Duplex Steels
Duplex Steels
Duplex Steels
VOLUME 1
METALLURGICAL EVALUATION
OF CAST DUPLEX STAINLESS STEELS
AND THEIR WELDMENTS
SUBMITTED TO
U. S. DEPARTMENT OF ENERGY
Award Number - DE-FC36-00 ID13975
SONGQING WEN
CARL D. LUNDIN
GREG BATTEN
CARL D. LUNDIN
PROFESSOR OF METALLURGY
MATERIALS JOINING GROUP
MATERIALS SCIENCE AND ENGINEERING
THE UNIVERSITY OF TENNESSEE
KNOXVILLE 37996-2200
TELEPHONE (865) 974-5310
FAX (865) 974-0880
lundin@utk.edu
ii
FOREWARD
The final report for the DOE Grant DE-FC36-00 IDI13975 consists of five volumes. The
volumes provide in depth information on Cast Duplex and Cast Super Duplex Stainless Steels.
Volume 1 is entitled Metallurgical Evaluation of Cast Duplex Stainless Steels and their
Weldments involves comparison of selected grades of Duplex Stainless Steels and their welds
with their wrought counterparts regarding corrosion performance, mechanical properties and
weldability. Volume 2 entitled The Development of Qualification Standards for Cast Duplex
Stainless Steel involves inter-laboratory testing and Volume 3 The Development of
Qualification Standards for Cast Super Duplex Stainless Steel provides information on the
testing of Super Duplex Stainless Steels to ASTM A923. Volume 4 is the Guidance Document
for the Evaluation of Super Duplex Stainless Steel and involves the applicability of ASTM
A923 to the Cast Super Duplex materials. Volume 5 is the data package for the incorporation of
ASTM A890-5A material into the ASTM A923.
In volume 1 selected grades of Duplex Stainless Steel castings and their welds, in
comparison with their wrought counterparts, were evaluated, regarding corrosion performance,
mechanical properties and weldability. Multiple heats of cast duplex stainless steel were
evaluated in the as-cast, solution annealed static cast and solution annealed centrifugal cast
conditions, while their wrought counterparts were characterized in the solution annealed
condition and in the form of as-rolled plate. Welding, including extensive assessment of
autogenous welds and a preliminary study of composite welds, Shielded Metal Arc Weld
(SMAW), was performed. The evaluations included Critical Pitting Temperature (CPT) testing,
Intergranular Corrosion (IGC) testing, ASTM A923 (Methods A, B and C), Charpy impact
testing, weldability testing (ASTM A494), ferrite measurement and microstructural evaluations.
Volume 2 deals with the Development of Qualification Standards for Cast Duplex
Stainless Steel (A890-4A) which is equivalent to wrought 2205. This volume involves testing of
cast Duplex Stainless Steel to several ASTM specifications, formulating and conducting industry
round robin tests and studying the reproducibility of the results. ASTM E562 (Standard Test
Method for Determining Volume Fraction by Systematic manual Point Count) and ASTM A923
iii
(Standard Test Methods for Detecting Detrimental Intermetallic Phase in Wrought Duplex
Austenitic/Ferritic Stainless Steels) were the specifications utilized in conducting this work. An
ASTM E562 industry round robin, ASTM A923 applicability study, ASTM A923 industry round
robin, and an ASTM A923 study of the effectiveness of existing foundry solution annealing
procedures for producing cast Duplex Stainless Steel without intermetallic phases were
implemented.
Volume 3 comprises of the Development of Qualification Standards for Cast Super
Duplex Stainless Steel (A890-5A) which is equivalent to wrought 2507. The objective of this
work was to determine the suitability of ASTM A923 Standard Test methods for Detecting
Detrimental Intermetallic Phase in Duplex Austenitic-Ferritic Stainless Steels for 25 Cr Cast
Super Duplex Stainless Steels (ASTM A890-5A). The various tests which were carried out were
ASTM A923 Test Method A, B and C (Sodium Hydroxide Etch Test, Charpy Impact Test and
Ferric Chloride Corrosion Test), ferrite measurement using Feritscope, ASTM E562 Manual
Point Count Method and X-Ray Diffraction, hardness measurement using Rockwell B and C and
microstructural analysis using SEM and EDS.
