0 6.0 5.6 1.0 – 6.0 Zr
CMSX-4 Bal . 9.0 6.5 0.6 6.0 6.5 5.6 1.0 – –
CMSX-6 Bal – 5.0 10.0 3.0 – 2.0 4.8 4.7 – –
CMSX-10 SC Bal – 1.5–9.0 1.8–4.0 0.25–2.0 3.5–7.5 7.0–10.0 5.0 – 7.0 0.1–1.2 – 6.0* Re
CoTaC 744 Bal – 2.0 10.0 – 10.0 – 4.0 – 0.6 4.9 Nb
Hastelloy X 50.0 18 1.0 21.0 9.0 1.0 – – – 0.1 –
Inconel 100 60.5 – 15.0 10.0 3.0 – – 5.5 5.0 0.18 0.01 B, 0.06 Zr, 1.0 V
Inconel 713C 74.0 – – 12.5 4.2 – 1.75 6.0 0.8 0.12 0.012 B, 0.1 Zr, 0.9 Nb
Inconel 713LC 75.0 – – 12.0 4.5 – 4.0 6.0 0.6 0.05 0.01 B, 0.1 Zr
Inconel 738 61.5 – 8.5 16.0 1.75 2.6 – 3.4 3.4 0.17 0.01 B, 0.1 Zr, 2.0 Nb
Inconel 792 60.0 – 9.0 13.0 2.0 4.0 – 3.2 4.2 0.2 0.02 B, 0.1 Zr, 2 .0 Nb
Inconel 718 53.0 18.0 – 19.0 3.0 – – 0.5 0.9 0.04 0.1 Cu, 5.0 Nb
X-750 73.0 7.0 – 15.0 – – – 0.7 2.5 0.04 0.25 Cu, 0.9 Nb
M-252 56.0 – 10.0 20.0 10.0 – – 1.0 2.6 0.15 0.005 B
MAR-M 200 59.0 1.0 10.0 9.0 – 12.5 – 5.0 2.0 0.15 0.015 B, 0.05 Zr, 1.0 Nb
MAR-M 246 60.0 – 10.0 9.0 2.5 10.0 1.5 5.5 1.5 0.15 0.015 B, 0.05 Zr
MAR-M 247 59.0 0.5 10.0 8.25 0.7 10.0 3.0. 5.5 1.0 0.15 0.015 B, 0.05 Zr, 1.5 Hf
PWA 1480 Bal – 5.0 10.0 – 4.0 12.0 5.0 1.5 – –
PWA 1484 Bal – 10.0 5.0 2.0 6.0 9.0 5.6 – – –
(continued)
Rene 41 55.0 – 11.0 19.0 10.0 – – 1.5 3.1 0.09 0.01 B
Rene 77 58.0 – 15.0 15.0 4.2 – – 4.3 3.3 0.07 0.015 B, 0.04 Zr
Rene80 60.0 – 9.5 14.0 4.0 4.0 – 3.0 5.0 0.17 0.015 B, 0.03 Zr
Rene 80 Hf 60.0 – 9.5 14.0 4.0 4.0 – 3.0 4.8 0.08 0.015 B, 0.02 Zr, 0.75 Hf
Rene 100 61.0 – 15.0 9.5 3.0 – – 5.5 4.2 0.18 0.015 B, 0.06 Zr, 1.0 V
Rene N4 62.0 – 7.5 9.8 1.5 6.0 4.8 4.2 3.5 0.06 0.004 B; 0.5 Nb, 0.15 Hf
RR 2000 Bal – 15.0 10.0 3.0 – – 5.5 4.0 – –
SRR 99 Bal – 5.0 8.0 – 10.0 3.0 5.5 2.2 – –
Rene N5 Bal – 8.0 7.0 2.0 5.0 7.0 6.2 – – –

