Alloy Phase Diagrams

Luckman Muhmood
Alloys
It is a material that exhibits properties of a metallic material but is
made of more than one element

Ideally an alloy is required to be designed when there is a

requirement of specific properties ( strength, ductility etc.) in
addition to the basic property of the metal

Fe & C – plain carbon steel

Fe, C, Cr, Ni and V – Stainless steel ( corrosion resistant)

Alloys have specific nomenclature !!

Alloy grades / classification

Aluminium

1xxx – min 99.5% aluminum

2xxx series – copper
3xxx series – manganese
4xxx series – silicon
5xxx series – magnesium
7xxx series – zinc
8xxx series – tin
9xxx series – other elements
Alloy grades / classification

Steel

Plain carbon
1010
1018
1045

Alloy
4130
4340
8620

Stainless
316L
What is a phase diagram ?

A phase diagram is a pictorial

representation of the
conditions (temperature,
pressure, composition) for a
phase to exist in equilibrium
with another phase for a
single or multi component
system
Component - chemically recognizable species (Fe and C in carbon steel,
H2O and NaCl in salted water). A binary alloy contains two components, a
ternary alloy – three, etc.

Phase – a portion of a system that has uniform physical and chemical

characteristics. Two distinct phases in a system have distinct physical or
chemical characteristics
(e.g. water and ice) and are separated from each other by definite phase
boundaries. A phase may contain one or more components.

A single-phase system is called homogeneous, systems with two or more

phases are mixtures or heterogeneous systems.
 History
1875 - First T-X diagram (Cu –Ag)
1877 – First high temperature thermocouple (Pt-Pt/10Rh)
1876 -1878 – Gibbs theoretical treatise on
thermodynamics
1878 -1899 – Gibbs study transferred from Maxwell to Van
der Waal to Rozenboom
1900 - The first T-X diagram of Fe-C incorporating Gibbs
phase rule
Sir William Chandler
Roberts-Austen

Henri Louise Le Josiah Willard Gibbs James Clark Maxwell Johannes Diderik van Hendrik Willem Bakhuis
Chatelier der Waals Roozeboom
Concept of equilibrium - single
component system
From second law of thermodynamics ;

G = H – T.S where H = ∫ cp.dT and S = ∫ (cp /T).dT

gas
P = 1 atm
G liquid

solid

Tm Tb
TEMPERATURE
Phase rule for single component systems
In the region between the lines
P=1
C=1
Independent variables =2
No. of variables required to defined the region = 2

On the lines between the regions

P=2
C=1
Independent variables =2
No. of variables required to defined the region = 1

At the meeting point

P=3
C=1
Independent variables =2
No. of variables required to defined the region = 0
F = C-P+2
H2O vs CO2

Clausius-Clapeyron equation : (dP/dT) =(Ss –Sl)/(Vs-Vl)

Binary system
Hume Rothery’s rules

Complete Solid solubility can happen if all the conditions are satisfied:

1. The atomic radii of the solute and solvent atoms should not differ
more than 15%
2. The crystal structure of both the solvent and solute atoms should be
similar
3. The valency of both metal atoms involved should be the same
(metal atoms with lower valency tends to dissolve metals with higher
valency)
4. The electro negativity of the solvent and the solute should be similar
Cu-Ni
Meta Structur Size Valency Electrone ΔHvap V’ Internal pressure
l e g. (kJ/mol) (g/cc) ΔHvap /V’
Cu FCC 1.28 +2 1.90 304.6 7.11 42.8
Ni FCC 1.25 +2 1.91 371.8 6.59 56.4
 The Lever Rule
Finding the amounts of phases in a two phase region:
1. Locate composition and temperature in diagram
2. In two phase region draw the tie line or isotherm
3. Fraction of a phase is determined by taking the length of the tie line to the phase
boundary for the other phase, and dividing by the total length of tie line

The lever rule is a mechanical analogy to the

mass balance calculation. The tie line in the
two-phase region is analogous to a lever
balanced on a fulcrum.
 The Lever Rule

WL = S / (R+S) = (Cα - Co) / (Cα- CL)

Mass fractions:
Wα = R / (R+S) = (Co - CL) / (Cα- CL)
Cooling curves
Binary phase diagrams (Isomorphous)
 NON-EQUILIBRIUM PHASES
• C changes as we solidify.
• Cu-Ni case: First  to solidify has C = 46wt%Ni.
Last  to solidify has C = 35wt%Ni.
• Fast rate of cooling: • Slow rate of cooling:
Cored structure Equilibrium structure
 MECHANICAL PROPERTIES: Cu-Ni System
• Effect of solid solution strengthening on:
--Tensile strength (TS) --Ductility (%EL,%AR)