Volume 4 is the guidance document for the evaluation of cast Super Duplex Stainless
Steel which deals with the various evaluation methods which were defined and used for the work
on volume 3 for the Development of Qualification Standards for Cast Super Duplex Stainless
Steel alloy A890-5A (2507 Wrought Equivalent). The document explains in detail each test
which was conducted. It also includes some of the results which were acquired during this work.
Volume 5 is the Data Package for the evaluation of Super Duplex Stainless Steel
Castings prepared at the end of work comprised in volumes 3 and 4. The document deals with
the various evaluation methods used in the work documented in volume 3 and 4. This document
covers materials regarding evaluation of the A890-5A material in terms of inclusion in ASTM
A923. The various tests which were conducted on the A890-5A material are included in this
document.
iv
ABSTRACT
Duplex stainless steels (DSS) are being specified for chloride containing environments
due to their enhanced pitting and stress corrosion cracking resistance. They exhibit improved
corrosion performance over the austenitic stainless steels. Duplex stainless steels also offer
improved strength properties and are available in various wrought and cast forms.
Selected grades of duplex stainless steel castings and their welds, in comparison with
their wrought counterparts, were evaluated, regarding corrosion performance and mechanical
properties and weldability. Multiple heats of cast duplex stainless steel were evaluated in the ascast, solution annealed (SA) static cast and SA centrifugal cast conditions, while their wrought
counterparts were characterized in the SA condition and in the form of as-rolled plate. Welding,
including extensive assessment of autogenous welds and a preliminary study of composite welds
(shielded metal arc weld (SMAW)), was performed. The evaluations included critical pitting
temperature (CPT) testing, intergranular corrosion (IGC) testing, ASTM A923 (Methods A, B
and C), Charpy impact testing, weldability testing (ASTM A494), ferrite measurement and
microstructural evaluations.
In the study, the corrosion performances of DSS castings were characterized and
assessed, including the wrought counterparts for comparison. The evaluation filled the pore of
lack of data for cast duplex stainless steels compared to wrought materials. A database of the
pitting corrosion and IGC behavior of cast and wrought materials was generated for a greater
depth of understanding for the behavior of cast duplex stainless steel. In addition, improved
evaluation methods for DSS castings were developed according to ASTM A923, A262, G48 and
A494.
The study revealed that when properly heat treated according to the specification,
(1) DSS castings have equal or better pitting and intergranular corrosion resistance than their
wrought counterparts; (2) Welding reduces the pitting and intergranular corrosion resistance for
both the wrought and cast duplex alloys; (3) Castings generally have better toughness than their
wrought counterparts in the temperature range of 80C to +20C; (4) All shield metal arc
(SMA) test welds in DSS castings, with recommended or over matching filler metal, indicate that
welding is not a significant factor when considering DSS applications.