Rene N6 Bal – 10.0–15.0 4.25–6 0.5 – 2.0 5.0–6.5 7.0–9.25 5.0–6.25 – – –
Udimet 500 53.0 2.0 17.0 18.0 4 – – 3.0 30 0.1 –
Udimet 700 53.5 – 18.5 15.0 5.25 – – 4.25 3.5 0.1 0.03 B
Udimet 710 55.0 – 15.0 18.0 3.0 1.5 – 2.5 5.0 0.13 0.08 Zr
Waspaloy 57.5 1.0 13.5 19.5 4.2 – – 1.2 3.0 0.07 0.005 B, 0.09 Zr
WAX-20(DS) 72.0 – – – – 20 – 6.5 – 0.20 1.5 Zr
Cobalt base superalloys
Haynes 21 3.0 1.0 64.0 27.0 5.0 – – – – 0.25 –
Haynes 25; L-605 10.0 1.0 54.0 20.0 – 15.0 – – – 0.1 1.5 Mn, 0.4 Si
J-1650 27.0 – 36.0 19.0 – 12.0 2.0 – 3.8 0.20 0.02 B
MAR-M 302 – 0.5 58.0 21.5 – 10.0 9.0 – – 0.85 0.005 B, 0.2 Zr
MAR-M 322 – 0.5 60.5 21.5 – 9.0 4.5 – 0.75 1.0 2 Zr
(continued)
335
336
MAR-M 509 10.0 – 54.5 23.5 – 7.0 3.5 – 0.2 0.6 0.5 Zr
MAR-M 918 20.0 – 52.0 20.0 – – 7.5 – – 0.05 0.1 Zr
NASA Co-W-Re – – 67.5 3.0 – 25.0 – – 1.0 0.40 1.0 Zr, 2 .0 Re
S-816 20.0 4.0 42.0 20.0 4.0 4.0 – – – 0.4 4.0 Nb, 1.2 Mn, 0.4 Si
V-36 20.0 3.0 42.0 25.0 4.0 2.0 – – – 0.27 2.0 Nb, 1.0 Mn, 0.4 Si
W-152 – 2.0 63.5 21.0 – 11.0 – – – 0.45 2.0 (Nb + Ta)
X-40 (Stellite 31) 10.0 1.5 57.5 22 – 7.5 – – – 0.50 0.5 Mn, 0.5 Si
* Maximum; SC Single crystal
Appendix B
Mechanical Properties
See Tables B.1 and B.2.
References
1. Donachie MJ (2002) Superalloys: a technical guide, 2nd edn. Chapter 2, ASM
International. ISBN 0-87,170-749-7
2. Data Sheet Inconel 690 alloy, 2021. https://www.specialmetals.com/documents/
technical-bulletins/inconel/inconel-alloy-690.pdf
3. Data Sheet Inconel 693 alloy, 2021. https://www.specialmetals.com/documents/
4. Data sheet Custom Age 625 PLUS Alloy, 2021. https://www.carpentertechno
logy.com/hubfs/7407324/Material%20Saftey%20Data%20Sheets/725.pdf
5. Data sheet HAYNES 242 alloy, 2021. http://haynesintl.com/docs/default-
source/pdfs/new-alloy-brochures/high-temperature-alloys/brochures/242-bro
chure.pdf?sfvrsn=a17229d4_28
6. Data sheet HAYNES 244 alloy, 2021. http://haynesintl.com/docs/default-
chure.pdf
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https://doi.org/10.1007/978-981-19-1562-8
338 Appendix B: Mechanical Properties
Table B.1 Room temperature tensile properties of selected wrought superalloys [1–6]
Alloy Product Yield Ultimate Elongation Thermal history
form strength tensile (%)
(MPa) strength
(MPa)
Nickel base alloys
Astroloy Bar 1050 1415 16 1093 °C/4 h/OQ +
871 °C/8 h/AC +
982 °C/4 h/AC +
649 °C/24 h/AC +
760 °C/8 h/AC
Cabot 214 – 560 915 38 1121 °C
Custom Age Bar 1007 1287 31 1038 °C/2 h/AC +
625 Plus 760 °C/8 h/FC +
650 °C/8 h/AC
Custom Age Bar 1324 1448 21 732 °C/8 h/FC +
625 Plus 620 °C/8 h/FC
Direct Age
Custom Age Bar 1007 1287 31 38% CW + 650 °C/8 h/FC
625 Plus CW +
& Age 580 °C/8 h/AC
C-2000 Bar 359 758 67 1150 °C/WQ
D-979 Bar 1005 1410 15 1038 °C/1 h/OQ +
815 °C/6 h/AC +
704 °C/16 h/AC
Hastelloy C-22 Sheet 405 800 57 1121 °C/RQ
Hastelloy G-30 Sheet 315 690 64 1177 °C/RAC-WQ
Hastelloy S Bar 455 845 49 1066 °C/AC
Hastelloy X Sheet 360 785 43 1177 °C/1 h/RAC
Haynes 242 Bar 845 1290 45.7 925–1120 °C/AC +
650 °C/48 h
Haynes 244 Sheet 894 1387 35 1120 °C/WQ + 760 °C
/16 h/ FC +
650 °C/32 h/AC
Haynes 230 Sheet 390 870 48 1232 °C/AC
Inconel 600 Bar 285 660 45 1121 °C/2 h/AC
Inconel 601 Sheet 455 740 40 1149 °C/1 h
Inconel 617 Bar 295 740 70 1177 °C/AC
Inconel 617 Sheet 345 770 55 1177 °C/0.2 h/AC
Inconel 625 Bar 490 965 50 1149 °C/1 h/WQ
Inconel 706 Bar 1005 1310 20 982 °C/1 h/AC +
815 °C/3 h/AC +
718 °C/8 h/FC +
621 °C/8 h/AC
(continued)
Appendix B: Mechanical Properties 339
Table B.1 (continued)