Adapted from Fig. 9.5(a), Callister 6e. Adapted from Fig. 9.5(b), Callister 6e.
 Regular solution model

G1 = XAGA + XBGB + ΔGMIX

For a regular solution

G1 = XAGA + XBGB + ΩXAXB + RT(XA lnXA +XB lnXB )

G1 = XAGA + XBGB
For a solution with ideal mixing (ΔHMIX = 0)

Gid = XAGA + XBGB + RT(XA lnXA +XB lnXB )

Regular solution model contd..
Some facts !!

(∂G/ ∂T)P = - S

HMIX= ΩXAXB Where Ω=Naz, z=bonds per atom = AB ½(AA +BB)

If Ω<0  A-B bonding preferred

If Ω >0  AA, BB bonding preferred

Free energies of solid A and B should

correspond to the same crystal
structure
Binary Phase diagram - Isomorphous
Ag-Cu
Meta Structur Size Valency Electrone ΔHvap V’ Internal pressure
l e g. (kJ/mol) (g/cc) ΔHvap /V’
Cu FCC 1.28 +2 1.90 304.6 7.11 42.8
Ag FCC 1.44 +1 1.93 255.1 10.7 23.8
 BINARY-EUTECTIC SYSTEMS
has a special composition
2 components with a min. melting T.
Cu-Ag
system

Adapted from Fig. 9.6,

Callister 6e. (Fig. 9.6 adapted
from Binary Phase Diagrams, 2nd ed., Vol. 1, T.B.
Massalski (Editor-in-Chief), ASM International,
Materials Park, OH, 1990.)
13
 BINARY-EUTECTIC SYSTEMS
has a special composition
2 components with a min. melting T.
Cu-Ag
system

Adapted from Fig. 9.6,

Callister 6e. (Fig. 9.6 adapted
from Binary Phase Diagrams, 2nd ed., Vol. 1, T.B.
Massalski (Editor-in-Chief), ASM International,
Materials Park, OH, 1990.)
13
 MICROSTRUCTURES
IN EUTECTIC SYSTEMS-I

• Co < 2wt%Sn
• Result:
--polycrystal of a grains.

Adapted from Fig. 9.9,

Callister 6e.

16
 MICROSTRUCTURES
IN EUTECTIC SYSTEMS-II

• 2wt%Sn < Co < 18.3wt%Sn

• Result:
--a polycrystal with fine
b crystals.

Pb-Sn
system

Adapted from Fig. 9.10,

Callister 6e.

17
 MICROSTRUCTURES
IN EUTECTIC SYSTEMS-III
• Co = CE
• Result: Eutectic microstructure
--alternating layers of a and b crystals.

Pb-Sn
system

Adapted from Fig. 9.12, Callister 6e.

(Fig. 9.12 from Metals Handbook, Vol.
9, 9th ed., Metallography and
Microstructures, American Society
for Metals, Materials Park, OH, 1985.)
Adapted from Fig. 9.11,
Callister 6e. 18
 MICROSTRUCTURES
IN EUTECTIC SYSTEMS-IV
• 18.3wt%Sn < Co < 61.9wt%Sn
• Result: a crystals and a eutectic microstructure

Pb-Sn
system

Adapted from Fig. 9.14,

Callister 6e.
19
 HYPOEUTECTIC &
HYPEREUTECTIC
Adapted from Fig. 9.7,
Callister 6e. (Fig. 9.7
adapted from Binary
Phase Diagrams, 2nd
ed., Vol. 3, T.B. Massalski
(Editor-in-Chief), ASM
International, Materials
Park, OH, 1990.)

(Figs. 9.12 and

9.15 from Metals
Handbook, 9th ed.,
Vol. 9,
Metallography and
Microstructures,
American Society
for Metals,
Materials Park,
OH, 1985.)