vi
TABLE OF CONTENTS
Chapter
Page
I. PROGRAM INTRODUCTION
1. INTRODUCTION
2. MATERIALS
11
a) Sigma Phase
11
b) Chi Phase
13
c) R Phase
17
d) p Phase
17
e) Secondary Austenite
17
g) Carbides
19
h) a-Prime
19
20
20
22
27
28
31
32
33
35
4. WELDING OF DSS
36
vii
36
36
37
45
4.2. Weldability
46
47
48
48
49
50
50
52
52
54
54
4.4.1. SMAW
55
4.4.2. GTAW
57
5. TOUGHNESS
59
60
6.1. Diagrams
60
63
63
64
66
67
Casting Production
67
ASTM A 890-99
68
69
71
71
viii
2. TEST METHODS
76
76
76
76
78
2.1.4 Procedure
79
79
80
80
80
81
81
2.2.4 Procedure
82
83
83
85
85
89
91
91
93
95
95
96
2.9. OLM
97
97
98
ix
98
98
ASTM A890-4A
98
ASTM A890-5A
101
ASTM A890-6A
102
ASTM A890-1B
103
CD7MCuN
105
1.2. IGC
106
ASTM A890-4A
106
ASTM A890-5A
109
ASTM A890-6A
109
112
114
114
121
3.1. CPT
123
3.2. IGC
126
126
129
131
131
135
136
7. MICROSTRUCTURE CHARACTERIZATION
142
ASTM A890-4A
143
ASTM A890-5A
167
ASTM A890-6A
171
182
VI. CONCLUSIONS
189
REFERENCES
191
SPECIFICATIONS
207
xi
LIST OF FIGURES
Figure
Page
Figure 3-1
Figure 3-2
10
Figure 3-4
14
Figure 3-5
16
25
Figure 3-7
25
25
Content
Figure 3-9
26
85C
Figure 3-10
xii
30
Figure 3-11
30
Figure 3-12
32
34
39
41
43
Figure 3-17
44
47
Figure 3-19
53
Resistance
Figure 3-20
58
Figure 3-21
61
Figure 3-22
64
Figure 3-23
65
Feritscope (b)
xiii
Figure 4-1
77
78
Figure 4-3
ICT Apparatus
82
Figure 4-4
84
Figure 4-5
87
this Study
Figure 4-6
87
Figure 4-7
88
Figure 4-8
90
Figure 4-9
94
Figure 5-1
117
119
Figure 5-3
119
Figure 5-4
120
Figure 5-5
120
xiv
Figure 5-6
128
130
133
134
134
135
144
Figure 5-10
145
Figure 5-11
145
Figure 5-12
147
Figure 5-13
148
Figure 5-14
150
xv
Oxalic
Figure 5-15
151
Oxalic
Figure 5-16
152
Oxalic
Figure 5-17
153
Oxalic
Figure 5-18
154
Figure 5-19
155
156
157
Figure 5-22
158
Figure 5-23
159
160
Figure 5-25
160
xvi
Figure 5-26
Secondary Image of the Fusion Boundary Area for EDS Line Scan
160
Figure 5-27
161
Figure 5-28
162
Figure 5-29
162
Figure 5-30
164
Figure 5-31
165
Figure 5-32
165
Figure 5-33
166
168
Figure 5-35
169
Figure 5-36
170
Figure 5-37
172
Figure 5-38
173
Figure 5-39
174
Heat 3, Glyceragia
xvii
Figure 5-40
175
Oxalic
Figure 5-41
177
178
Figure 5-43
178
Figure 5-44
179
Figure 5-45
179
Figure 5-46
180
Figure 5-41
Figure 5-47
180
Figure 5-48
181
183
Figure 5-50
185
Figure 5-51
186
xviii
Figure 5-52
xix
187
LIST OF TABLES
Table
Page
Table 3-1
Table 3-2
15
Table 3-3
29
Table 3-4
70
Sector
Table 4-1
71
Table 4-2-1.
72
Table 4-2-2
73
Table 4-2-3
74
Table 4-2-4
75
Table 4-2-5
75
Table 4-3
92
Table 5-1-1
99
xx
102
103
104
105
107
110
111
113
xxi
114
Table 5-3
117
Table 5-4
122
Table 5-5-1
124
125
129
Table 5-7
136
Table 5-8-1
137
138
139
xxii
140
Table 5-8-5
xxiii
141
I.
Program Introduction
Duplex stainless steels, cast and wrought forms, have been in use since the 1930s. The
first duplex stainless steel chemical tanks were built in the 1970 using alloy UR 50. Never-theless, it is only until recently, that the duplex alloys became popular, due to the use of AOD
refining technology combined with improved casting processes. This combination made it
possible to effect rigid control over the chemical composition of the cast product so that the
outstanding combination of corrosion resistance and toughness became an ease of control and,
simultaneously, reduced the cost of the product.
Now, duplex stainless steels, which are now more and more considered to be industrial
steels but no longer exotic alloys, have found widespread applications in the pulp and paper
industry, chemical industry, transport/chemical tanks and pollution control equipment
manufacture, offshore-gas and petroleum industry and a number of naval applications.