(MPa) strength
(MPa)
Inconel 718 Bar 1185 1435 21 980 °C/1 h/AC +
718 °C/8 h/FC +
621 °C/18 h/AC
Inconel 718 Bar 1365 1530 16 718 °C/8 h/SC +
Direct Age 621 °C/8 h/AC
Inconel 718 Bar 1105 1350 16 927 °C/1 h/AC +
Super 718 °C/8 h/SC +
621 °C/8 h/AC
Inconel 690 Rod 334 690 50 1040 °C
Inconel 693 Rod 827 1210 47 1010 °C/0.5 h/AC +
650 °C/1000 h/AC
Inconel X750 Bar 815 1200 27 1150 °C/2 h/AC + 843 °C
/24 h/AC +
705 °C/20 h/AC
M-252 Bar 840 1240 16 1038 °C/4 h/AC +
760 °C/16 h/AC
Nimonic 75 Bar 285 745 40 1052 °C/1 h/AC
Nimonic 80A Bar 620 1000 39 1079 °C/8 h/AC +
704 °C/16 h/AC
Nimonic 90 Bar 810 1235 33 1079 °C/8 h/AC +
704 °C/16 h/AC
Nimonic 105 Bar 830 1180 16 1149 °C/4 h/AC +
1060 °C/16 h/AC +
849 °C/16 h/AC
Nimonic 115 Bar 865 1240 27 1191 °C/1.5 h/AC +
1099 °C/6 h/AC
Nimonic 263 Sheet 580 970 39 1149 °C/0.2 h/WQ +
799 °C/8 h/AC
Nimonic PE 11 Bar 720 1080 30 -
Nimonic PE 16 Bar 530 885 37 1038 °C/4 h /AC +
799 °C/2 h/AC +
699 °C/16 h /AC
Nimonic PK Sheet 780 1180 30 1099–1156 °C/0.25 h/AC
33 +
849 °C/4 h/AC
Pyromet 860 Bar 835 1295 22 -
Rene 41 Bar 1060 1420 14 1066 °C/4 h/AC +
760 °C/16 h/AC
(continued)

(MPa) strength
(MPa)
Rene 95 Bar 1310 1620 15 899 °C/24 h +
1121 °C/1 h/OQ +
732 °C/64 h/AC
Udimet 500 Bar 840 1310 32 1079 °C/4 h/AC +
815 °C/24 h/AC +
760 °C/16 h/AC
Udimet 520 Bar 860 1310 21 1107 °C/4 h/AC +
815 °C/24 h/AC +
760 °C/16 h/AC
Udimet 700 Bar 965 1410 17 1177 °C/4 h/AC +
1079 °C/4 h/AC +
815 °C/24 h/AC +
760 °C/16 h/AC
Udimet 710 Bar 910 1185 7 1177 °C/4 h/AC +
1079 °C/4 h/AC +
815 °C/24 h/AC +
760 °C/16 h/AC
Udimet 720 Bar 1195 1570 13 1113 °C/2 h/AC +
1079 °C/4 h/OQ +
649 °C/24 h /AC +
760 °C/8 h/AC
Unitemp Bar 1015 1560 20 1149 °C/4 h/AC +
AF2-1DA6 760 °C/16 h/AC
Waspaloy Bar 795 1275 25 1079 °C/4 h/AC +
815 °C/24 h/AC +
760 °C/16 h/AC
Iron-base alloys
A-286 Bar 725 1005 25 982 °C/1 h/OQ +
718 °C/16 h/AC
Alloy 901 Bar 895 1205 14 1093 °C/2 h/WQ +
788 °C/2 h/AC +
718 °C/24 h/AC
Discaloy Bar 730 1000 19 1010 °C/2 h/OQ +
732 °C/20 h/AC +
649 °C/20 h/AC
Haynes 556 Sheet 410 815 48 1177 °C/AC
Incoloy 800 Bar 250 595 44 980 °C/0.25 h
Incoloy 825 Bar 310 690 45 940 °C/1 h
(continued)