Adapted from Adapted from Fig. 9.15,

Fig. 9.15, Callister 6e. Adapted from Fig. 9.12, Callister 6e. (Illustration
Callister 6e. only)
20
COMPLEX PHASE DIAGRAMS: Cu-Zn
 IRON-CARBON (Fe-C) PHASE DIAGRAM

• Pure iron: 3 solid

phases
– BCC ferrite ( )
– FCC Austenite ()
– BCC 
• Beyond 6.7% C
cementite (Fe3C)
• Eutectic: 4.3% C
– L   + Fe3C
– (L  solid + solid)
• Eutectoid: 0.76% C
–    + Fe3C
– (solid  solid +
solid)
 IRON-CARBON (Fe-C) PHASE
DIAGRAM

(Adapted from Fig. 9.24, Callister 6e. Adapted from Fig. 9.21,Callister 6e. (Fig. 9.21
(Fig. 9.24 from Metals Handbook, 9th ed., adapted from Binary Alloy Phase Diagrams, 2nd ed.,
Vol. 9, Metallography and Vol. 1, T.B. Massalski (Ed.-in-Chief), ASM
Microstructures, American Society for International, Materials Park, OH, 1990.)
Metals, Materials Park, OH, 1985.)
21
HYPOEUTECTOID STEEL

Adapted from Figs.

9.21 and 9.26,Callister
6e. (Fig. 9.21 adapted
from Binary Alloy
Phase Diagrams, 2nd
ed., Vol. 1, T.B.
Massalski (Ed.-in-
Chief), ASM
International, Materials
Park, OH, 1990.)

Adapted from
Fig. 9.27,Callister
6e. (Fig. 9.27 courtesy Republic Steel Corporation.) 22
HYPEREUTECTOID STEEL

Adapted from Figs.

9.21 and 9.29,Callister
6e. (Fig. 9.21 adapted
from Binary Alloy
Phase Diagrams, 2nd
ed., Vol. 1, T.B.
Massalski (Ed.-in-
Chief), ASM
International, Materials
Park, OH, 1990.)

Adapted from
Fig. 9.30,Callister
6e. (Fig. 9.30
copyright 1971 by United States Steel Corporation.) 23
δ ferrite:
Interstitial solid solution of carbon in iron of body centred
cubic crystal structure (Fig ) (δ iron ) of higher lattice
parameter (2.89Å) having solubility limit of 0.09 wt% at
1495°C with respect to austenite. The stability of the phase
ranges between 1394-1539°C.

Fig: Crystal structure of ferrite

This is not stable at room temperature in plain carbon steel.

However it can be present at room temperature in alloy steel
specially duplex stainless steel.

41
γ phase or austenite:
Interstitial solid solution of carbon in iron of face centred cubic
crystal structure (Fig) having solubility limit of 2.11 wt% at 1147°C
with respect to cementite. The stability of the phase ranges between
727-1495°C and solubility ranges 0-0.77 wt%C with respect to alpha
ferrite and 0.77-2.11 wt% C with respect to cementite, at 0 wt%C the
stability ranges from 910-1394°C.

Fig: Crystal structure of austenite

42
Fig. 3(b): Polished sample held at austenitisation temperature.
Grooves develop at the prior austenite grain boundaries due to the
balancing of surface tensions at grain junctions with the free
surface. Micrograph courtesy of Saurabh Chatterjee.

43
α-ferrite:
Interstitial solid solution of carbon in iron of body centred
cubic crystal structure (α iron )(same as Fig) having solubility
limit of 0.0218 wt % C at 727°C with respect to austenite.
The stability of the phase ranges between low temperatures to
910°C, and solubility ranges 0.00005 wt % C at room
temperature to 0.0218 wt%C at 727°C with respect to
cementite.
There are two morphologies can be observed under
equilibrium transformation or in low under undercooling
condition in low carbon plain carbon steels. These are
intergranular allotriomorphs (α)(Fig) or intragranular
idiomorphs(αI) (Fig)

44
Fig. 4: Schematic diagram of grain boundary allotriomoph
ferrite, and intragranular idiomorph ferrite.

45
Fig.5: An allotriomorph of ferrite in a sample which is partially
transformed into α and then quenched so that the remaining γ
undergoes martensitic transformation. The allotriomorph grows
rapidly along the austenite grain boundary (which is an easy
diffusion path) but thickens more slowly. 46
Fe3C or cementite:

Interstitial intermetallic compound of C & Fe with a carbon content

of 6.67 wt% and orthorhombic structure consisting of 12 iron atoms
and 4 carbon atoms in the unit cell.
Stability of the phase ranges from low temperatures to 1227°C

Fig.9(a): Orthorhombic crystal structure of cementite. The purple

atoms represent carbon. Each carbon atom is surronded by eight iron
atoms. Each iron atom is connected to three carbon atoms.
47
Critical temperatures:
A=arret means arrest