Although duplex stainless steels have enjoyed rapidly increasing popularity in recent
years, the availability of these alloys in the cast form has fallen behind the availability of the
wrought form. Duplex stainless steel castings are often used in pumps and valves in a variety of
applications and are important components in the systems, where unexpected service failures can
result in significant operational problems and expense. The performance is critical. Thus, of
concern is variability and insufficient performance characteristics of duplex stainless steels in all
forms, which can be related to significant in-service problems. And it is also of necessity to have
available, suitable methods and procedures for defining performance characteristics prior to
service of duplex stainless steel cast materials.
II.
Project Goals
This program involves two major areas of endeavor, interrelated and leading to a more
fundamental understanding of the corrosion and fabrication behavior of duplex stainless steel
castings and their welds in comparison with the wrought materials.
Therefore, foundries and component suppliers can reduce lead times and provide better
duplex stainless steel castings for critical service in marine and industrial environments as a
result of information developed in this study.
Evaluation for cast duplex stainless steel materials and their welds, in
comparison with the wrought counterparts, regarding microstructure,
corrosion resistance, weldability and mechanical properties
III.
Literature Review
1. Introduction
Duplex Stainless Steel (DSS) is defined as the group of stainless steels that
contains a two-phase structure (ferrite-austenite) and is more often a descriptor of an
alloy where both phases are present in significant quantities [1]. DSSs offer improved
corrosion and mechanical properties over austenitic stainless steels, so that they are
regarded to have higher potential in extending life of process components.
DSSs have been around since the early 1900. Fairly amount of evaluation work
has been conducted on DSS ever since. Publications of the research work can be found
dated from 1930s. Six international conferences have been held on DSS since 1982.
However, it was not until the 1970s that came in the most rapid alloy development and
appliance. Furthermore, most of the study of DSS was on wrought materials, which
made the understanding of cast DSS to fall behind. In addition, as welding is used to
upgrade castings before final solution heat treatment and is employed in fabrication of
cast-to-cast, wrought-to-cast and wrought-to-wrought components. The welding
processes employed and utilizing of filler metal for the welding can lead to degradation
of parent materials properties, especially corrosion performance in varies regions of the
weldment.
2. Materials
2.1. The Duplex Family - Development History, Chemistry, Applications
Duplex Stainless Steels were first produced by Avesta Jernverk in the year 1929
with an alloy called 453E (25%Cr-5%Ni). Another record of the earliest production of
duplex stainless steel products dates back to 1933 through an alloying error at J. Holtzer
Company, France. An 18%Cr-9%Ni-2.5%Mo austenitic stainless steel grade was made
to a 20%Cr-8%Ni-2.5%Mo composition containing a high volume of ferrite in an
austenitic matrix. This two-phase material was then studied and it was found that when it
was properly solution heat treated, the alloy was not sensitive to Intergranular Corrosion
(IGC) in various corrosive environments; a significant advantage compared to fully
austenitic stainless steel [1, 2].
After the first discovery, several duplex alloys were patterned. But it was not
until the 1950s, when the nickel shortage come up during Korean War that spurred new
duplex alloy development [3]. However, due to the limitation on understanding of
physical metallurgy and refining technique, the development of duplex alloys suffered
from many problems such as corrosion, ductility and welding. The real rapid
development occurred in 1970s with improved chemistry analysis capability and the
introduction of Argon-Oxygen-Decarburization (AOD) refining process. The control of
alloy chemistry and the removal of oxygen and sulfur were significantly improved.
In the early 1970s, the 22%Cr commercial grade duplex was developed in
Germany and Sweden. It was claimed that this grade of duplex was not sensitive to IGC
upon welding due to balanced chemistry.
In The 1980s, higher alloyed DSS grades came in favor, and developed into super
DSS. They are made to withstand more aggressive environments, but also bearing higher
risk of precipitation due to the higher alloying element content. In the making of super
DSS, Cr and Ni forming elements are balanced and more nitrogen is added. The super
DSSs are usually characterized by having a pitting resistance equivalent number
(PREN*) greater than 40. The minimum PREN for the heat is often part of the purchase
specification [5].