(MPa) strength
(MPa)
Incoloy 903 Bar 1105 1310 14 815 °C/1 h/WQ +
718 °C/8 h/FC +
621 °C/8 h/AC
Incoloy 907 … 1110 1365 12 980 °C/1 h/AC +
720 °C/8 h/FC +
620 °C/8 h/AC
Incoloy 909 Bar 1020 1310 16 982 °C/1 h/WQ +
718 °C/8 h/FC +
621 °C/8 h/AC
N-155 Bar 400 815 40 1177 °C/1 h/WQ +
816 °C/4 h/AC
V-57 Bar 830 1170 26 982 °C/2–4 h/OQ +
732 °C/16 h/AC
Cobalt base Alloys
Haynes 188 Sheet 485 960 56 1177 °C/1 h/RAC
L-605 Sheet 460 1005 64 1232 °C/1 h/RAC
MAR-M918 Sheet 895 895 48 1191 °C/4 h/AC
MP35N Bar 1620 2025 10 53% CW + 566 °C/4 h/AC
MP159 Bar 1825 1895 8 48% CW + 679 °C/4 h/AC
Stellite 6B Sheet 635 1010 11 1232 °C/AC
OQ Oil quench; AC Air cooled; RQ Rapid quench; RAC Rapid air cooled; WQ Water Quenched;
FC Furnace cooled; CW Cold worked; SC Slow cooled
Table B.2 Room

Alloy 0.2% Yield Ultimate Tensile
temperature tensile properties
strength tensile elongation
of selected cast superalloys
(MPa) strength (%)
[1, 7]
(MPa)
Nickel base
B-1900 825 970 8
CMSX-2(a) 1135 1185 10
CoTaC 744 – 1505 13
DS(b)
GMR-235 640 710 3
IN-100 850 1018 9
IN-162 815 1005 7
IN-625 350 710 48
IN-713 C 740 850 8
IN-713 Hf(c) 760 1000 11
IN-713 LC 750 895 15
IN-718 915 1090 11
IN-731 725 835 6.5
IN-738 950 1095 -
IN-792 1060 1170 4
IN-939 800 1050 5
M-22 685 730 5.5
MM 002(d) 825 1035 7
MAR-M 200 825 1035 5
Hf(e)
MAR-M200 840 930 7
MAR-M246 860 965 5
MAR-M 246 860 1105 6
Hf(f )
MAR-M247 815 965 7
MAR-M421 930 1085 4.5
MAR-M432 1070 1240 6
MC-102 605 675 5
Nimocast 75 179 500 39
Nimocast 80 520 730 15
Nimocast 90 520 700 14
Nimocast 242 300 460 8
Nimocast 263 510 730 18
PWA-1480(a) 895 - 4
Rene 125 Hf(g) 825 1070 5
(continued)

Alloy 0.2% Yield Ultimate Tensile
strength tensile elongation
(MPa) strength (%)
(MPa)
Udimet 500 815 930 13
Udimet 710 895 1075 8
Cobalt-base
Haynes 1002 470 770 6
MAR-M 302 690 930 2
MAR-M 322 630 830 4
MAR-M 509 570 785 4
W-152 585 750 5
X-40 525 745 9
(a) Single crystal [001]; (b) Directionally solidified; (c) MM 004;
(d) RR-7080; (e) MM 009; (f ) MM 006; (g) M 005
Appendix C
Physical Properties of Alloy 625
This appendix gives important physical, thermal and electrical constants and
hydrogen permeability of Alloy 625 as a function of temperature. [1,2,3]
1. Thermal Conductivity, Electrical Resistivity and Coefficient of Thermal