A0= a subcritical temperature (<A1) = Curie temperature of

cementite=210°C

A1=Lower critical temperature=eutectoid temperature=727°C

A2=Curie temperature of ferrite=768/770°C

A3=upper critical temperature=γ+α /γ phase field boundary

=composition dependent=910-727°C

A4=Eutectic temperature=1147°C

A5=Peritectic temperature=1495°C
48
 Acm=γ/γ+cementite phase field boundary=composition dependent =727-
1147°C
In addition the subscripts c or r are used to indicate that the temperature is
measured during heating or cooling respectively.
c=chaffauge means heating, Ac
r=refroidissement means cooling, Ar

Types/morphologies of phases in Fe-Fe3C system

Cementite=primary (CmI), eutectic (Cmeu), secondary (CmII)(grain
boundary allotriomophs, idiomorphs), eutectoid (Cmed) and tertiary(CmIII).

Austenite= austenite(γ)(equiaxed), primary (γI), eutectic (γeu), secondary

(γII) (proeutectoid),

α-ferrite=ferrite (α) (equiaxed), proeutectoid or primary (grain boundary

allotriomorphs and idiomorphs)(αI), eutectoid(αeu) and ferrite (lean in
carbon) (α’).
Phase mixtures
49
Pearlite (P) and ledeburite(LB)
Important Reactions
Peritectic reaction
Liquid+Solid1↔Solid2
L(0.53wt%C)+δ(0.09wt%C)↔γ(0.17wt%C) at 1495°C
Liquid-18.18wt% +δ-ferrite 81.82 wt%→100 wt% γ

Fig.10: δ-ferrite in dendrite form in as-cast Fe-0.4C-

2Mn-0.5Si-2 Al0.5Cu, Coutesy of S. Chaterjee et al.
M. Muruganath, H. K. D. H. Bhadeshia
50
Eutectic reaction
Liquid↔Solid1+Solid2
Liquid (4.3wt%C) ↔ γ(2.11wt%C) + Fe3C (6.67wt%C) at 1147˚C
Liquid-100 wt% →51.97wt% γ +Fe3C (48.11wt%)
The phase mixture of austenite and cementite formed at eutectic
temperature is called ledeburite.

Fig.11: Microstructure of white cast iron containing

massive cementite (white) and pearlite etched with 4%
nital, 100x. After Mrs. Janina Radzikowska, Foundry
Research lnstitute in Kraków, Poland 51
Fig. 12: High magnification view (400x) of the white cast iron
specimen shown in Fig. 11, etched with 4% nital. After Mrs.
Janina Radzikowska, Foundry Research lnstitute in Kraków,
Poland

52
Fig. 13: High magnification view (400x) of the white cast
iron specimen shown in Fig. 11, etched with alkaline sodium
picrate. After Mrs. Janina Radzikowska, Foundry Research
lnstitute in Kraków, Poland

53
Eutectoid reaction
Solid1↔Solid2+Solid3
γ(0.77wt%C) ↔ α(0.0218wt%C) + Fe3C(6.67wt%C) at 727°C
γ (100 wt%) →α(89 wt% ) +Fe3C(11wt%)
Typical density
α ferrite=7.87 gcm-3
Fe3C=7.7 gcm-3
volume ratio of α- ferrite:Fe3C=7.9:1

54
Fig. 15 : The appearance of a pearlitic
microstructure under optical microscope.

55
Fig. 16: A cabbage filled with water analogy of the three-
dimensional structure of a single colony of pearlite, an
interpenetrating bi-crystal of ferrite and cementite.

56
Fig. 17: Optical micrograph showing colonies
of pearlite . Courtesy of S. S. Babu.

57
 Types of Cast Iron
Gray iron
• graphite flakes
• weak & brittle under tension
• stronger under compression
• excellent vibrational dampening
• wear resistant Adapted from Fig. 11.3(a) & (b), Callister 7e.

Ductile iron
• add Mg or Ce
• graphite in nodules not flakes
• matrix often pearlite - better
ductility
Chapter 11 - 58
 Types of Cast Iron
White iron
• <1wt% Si so harder but brittle
• more cementite

Adapted from Fig. 11.3(c) & (d), Callister 7e.

Malleable iron
• heat treat at 800-900ºC
• graphite in rosettes
• more ductile

Chapter 11 - 59
 Production of Cast Iron

Adapted from Fig.11.5,

Callister 7e.