PREN is the pitting resistance equivalent number defined as: PREN = Cr + 3.3
Mo + 16 N [4]
Duplex stainless steels are usually classified into four categories [5, 9]:
a. Lean Alloy
The low cost molybdenum free DSS of the type 23Cr-4Ni-0.1N, provide
alternatives to AISI 304 and 316. However, the market for these steels has declined.
b. Standard 22%Cr
DSS of the type 22Cr-5Ni-3Mo-0.17N: these steels, which include SAF Alloy
2205 (cast: ASTM A890-4A), are the most popular and the least expensive in the duplex
family. In addition, these alloys have a PREN ranging from 30 to 36, and corrosion
resistance that lies between AISI 316 and 6 Mo superaustenitic stainless steels.
c. High Alloy
DSSs of the 25 Cr varieties have varying contents of Mo and N and also
containing Cu or W as alloy elements. Wrought Ferralium 255 and cast ASTM A890-1B
fit this category. This grade has a PREN ranging from 32 to 40.
d. Super Duplex
Super DSS of the type 25 Cr-7Ni-3.5Mo-0.27N has PREN values greater than 40.
SAF Alloy 2507 (cast: ASTM A890-5A) and Zeron 100 (cast: ASTM A890-6A) fit this
category [2, 3, 5-7].
Table 3-1 presents some of the typical duplex stainless steels in ASTM and other
standard systems.
UNS (Cast)
UNS (Wrought)
ACI
Trademark
A890-4A
J92205
S31803
CD-3MN
A890-5A
J93404
S32750
CE-3MN
A890-6A
J93380
S32760
CD-3MWCuN
Zeron 100
A890-1B
___
S32550
CD-4MCuN
Ferralium 255
Figure 3-1. Typical microstructure of DSS in wrought (a) and cast (b) form
Generally, the ratio of ferrite to austenite in DSS depends mainly upon the
chemical composition. The presence of ferrite with austenite provides better
intergranular corrosion (IGC) resistance and stress corrosion cracking (SCC) resistance
compared to fully austenitic stainless steels [2, 4]. Figure 3-2 shows the comparison of
SCC of susceptibility for various stainless steels. In addition, ferrite is also beneficial in
welding for it improves hot-cracking resistance.
In spite of the positive affects, the presence of ferrite in austenite may also cause
complex metallurgical reactions that include formation of a variety of secondary phases,
all of which have adverse effects on corrosion resistance or mechanical properties,
particularly impact toughness. Figure 3-3 shows the possible precipitates in DSS and it is
evident that most of these precipitates concern ferrite or ferrite-promoting element such
as Cr, Mo and W. These metallurgical reactions can take place over a wide temperature
range from 300C (572F) to 1000C (1832F).
10
a) Sigma Phase
The most commonly formed and observed detrimental phase in duplex stainless steels
is sigma () phase [2-3, 8-12, 13-19, 22, 24, 90]. Typical chemical composition of sigma
phase is Fe-30Cr-4Ni and 4-7 Mo [2], but sometimes as high as 10 Mo [8], depending on
the original Mo composition of the alloy. Sigma phase has harmful effects on the
mechanical properties, ductility and toughness, and it is detrimental to corrosion
resistance of stainless alloys due to its chemical composition. It is evident from the
typical composition for sigma phase that the higher Cr and Mo content (compared to the
matrix) indicates that the matrix surrounding the sigma phase is depleted in Cr and Mo,
which, in general, is detrimental to corrosion resistance.
Sigma precipitates in duplex stainless steels over a wider temperature range and in
a shorter time [2, 8-9]. The presence of ferrite enhances the precipitation of sigma phase
in many ways [2]. First of all, the composition of sigma is close to that of ferrite.
Secondly, the diffusion rate of sigma-forming elements such as Cr, Mo and W in ferrite is
100 times faster in ferrite than that in austenite. Finally, ferrite/austenite interfaces are
favorable sites for sigma phase nucleation.