Expansion
Figure C.1 shows variation in thermal conductivity (K), electrical resistivity (ρ) and
coefficient of thermal expansion (α) as a function of temperature, which can be
expressed in the form of polynomial relationships.
1.1.Thermal Conductivity (in W/m·°C): …..K = 9.3+0.016 T
1.2.Electrical Resistivity (in μ·cm): ….. ρ = 129.08+0.03 T – 2.02 × 10-5 T 2
1.3.Coefficient of Thermal Expansion (in μm/ μ·°C): ..…α = 12.65+0.01
T –3.47 × 10-6 T 2 –5.91 × 10-10 T 3
2. Modulus of Elasticity
Modulus of elasticity in tension and shear are commonly known as Young’s modulus
(E) and shear modulus (G). Fig.C.2 shows variations in the two moduli of Alloy 625
as a function of temperature. These moduli of the alloy, in solution treated and
annealed conditions, can be expressed as:
ESolution Treated = 205.58 – 0.052 T – 1.52 × 10-5 T 2

EAnnealed = 207.45 – 0.035 T – 3.75 × 10-5 T 2
GAnnealed = 82.02 – 0.019 T – 1.27 × 10-5 T 2
GSolution Treated = 78.47 – 0.02 T – 5.08 × 10 -5 T 2
Where moduli are expressed in GPa and temperature in degree Celsius.
3. Hydrogen Gas Permeability

The hydrogen permeation of Alloy 625 is controlled by bulk diffusion of hydrogen.
The permeation rate (φ) of hydrogen as a function of temperature across a sheet
https://doi.org/10.1007/978-981-19-1562-8
346 Appendix C: Physical Properties of Alloy 625
Fig. C.1 Coefficient of thermal expansion (CTE), thermal conductivity and electrical resistivity of
Alloy 625 as a function of temperature
Fig. C.2 Variaton in the (a) Young’s and (b) shear moduli of Alloy 625, in solution treated and
annealed conditions, as a function of temperature.
of Alloy 625 of surface area (A) and thickness (x) obeys a half-power pressure (P)
dependence given by the equation [3]

A 60, 128
φ = φo P 1/2 exp
x RT
Appendix C: Physical Properties of Alloy 625 347
where φ is in units of μmol (of H2 )/s, φ o =8.113 μmol (of H2 )/m·s·kPa1/2 , P is in kPa,
T is temperature in Kelvin (K), x and A are in m and m2 , respectively, R = 8.3147
J/mol·K.
References
1. Inconel alloy 625 Data Sheet, 2021,https://www.specialmetals.com/documents/
2. Haynes 625 alloy Data sheet, 2021, https://www.haynesintl.com/docs/default-
chure.pdf?sfvrsn=967229d4_26
3. E.H. Van Deventer and V.A. Maroni, Journal of Nuclear Materials, vol. 92,
(1980) pp.103-111.
Appendix D
Metallography of Alloy 625
Alloy 625 sample preparations for metallographic examination is relatively straight-

forward. Still, special precautions are required during sample preparations to reveal
the actual microstructure comprising of the various hardening phases. Further, the
alloy’s high corrosion resistance makes its etching somewhat tricky. This appendix
gives some guidelines to prepare metallography samples of Alloy 625. Though
most procedures are standard for all superalloys, specific ones for Alloy 625 are
highlighted.
Grinding and Polishing
Sectioning of samples is recommended by quality carborundum/diamond cut-off