Chapter 11 - 60
 Objectives of heat treatment (heat treatment processes)

The major objectives are

• to increase strength, harness and wear resistance (bulk hardening,
surface hardening)

• to increase ductility and softness (tempering, recrystallization

annealing)

• to increase toughness (tempering, recrystallization annealing)

• to obtain fine grain size (recrystallization annealing, full

annealing, normalising)

• to remove internal stresses induced by differential deformation by

cold working, non-uniform cooling from high temperature during
61
casting and welding (stress relief annealing)
• to improve machineability (full annealing and normalising)

• to improve cutting properties of tool steels (hardening and

tempering)

• to improve surface properties (surface hardening, corrosion

resistance-stabilising treatment and high temperature
resistance-precipitation hardening, surface treatment)

• to improve electrical properties (recrystallization, tempering,

age hardening)

• to improve magnetic properties (hardening, phase

transformation)
62
63
Fe-Cementite metastable phase diagram (microstructural)
L=liquid, Cm=cementite, LB=ledeburite, δ=delta ferrite, α=
1539˚C δ+L L alpha ferrite, α’= alpha ferrite(0.00005 wt%C) γ=austenite,
δ A5=1495˚C P=pearlite, eu=eutectic, ed=eutectoid, I=primary,
0.09 0.53 II=secondary, III=tertiary
δ+γ 0.17
1227˚C

1394˚C
L+γI 4.30 L+CmI
γ γI+LB LB+CmI A4=1147˚C
Temperature, °C

2.11
LB’ (γeu(γII
γI’(γII+CmII)+LB’ (γ’eu(γII
+CmII)+Cmeu)
+CmII)+Cmeu)
+CmI
A B C

Ledeburite=LB(γeu+Ceu)
910˚C D E F
A2 A3
=668/ Cm
770˚C 0.77
αI+γ γII+CmII
0.0218 A1=727˚C
α αI+ (P(αed P(αed+Cmed) (P(αed+Cmed)+CmII)+ LB’ (P(αed+Cmed) LB’ (P(αed+Cmed)
Pearlite

+CmII +CmII+Cmeu) +CmII)+Cmeu)+CmI

+Cmed)

αI(α’+CmIII)+ P(α (α’

ed ed (P(αed(α’ed+CmIII)+Cmed) +CmII)+ LB’
(P(αed(α’ed+C
+CmIII)+Cmed) LB’ ((P(αed(α’ed+CmIII)+Cmed) ((P(αed(α’ed+CmIII)+Cmed)
mIII)+Cmed) +Cm +CmII)+Cmeu) +CmII)+ Cmeu)+CmI
II
Ao=210˚C
α’+CmIII
6.67
0.00005
Weight percent carbon 64
 Annealing
Heating to above upper critical temperatures and
furnace cooling (slow)

Reduces hardness
Stress relieve (internal)
Improve machinability
Facilitate cold working by increasing ductility

Types

Full Annealing
Box Annealing
Bright Annealing

65
 Normalizing
Heating to above upper critical temperatures and
cooling in air or other media (cooling rate faster than
annealing)

Eliminate coarse grain structure

Improve machinability

Material becomes harder and less ductile as compared

to annealing (finer pearlite and pearlite phase is higher

66
Hardening /Quenching
Heating to above upper critical temperatures and rapid
cooling in water medium, salt or oil

Formation of Martensite
Very hard and brittle

Hardness depends on austenizing temperature and

rate of quenching

Improper quench results in retained austenite in the

sample

67
Tempering
• Almost always done following heat treat
as part of the austenitizing process!
• Because of lack of adequate toughness
and ductility after heat treat, high carbon
martensite is not a useful material
despite its great strength (too brittle).
• Tempering imparts a desired amount of
toughness and ductility (at the expense
of strength)
Tempering
• Typical HT steps (Summarized Again):
– Austenize: Heat into stable single phase region and
HOLD for uniform chemistry single phase austenite.
– Quench: Rapid cool – crystal changes from
Austenite FCC to Martensite BCT which is hard but
brittle.
– Temper: A controlled reheat (BELOW AUSTENITE
REGION). The material moves toward the
formation of a stable two phase structure – tougher
but weaker.
– Quench: The properties are then frozen in by
dropping temperature to stop further diffusion
71
72
73
 Time temperature transformation (schematic) diagram for plain carbon eutectoid
% of Phase steel
100
T1 T2 At T1, incubation
50%
period for pearlite=t2,
0 Pearlite finish time
=t4
Ae1
T2 Minimum incubation
period t0 at the nose
Pearlite
T1
of the TTT diagram,
t1 t2 t3 t4 t5 Fine pearlite
t0