It was also found that sigma phase nucleates preferentially at various locations in
duplex stainless steels [2, 9-15]. It can be at ferrite/ferrite/austenite triple points or grow
along ferrite/ferrite boundaries [12]. It is further suggested that nucleation is
heterogeneous in nature and does not strongly depend on the crystallographic orientation
relationships between the phases [12]. In addition, the reason why sigma phase
11
12
Solution annealing with fast cooling can remove sigma phase in the as-cast or asrolled materials. It is also interesting to find that solution annealing at higher
temperatures decreases the tendency to form sigma phase [11, 14-15, 17, 18]. The reason
behind this phenomenon is that a high solution annealing temperature tends to increase
the volume fraction of ferrite, which consequently is diluted with respect to ferriteforming elements.
The morphology of sigma phase is different when it precipitates at the
ferrite/austenite or at ferrite/ferrite interface or co-precipitates with secondary austenite
[10,14]. Figure 3-4 shows two micrographs that illustrate different sigma-phase
morphologies [12]. Identification of precipitates can be combined with crystallographic
criteria. Chi phase, for example, is a type of precipitate that has a composition close to
sigma phase but has a completely different crystalline structure [15, 19, 20]. Table 3-2
shows the lattice type, lattice parameters, and space group for sigma and chi and other
types of precipitates.
b) Chi Phase
Chi () phase is commonly found in duplex stainless steels but is usually present
in much smaller quantities than sigma phase [8, 11, 17, 18, 21-23], however, it is just as
harmful as sigma phase to the properties. In fact, because chi phase not only has a
similar Cr content, compared to sigma phase, but also a significantly higher Mo content
(~20%), chi phase is more detrimental to pitting corrosion resistance than sigma phase.
13
14
Type of Precipitate
Lattice Type
Space Group
Lattice Parameter
()
BCC
Im3m
a=2.86-2.88
/ (2)
FCC
Fm3m
a=3.58-3.62
tetragonal
P42/mnm
a=8.79, c=4.54
cubic
I43m
a=8.92
rhombohedral
R3
a=10.90, c=19.34
cubic
P4132
a=6.47
hexagonal
P31m
a=4.80, c=4.47
M23C6
cubic
Fm3m
a=10.56-10.65
M7C3
hexagonal
Pnma
a=4.52, b=6.99
-nitride
Cr2N
c=12.11
15
Chi phase and sigma phase are not distinguishable using optical light microscopy.
However, the two phases can be distinguished by TEM crystallographically.
Identifications can also be made easier by using backscattering (BS) SEM due to the
difference in chemical composition (i.e., Mo) between the two precipitates.
Chi phase causes a much brighter contrast on BS SEM image than sigma phase.
Figure 3-5 shows a micrograph illustrating this effect. For tungsten-containing super
duplex stainless steels, the tungsten content in chi phase is also substantially higher than
that in sigma phase [21].
Chi phase precipitates in the range of 700 to 900 C (1292 to 1652 F) and it
precipitates faster at 800 to 850 C (1472 to 1562 F). However, upon long-term aging,
chi phase will convert into sigma phase.
Figure 3-5. Micrograph Showing Different Contrast for Chi Phase and Sigma
Phase Due to Difference in Chemical Composition. [16]
16
c) R Phase
R phase precipitates at 550 to 800 C (1022 to 1472 F) both intergranularly and
intragranularly with an approximate composition of 30Fe-25Cr-35Mo-6Ni-4Si. R phase
is extremely deleterious to pitting corrosion resistance and, like other intermetallic
precipitates, detrimental to the toughness of the material.
R phase forms the fastest at the temperature range from 550 to 650 C (1022F to
1202 F). At higher temperatures, the formation of R is rare and R phase particles are
converted into sigma-phase after a relatively short aging time.
d) Phase
phase, which is often recognized as a nitride, has a proposed ideal chemical
formula Fe7Mo13N4. However, it was found that phase contains approximately 28%
Fe, 35% Cr, 3% Ni and 34% Mo. The approximate formation temperature for phase is
600 C (1112 F). Similar to other intermetallic precipitates discussed above, phase is
also detrimental to toughness and pitting corrosion resistance [15, 18].
e) Secondary Austenite
Secondary austenite [10, 11, 14, 15, 18, 21, 24-28] is also a transformation
product of ferrite with FCC crystal structure. The reason that this phase is termed
secondary austenite is opposed to primary austenite. The significant difference that exists
between the two types of austenite is the chemical composition.