wheels to minimise damage to the sample. Grinding of the alloy must be performed
using a series of water-lubricated SiC papers of 120, 240, 320, 400 and 600 grit
sizes. The sample must be ground for about 1 – 2 min with each grit paper on
a rotating wheel at a speed of about 240–300 rpm or on a belt with equivalent
speed. The specimen must be rotated by 45° to 90° between papers to remove the
effects of grinding direction. Table D.1 gives metallography steps and parameters
Table D.1 Steps and parameters recommended for the preparation of metallography samples of
Alloy 625
Preparation steps Abrasive type Speed (rpm) Time (minutes)
Grinding SiC water-cooled paper (Size 120 – 600 250–300 Until plane surface
grit)
Polishing Diamond suspension/paste (9 μm) 100–150 5
Diamond suspension/paste (3 μm) 100–150 4
Diamond suspension/paste (1 μm) 100–150 3
Finishing Alumina slurry (0.05 μm) 80–150 2
https://doi.org/10.1007/978-981-19-1562-8
350 Appendix D: Metallography of Alloy 625
for preparing Alloy 625 samples. The samples must be washed thoroughly using a
soap solution or a suitable solvent while going to the higher grit size paper. If the
samples are likely to contain pores and cracks, ultrasonic cleaning is recommended
during their washing. The ground samples should be polished following a four-step
polishing commencing with a 9 or 6 μm diamond abrasive paste or slurry with
an appropriate liquid extender/lubricant on a cloth pad. Wheel speeds are lower
for polishing, generally 100–150 rpm. The polishing steps are listed in Table D.1.
Careful cleaning of the sample between polishing steps, as in grinding, is required
during polishing. The finishing polish must be with abrasive alumina of 0.3 μm
alpha-alumina or 0.05 μm gamma-alumina suspension. The use of colloidal silica
for the final polish may be problematic as it may darken the surface while etching, as
noted later. After the final polish, clean the surface carefully to remove abrasives by
scrubbing with a cotton soaked in a liquid detergent solution. Dry the surface with
hot air.
Etching
The use of etchant depends upon the specific feature to be revealed. Alloy 625
microstructure may contain various second-phase particles in an austenitic matrix.
The alloy may contain particles of the γ , δ, nitrides or carbides of MC, M23 C6
and M6 C types and topologically-close packed phases. The precipitation-hardenable
variant of the alloy, Alloy 625 PLUS, may also contain γ phase particles. Particles of
the γ or γ phase are too fine to resolve by optical microscopy. However, overaged
γ phase particles can be seen in a scanning electron microscope equipped with a
field emission gun. Optical microscopy can reveal the dendritic structure of a cast
alloy, and grain boundaries and coarse particles of the δ and carbide phases of a
wrought alloy. Figure D.1 shows an optical microstructure of cast Alloy 625.
Etchants commonly used to reveal the general structure of superalloys are listed
in Table D.2. Due to the excellent corrosion resistance of superalloys, most etchants
work best by swabbing the specimen with cotton soaked in the etchant. Immersion
etching without stirring may result in irregular etching. Most etchants must be mixed
fresh and used within a short period. Glyceregia is the mildest of all. Etchants 2 and
3 are listed in increasing strength. The quality of etching of Alloy 625 is sensitive to
the surface finish, especially for wrought alloys. The surface must be scratch-free to
reveal the structure properly. Figure D.2 compares the quality of the microstructures
of a sample after different levels of the surface finish.
Etching of a polished surface with scratches, particularly with chloride ion
containing etchants like Glyceregia. Glyceregia takes about a minute of swabbing
to reveal the microstructure. However, reagents like Glyceregia with chloride ions
may cause ‘flashing’ of the surface upon etching, particularly when colloidal silica
is used for the final surface polish. Flashing refers to the darkening of the surface
immediately upon etching. Examination of the surface shows deep scratches while
Appendix D: Metallography of Alloy 625 351
Table D.2 A list of etchants that can be used to etch Alloy 625 samples. It is recommended to
prepare fresh etchants every time and use them for a short period
S. No Etchant Comment
Acid solution Common name
1 15 ml HCl, 10 ml glycerol, Glyceregia General-purpose etching.
5 ml HNO3 Swab for about 30 s to a
minute
2 15 ml HCl, 10 ml Acetic Acetic glyceregia General-purpose etching.
acid, 5 ml HNO3 , 2 drops Swab for about 30 s to a
glycerol minute
3 15 ml HCl, 10 ml Acetic 15–10–10 reagent General-purpose etching.
acid, 10 ml HNO3 Swab for a few seconds
4 5 g CuCl2 , 100 ml HCl, Waterless Kalling’s reagent Good grain boundary
100 ml ethanol etching. Swab for a few
seconds
5 150 ml HCl, 50 ml lactic Lucas reagent General-purpose etchant.
acid, 3 g oxalic acid Etch the surface
electrolytically at 1–2 V dc
for 10 – 20 s
the microstructure is poorly revealed. Flashing occurs due to the passivation of the
surface. The surface needs to be re-polished to remove these scratches.
Colour etching of nickel-based superalloys is rather tricky. Very high-quality
surface polish is required to develop the tint. After the final polish, the sample
should be electropolished in a supersaturated oxalic acid solution at ~ 2 V at
about −40 °C. After electropolishing, the sample surface must be cleaned care-
fully with cotton soaked in a soap solution to remove any residue interfering
with film formation in tint etching. For tint etching, an etchant comprising 50 ml
demineralised water, 50 ml HCl, 0.8 g Potassium Metabisulfite (K2 S2 O5 ) and
15 g Ammonium bifluoride (NH4 HF2 ) may be used. The etchant should be prepared
in a polypropylene beaker by first adding 50 ml HCl to 50 ml DM water and stirring.
0. 8 g K2 S2 O5 and 15 g NH4 HF2 are added by continuous stirring until they dissolve
completely. Etching must be done by immersing the electropolished sample in the
solution for about 15 min until a blue surface colouration is developed. A continuous
gentle swirling is required to avoid settling any reaction by-products on the sample
surface. After etching, wash the sample with water and dry. Examine the etched
surface under an optical microscope with bright field illumination using the colour
filter. The δ phase appears as light blue and carbides as golden yellow in a light brown
background of the γ phase matrix (Fig. D.3).
352 Appendix D: Metallography of Alloy 625
Fig. D.1 Optical