Hardness
50% very fine pearlite + 50% upper bainite MS=Martensite
start temperature
M50=temperature
Temperature

Upper bainite
for 50%
martensite
formation
MF= martensite
Lower bainite
finish temperature
MS, Martensite start temperature
M50,50% Martensite
Metastable austenite +martensite
MF, Martensite finish temperature

Martensite
74
Log time
TTT diagram gives
Nature of transformation-isothermal or athermal (time
independent) or mixed
Type of transformation-reconstructive, or displacive
Rate of transformation
Stability of phases under isothermal transformation
conditions
Temperature or time required to start or finish
transformation
Qualitative information about size scale of product
Hardness of transformed products

75
76
Factors affecting TTT diagram

Composition of steel-
(a) carbon wt%,
(b) alloying element wt%
Grain size of austenite
Heterogeneity of austenite

77
Schematic Fe-Fe3C metastable equilibrium diagram and TTT
diagrams for plain carbon hypoeutectoid, eutectoid and
hypereutectoid steels
γ=austenite M=martensite
P=pearlite
α=ferrite FP=fine pearlite MS=Martensite start temperature
CP=coarse UB=upper bainite M50=temperature for 50% martensite
pearlite LB=lower bainite formation
MF= martensite finish temperature

(a) Fe-Fe3C (b) TTT diagram for (c ) TTT diagram (d) TTT diagram for
metastable phase hypoeutectoid steel for eutectoid steel hypereutectoid steel
diagram

MS
78
The process by which a colony of pearlite evolves in
a hypoeutectoid steel.

79
Summary of the mechanism of the bainite reaction.

80
(a) Optical micrograph showing thin and spiny lower bainite
formed at 190°C for 5 hours in an Fe-1.1 wt% C steel. (b)
Transmission electron micrograph showing lower bainite midrib in
same steel. Courtesy of M. Oka

81
Morphology and crystallography of (bcc or bct) martensite in ferrous
alloys
Lath Lenticular Thin plate
Courtesy of (Fe-9%Ni-0.15%C) (Fe-29%Ni-0.26%C) (Fe-31%Ni-0.23%C)
T. Maki

Dislocation
Substructure Dislocation Twin
Twin (midrib)
{111}A {259}A
Habit plane {3 10 15}A
{557}A {3 10 15}A
N-W
O.R. K-S G-T
G-T
Ms high low
82
Lath martensite

Courtesy of
T. Maki
83
 Fig. 31: effect of carbon
on martensite lath size
Packet: a group of laths
with the same habit plane
( ~{111}g )

Block : a group of laths

with the same orientation
(the same K-S variant)

(T. Maki，K. Tsuzaki, I. Tamura: Trans. ISIJ, 20(1980), 207.)

84
 Lenticular martensite
(Optical micrograph)

Courtesy of
T. Maki

Fig.32: Fe-29%Ni-0.26%C
(Ms=203K)

Fig. 33: Fe-31%Ni-0.28%C

(Ms=192K) Fig.34: schematic diagram for
lenticular martensite 85
Fig. 37: Optical microstructure of lath martensite (Fe-C alloys)
Courtesy of
T. Maki

0.0026%C 0.18%C

86
0.38%C 0.61%C
 Applications of TTT diagrams
• Martempering
• Austempering
• Isothermal Annealing
• Patenting

Martempering : This heat treatment is given to oil hardenable

and air hardenable steels and thin section of water hardenable
steel sample to produce martensite with minimal differential
thermal and transformation stress to avoid distortion and
cracking. The steel should have reasonable incubation period
at the nose of its TTT diagram and long bainitic bay. The
sample is quenched above MS temperature in a salt bath to
reduce thermal stress (instead of cooling below MF directly)
(Fig. 44)
87
Surface cooling rate is greater than at the centre. The cooling
schedule is such that the cooling curves pass behind without
touching the nose of the TTT diagram. The sample is
isothermally held at bainitic bay such that differential cooling
rate at centre and surface become equalise after some time.
The sample is allowed to cool by air through MS-MF such
that martensite forms both at the surface and centre at the
same time due to not much temperature difference and thereby
avoid transformation stress because of volume expansion.
The sample is given tempering treatment at suitable
temperature.