17
18
f) Cr2N
The formation of Cr2N is likely to occur during rapid cooling from a high
solution temperature because supersaturation of nitrogen in ferrite will occur as a
consequence. The precipitation of Cr2N is observed in the temperature range 700-900 C
(1292-1652 F) and is mainly seen in high ferrite content regions [9, 11, 18, 29-32].
Nitrogen content affects the formation of Cr2N. For a given cooling rate there is an
intermediate nitrogen content that will result in the largest amount of Cr2N [29].
Cr2N was found to be elongated particles often precipitate intragranularly and
globular particles intergranularly precipitate either at ferrite/ferrite grain boundaries or
ferrite/austenite phase boundaries [9, 30].
g) Carbides
Carbides precipitate particular during processing in the temperature range of
800F - 1500F, predominantly at ferrite/austenite boundaries and result in reduction in
intergranular corrosion resistance. They are not as significant in super duplex stainless
steels than in traditional duplex stainless steels due to the lower carbon content.
h) -Prime
-Prime is a chromium-rich precipitate. Its precipitation is very much
temperature dependent during the temperature range of 650F-950F and with increasing
ferrite and Mo content. At 885F, -Prime forms in about ten hours. At 570F, material
19
will loose toughness in 25 years. This limits the DSS to a maximum operation
temperature of 550F [3].
20
21
Cr:
It is well known that chromium is the essential element that makes steels stainless.
Cr contents over 22% show marked increase in pitting corrosion resistance and crevice
corrosion resistance. However, because Cr is also a strong sigma and ferrite former, it is
usually held below 27% in order to retain ductility, toughness and corrosion resistance. It
is noted that in heavy section castings, Cr is generally held to the low side of the range to
reduce cracking in the as-cast condition [36].
Mo:
Mo, like chromium, it is also a strong ferrite former, and has similar effects as Cr
does on properties. Also, in case of heavy sections, Mo shall be held at the low side of
the specified range for the reason of increased cracking susceptibility. However, research
shows that if chloride stress corrosion cracking is a potential problem, Mo content should
be held to a minimum of 3.5%.
Ni:
microstructure to provide the proper ferrite/austenite ratio. It also affects the corrosion
and mechanical properties as well as the formation of secondary particles because Ni
22
stabilizes austenite [22, 36-39]. But excessive Ni results in an increase in the austenite
content, promoting a greater concentration of ferrite stabilizer elements (Cr, Mo) in the
remaining ferrite. This highly alloyed ferrite is more susceptible to the precipitation of
sigma phase. Moreover, according to Varol et al. [22], Ni effectively increases the
temperatures range over which sigma phase forms.
N:
1) It improves localized corrosion resistance and raises the critical pitting temperature
and is 16 times more effective than chromium in this respect (see PREN equation);
2) It is a strong austenite former. In fact, nitrogen is about 20 times more effective than
Ni as an austenite stabilizer on a weight percent basis [22], therefore, savings with
regard to nickel often can be made;
3) It increases yield strength by solid solution strengthening, and unlike carbon, does not
promote sensitization.
However, like other elements, the introduction of nitrogen also introduces
metallurgical complexity into the duplex stainless steels. The solubility of nitrogen in
liquid steel is the first concern. The importance of this is to prevent the occurrence of
nitrogen degassing on casting solidification [40]. The nitrogen solubility in steels is
highly composition dependent [22, 26, 40]. It was found that increasing the Cr, Mo and
Mn content results in an increase in the equilibrium nitrogen solubility of the steel, while
increasing the Si, Cu and content results in a decrease Ni [22, 26, 27, 37, 40]. Duplex
stainless steels have been made with up to 0.87% N in a pressurized electroslag process
[9].