microstructure of cast Alloy
625 etched with 15–10-10
etchant
Fig. D.2 Optical microstructure of a service exposed wrought Alloy 625 etched with 15-10-10
etchant. The quality of the surface after the final polish in (a) was relatively poor compared to that
in (b)
Appendix D: Metallography of Alloy 625 353
Fig. D.3 Tint microstructure of the wrought Alloy 625 shown in fig.D.2 showing a the δ phase
particles in light blue and b a primary carbide particle in golden yellow in a light brown background
of the γ phase matrix.
Appendix E
Hardness Conversion Table
The hardness of a material can be measured using various techniques. All these
techniques have their own scales. The use of a technique and the scale depends on
the material’s strength and work-hardening behaviour. The scales and their ranges are
limited by the type of indenter (penetrator), and the capacity of the load applied. The
most commonly used hardness techniques are Rockwell hardness, Vickers hardness
and Brinell hardness. The Brinell hardness tester uses a 10-mm-diameter steel ball at a
load of 3000 kg, while the Vickers tester uses a square-base diamond pyramid indenter
with an angle of 136° between the opposite faces. Vickers and Brinell hardness
numbers are designated by VHN and BHN, respectively. The Rockwell technique
uses many indenters with different loads. The Rockwell technique measures hardness
over a wide range and rates it on multiple scales depending upon the indenter and the
load used. Different Rockwell hardness scales are identified by letters indicating A,
B, C, D, etc. For example, HRA refers to Rockwell hardness scale A, HRB refers to
Rockwell hardness scale B, etc. Rockwell A, B and C scales are the most commonly
used. Rockwell A and C use a 120° diamond cone indenter with a slightly rounded
point, called a Braze indenter, at 60 kg and 150 kg loads, respectively. The Rockwell
C scale is used for harder materials with a range of about 20 to 70 HRC. On the
other hand, the Rockwell A scale provides the most extended Rockwell hardness
scale for various materials over a wide range of hardness values. The softer materials
are usually tested on the Rockwell B scale with a 1.6 mm diameter steel ball and a
100 kg load. The range of the Rockwell B scale is from 0 to 100 HRB.
A direct correlation between different hardness scales is difficult to establish
because of inaccuracies associated with its measurements by different indenters and
the local variations in the material’s strength. Nonetheless, some empirical hardness
conversion tables have been established based on the vast data for various steel grades.
Besides, the hardness of steels has also been correlated with their ultimate tensile
strengths. This appendix gives these tables, which can help convert the hardness of
one scale to another in the overlapping hardness range (Table E.1).
https://doi.org/10.1007/978-981-19-1562-8
356 Appendix E: Hardness Conversion Table
Table E.1 Table correlates the room temperature hardness on different hardness scales and tensile
strength of steels
Rockwell C Rockwell B Rockwell A Brinell (HBN) Vickers Tensile
(HRC) (HRB) (HRA) (HVN) strength
(MPa)
56.2 95 100 320
62.3 105 110 350
66.7 114 120 385
71.2 124 130 415
75.0 133 140 450
78.7 143 150 480
81.7 152 160 510
85.0 162 170 545
87.1 171 180 575
89.5 181 190 610
91.5 190 200 640
93.5 199 210 675
95.0 209 220 705
96.7 219 230 740
20 97.6 60.5 226 238 760
21 98.1 61 231 243 770
22 99.0 61.5 237 248 790
23 62 243 254 810
24 62.4 247 260 820
25 62.8 253 266 850
26 63.3 258 272 860
27 63.8 264 279 880
28 64.3 271 286 900
29 64.6 279 294 930
30 65.3 286 302 950
31 65.8 294 310 970
32 66.3 301 318 1010
33 66.8 311 327 1030
34 67.4 319 336 1050
35 67.9 327 345 1080
36 68.4 336 354 1110
37 68.9 344 363 1140
38 69.4 353 372 1180
39 69.9 362 382 1220
(continued)
Appendix E: Hardness Conversion Table 357
Table E.1 (continued)