88
 Martempering heatreatment superimposed on TTT diagram for plain
carbon hypoeutectoid steel
Ae3

Ae1
γ=austenite
α+CP
α=ferrite
α+P CP=coarse pearlite
t0 FP P=pearlite
FP=fine pearlite
t0=minimum incubation
50% FP + 50% UB
Temperature

period
UB UB=upper bainite
LB=lower bainite
M=martensite
Metastable γ Tempering MS=Martensite start
temperature
LB M50=temperature at which
MS 50% martensite is obtained
MF= martensite finish
M50 Metastable γ + martensite temperature
MF

Martensite Tempered martensite

Log time 89
 Austempering

Austempering heat treatment is given to steel to produce lower

bainite in high carbon steel without any distortion or
cracking to the sample. The heat treatment is cooling of
austenite rapidly in a bath maintained at lower bainitic
temperature (above Ms) temperature (avoiding the nose of the
TTT diagram) and holding it here to equalise surface and centre
temperature (Fig. 45) and . till bainitic finish time. At the end of
bainitic reaction sample is air cooled. The microstructure
contains fully lower bainite. This heat treatment is given to 0.5-
1.2 wt%C steel and low alloy steel. The product hardness and
strength are comparable to hardened and tempered martensite
with improved ductility and toughness and uniform mechanical
properties. Products donot required to be tempered.

90
 Austempering heatreatment superimposed on TTT diagram for plain
carbon hypoeutectoid steel
Ae3

Ae1
γ=austenite
α+CP
α=ferrite
α+P CP=coarse pearlite
t0 FP P=pearlite
FP=fine pearlite
t0=minimum incubation
50% FP + 50% UB
Temperature

period
UB UB=upper bainite
LB=lower bainite
M=martensite
Metastable γ Tempering MS=Martensite start
temperature
LB M50=temperature at which
MS 50% martensite is obtained
MF= martensite finish
M50 temperature
Metastable γ + martensite
MF
Martensite
Lower bainite

Log time 91
 Patenting

Patenting heat treatment is the isothermal annealing at the nose

temperature of TTT diagram (Fig. 47). Followed by this the
products are air cooled. This treatment is to produce fine
pearlitic and upper bainitic structure for strong rope, spring
products containing carbon percentage 0.45 %C to 1.0%C. The
coiled ropes move through an austenitising furnace and enters
the salt bath maintained at 550°C(nose temperature) at end of
salt bath it get recoiled again. The speed of wire and length of
furnace and salt bath such that the austenitisation get over
when the wire reaches to the end of the furnace and the
residency period in the bath is the time span at the nose of the
TTT diagram. At the end of salt bath wire is cleaned by water
jet and coiled.

92
 Patenting heat treatment superimposed on TTT diagram of plain
carbon hypoeutectoid steel

Ae3

Ae1
γ=austenite
α+CP
α=ferrite
α+P CP=coarse pearlite
FP P=pearlite
t0 FP=fine pearlite
t0=minimum incubation
50% FP + 50% UB
Temperature

period
UB UB=upper bainite
LB=lower bainite
M=martensite
Metastable γ MS=Martensite start
temperature
LB M50=temperature at which
MS 50% martensite is obtained
MF= martensite finish
M50 temperature
Metastable γ + martensite
MF
Martensite
fine pearlite and upper bainite

Log time 93
94
 Hardenability--Steels
• Ability to form martensite
• Jominy end quench test to measure hardenability.
Adapted from Fig. 11.11,
flat ground Callister 7e. (Fig. 11.11
specimen adapted from A.G. Guy,
(heated to g Essentials of Materials
Science, McGraw-Hill Book
phase field) Rockwell C Company, New York,
1978.)
24°C water hardness tests

• Hardness versus distance from the quenched end.

Hardness, HRC

Adapted from Fig. 11.12,

Callister 7e.

Distance from quenched end

Chapter 11 - 95
 Why Hardness Changes W/Position
• The cooling rate varies with position.

Hardness, HRC
60

40

20 distance from quenched end (in)

0 1 2 3
T(°C) 0%
600 100%
Adapted from Fig. 11.13, Callister 7e.
(Fig. 11.13 adapted from H. Boyer (Ed.)
400 Atlas of Isothermal Transformation and
Cooling Transformation Diagrams,
M(start) American Society for Metals, 1977, p.
200 376.)
AM

0 M(finish)

0.1 1 10 100 1000

Time (s)
Chapter 11 - 96
 Hardenability vs Alloy Composition
100 10 3 2 Cooling rate (°C/s)
• Jominy end quench
60

Hardness, HRC
results, C = 0.4 wt% C 100

4340 80 %M
50
40 4140

Adapted from Fig. 11.14, Callister 7e.

8640
(Fig. 11.14 adapted from figure furnished 5140
courtesy Republic Steel Corporation.) 20
0 10 20 30 40 50
Distance from quenched end (mm)

• "Alloy Steels" 800

(4140, 4340, 5140, 8640) T(°C) TE
600 shift from
--contain Ni, Cr, Mo A B A to B due
(0.2 to 2wt%) 400 to alloying
--these elements shift
the "nose". M(start)
200
--martensite is easier M(90%)
to form. 0 -1
10 10 103 105 Time (s)
Chapter 11 - 97
 Quenching Medium & Geometry
• Effect of quenching medium:
Medium Severity of Quench Hardness
air low low
oil moderate moderate
water high high
• Effect of geometry:
When surface-to-volume ratio increases:
--cooling rate increases
--hardness increases
Position Cooling rate Hardness
center low low
surface high high

Chapter 11 - 98
 Precipitation Hardening
• Particles impede dislocations.
700
• Ex: Al-Cu system
T(°C) L CuAl2
• Procedure:
--Pt A: solution heat treat
600
a a+L q+L
A
(get a solid solution) 500 q
--Pt B: quench to room temp. C a+q
400
--Pt C: reheat to nucleate
small q crystals within 300
0 B 10 20 30 40 50
a crystals. (Al) wt% Cu
composition range
• Other precipitation needed for precipitation hardening
systems: Adapted from Fig. 11.24, Callister 7e. (Fig. 11.24 adapted from J.L.
• Cu-Be Temp. Murray, International Metals Review 30, p.5, 1985.)
Pt A (sol’n heat treat)
• Cu-Sn
• Mg-Al
Pt C (precipitate q)
Adapted from Fig.
11.22, Callister 7e. Time
Pt B
Chapter 11 - 99
 Precipitate Effect on TS, %EL
• 2014 Al Alloy:
• TS peaks with • %EL reaches minimum
precipitation time. with precipitation time.
• Increasing T accelerates
process.

30
tensile strength (MPa)

%EL (2 in sample)
400
20
300
149°C 10
200 204°C 149°C
204°C
100 0
1min 1h 1day 1mo 1yr 1min 1h 1day 1mo 1yr
precipitation heat treat time precipitation heat treat time
Adapted from Fig. 11.27 (a) and (b), Callister 7e. (Fig. 11.27 adapted from Metals Handbook:
Properties and Selection: Nonferrous Alloys and Pure Metals, Vol. 2, 9th ed., H. Baker (Managing Chapter 11 -100
Ed.), American Society for Metals, 1979. p. 41.)
Direct Hardening - Selective
Hardening
• Same requirements as austenitizing:
– Must have sufficient carbon levels (>0.4%)
– Heat to austenite region and quench
• Why do?
– When only desire a select region to be hardened:
Knives, gears, etc.
– Object to big to heat in furnace! Large casting w/
wear surface
• Types:
– Flame hardening, induction hardening, laser beam
hardening
Flame Hardening:
Induction Hardening
Diffusion Hardening (aka Case
Hardening):
• Why do?
– Carbon content too low to through harden with
previous processes.
– Desire hardness only in select area
– More controlled versus flame hardening and induction
hardening.
– Can get VERY hard local areas (i.e. HRC of 60 or
greater)
– Interstitial diffusion when tiny solute atoms diffuse into
spaces of host atoms
– Substitiutional diffusion when diffusion atoms too big
to occupy interstitial sites – then must occupy
vacancies
Diffusion Hardening:
• Requirements:
– High temp (> 900 F)
– Host metal must have low concentration of
the diffusing species
– Must be atomic suitability between diffusing
species and host metal
Diffusion Hardening:
• Most Common Types:
– Carburizing
– Nitriding
– Carbonitriding
– Cyaniding
Diffusion Hardening - Carburizing
• Pack carburizing most common:
– Part surrounded by charcoal treated with
activating chemical – then heated to austenite
temperature.
– Charcoal forms CO2 gas which reacts with
excess carbon in charcoal to form CO.
– CO reacts with low-carbon steel surface to
form atomic carbon
– The atomic carbon diffuses into the surface
– Must then be quenched to get hardness!
Diffusion Hardening - Nitriding
• Nitrogen diffused into surface being
treated. Nitrogen reacts with steel to form
very hard iron and alloy nitrogen
compounds.
• Process does not require quenching – big
advantage.
• The case can include a white layer which
can be brittle – disadvantage
• More expensive than carburizing
Source of nitrogen

Reduction process: 2NH3 2N + 3H2