Rockwell C Rockwell B Rockwell A Brinell (HBN) Vickers Tensile
(HRC) (HRB) (HRA) (HVN) strength
(MPa)
40 70.4 371 392 1250
41 70.9 381 402 1300
42 71.5 390 412 1340
43 72 400 423 1390
44 72.5 409 434 1430
45 73.1 421 446 1480
46 73.6 432 458 1520
47 74.1 442 471 1580
48 74.7 455 484 1640
49 75.2 468 498 1700
50 75.9 482 513 1760
51 76.3 496 528 1820
52 76.8 512 544 1880
53 77.4 525 560 1950
54 78 543 577 2010
55 78.5 560 595 2070
56 79 577 613 2160
57 79.6 595 633 2240
58 80.1 615 653 2330
59 80.7 634 674 2420
60 81.2 654 697 –
61 81.8 670 720 –
62 82.3 688 746 –
63 82.8 706 772 –
64 83.4 722 800 –
65 83.9 739 832 –
66 84.5 – 865 –
67 85 – 900 –
68 85.6 – 940 –

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Materials Horizons: From Nature to Nanomaterials

More information about this series at https://link.springer.com/bookseries/16122

ISSN 2524-5384 ISSN 2524-5392 (electronic)

Dr. Ajit Kumar Mohanty

Mumbai, India Jung Bahadur Singh

I acknowledge my indebtedness to Heavy Water Board (HWB) for entrusting its

Jung Bahadur Singh

2.3.3 The Ewald Sphere . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45

4 Mechanical Behavior of Alloy 625 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111

6.3.1 Conventional Machining . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 203

7.6.3 Sulfidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 276

Appendix A: Superalloy Compositions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 327

The ever-increasing requirement for high-temperature strength and better corrosion-

1.1 High-Temperature Materials Called Superalloys

Superalloys are highly concentrated alloys, based on Group VIII A elements,

Table 1.1 Typical

1.2 Journey of Superalloys

The insatiable thirst for high-temperature strength and better corrosion-resistant

1.3 Alloying Additions in Superalloys

Many elements in various combinations are added to superalloys to produce desired

Table 1.3 (continued)

Table 1.3 (continued)

to catastrophic oxidation [16]. A limited number of superalloys that are known to

1.4 Types of Superalloys

1.4.1 Nickel-Base Superalloys

Fig. 1.3 Classification of nickel-base superalloys

1.4.2 Iron-Base Superalloys

1.4.3 Cobalt-Base Superalloys

Cobalt crystallizes as the hexagonal close-packed phase at lower temperatures and

1.5 Melting and Consolidation of Superalloys

removed by flotation or chemical and physical processes during secondary melting.

powder-metallurgy route. In addition, the powder-metallurgy route produces billets

1.6 Product Forms

1.7 Market Outlook

The prominence of superalloys as high-performance alloys stems from their opera-

1.7.1 Major Drivers

1.7.2 Market Size

Nickel-based superalloys comprise about 80% of the global superalloys market. In

1.7.3 Major Players and Tradenames

Table 1.5 A list of some

1.8 Alloy 625

Alloy 625 is a nickel–chromium-molybdenum based alloy known for its unique

1.9 Why a Book on Alloy 625?

Table 1.6 Major applications of Alloy 625 in various industries

Alloy 625, originally designed as a single-phase solid-solution alloy, contains high

2.1 Definitions of Phase, Crystal Structure

A phase is defined as a chemically homogeneous and physically uniform state of

2.2 Crystal Structures of Phases in Alloy 625

2.2.1 Gamma (γ) Phase

The γ phase is a disordered solid solution of nickel-containing other alloying

N i : 0, 0, 0; 1/2, 1/2, 0; 1/2, 0, 1/2; 0, 1/2, 1/2

2.2.2 Gamma Double Prime (γ ) Phase

The γ phase is an intermetallic compound of N3 M stoichiometry with an ordered

M : 0, 0, 0; 1/2, 1/2, 1/2

This arrangement of atoms in the D022 structure is related to the arrangement

Fig. 2.2 The unit cell of the

(001)γ " //{001}

2.2.3 Ni2 (Cr, Mo) Phase

The Ni2 (Cr, Mo) phase is an intermetallic compound of N2 M stoichiometry with

Table 2.5 Lattice

FsN2 M = 2( f N − f M ) for k = 3, 6 . . . (2.15)

Table 2.8 Lattice

Table 2.11 Lattice

Table 2.11 (continued)