23
SCRATA [36] recommends, from a foundry point of view, that nitrogen should
not exceed about 0.14%, which is near the lower end of ASTM A890 specified range
0.10-0.30. Anson et al. [40], however, have shown that it is possible to safely increase the
level of nitrogen in a duplex stainless alloy, at least for the 22Cr-5Ni-4Mo types. In
addition, it has been reported that castings can have nitrogen levels as high as 0.28%
without gas porosity defects [3].
The effect of nitrogen in stabilizing austenite is shown in Figure 3-7 [26]. The
figure clearly shows that the addition of nitrogen is associated with an increase in the A0
temperature, leading not only to an increase in austenite content at peak temperatures, but
also transformation starts at higher temperatures during casting or welding cooling cycles
[22]. Figure 3-8 also illustrates the effect of nitrogen on ferrite/austenite content [3].
W and Cu:
W and Cu are two minor elements that are added to improving corrosion
resistance. However, the addition of these two elements also complicates the already
heterogeneous metallurgical system in DSS.
The addition of W causes more rapid kinetics with regard to intermetallic phase
formation and a higher dissolution temperature for intermetallic phases compared with
W-free DSS [21]. Hertzman et al. [41, 42] showed that super DSS welded with W-rich
or W-Cu-rich filler metal are prone to precipitation of Chi-phase and secondary austenite.
In addition, W acting like Cr and Mo, promotes sigma phase formation [12] and., it was
indicated that the amount of Cr2N tended to be increased by W additions.
24
Figure 3-7.
Figure 3-8. Effects of Peak Temperature and Nitrogen Content on the Ferrite Content [2]
25
Both Ogawa et al. [42] and Nilsson et al. [21] indicated that tungsten is generally
beneficial when below 2%. Noted that CD-3MWCuN (cast Zeron 100), the only
tungsten bearing ASTM standardized casting, contains only 0.5 to 1% tungsten, which is
well below the maximum 2% limit that Ogawa et al. and Nilsson et al. suggest.
Cu promotes austenite formation if in a significant amount, such as 2% [43]. In
applications like sulphuric acid or pollution equipment, Cu is really needed to impart the
corrosion resistance [44]. Figure 3-9 shows the effect of Cu on corrosion rate in
sulphuric acid environment [45].
Figure 3-9. Corrosion Rate in 10% H2SO4 + 500 ppm Cl-Aerated, at 80Cand 85C [45]
26
Mn:
found to have good corrosion resistance, it is also stated that Mn tends to combine with
sulfur to form inclusions which weaken the passive film. The inclusions also promote
galvanic cells and form hydrogen sulfide gas in acid solutions [3]. However, DSSs with
up to 12% Mn addition have been developed in recent years [46-48]. Research showed
that Mn-bearing DSS with about 0.2% N provide an economic grades capable of
competing with traditional grades of stainless steels [46].
Si:
Si is added to cast alloys to increase fluidity of the liquid metal. However, high
silicon levels should be avoided as silicon is a strong sigma former [3, 36, 49]. Taylor [3]
indicates that "silicon in combination with molybdenum can be particularly dangerous".
SCRATA recommends that a 0.5-0.6% Si content is the best choice for duplex stainless
castings.
27
influence of elements on the stability of secondary phases also has a bearing on selecting
solution annealing temperatures for duplex stainless alloys. Table 3-3 cites the exact heat
treatment requirements given by ASTM A890-94a for some of the cast DSS alloys in
A890.
28
Grade
4A
Heat Treatment
Heat to 1120 C (2050 F) for sufficient time to heat casting uniformly to
temperature and water quench, or the casting may be furnace cooled to 1010
C (1850 F) minimum, hold for 15 minutes minimum and then water quench.
A rapid cool by other means may be employed in lieu of water quench.
5A
Heat to 1120 C (2050 F) minimum, hold for sufficient time to heat casting to
temperature, furnace cool to 1045 C (1910 F) minimum, quench in water or
rapid cool by other means.
6A
Heat to 1100 C (2010 F) minimum, hold for sufficient time to heat casting
uniformly to temperature, quench in water or cool rapidly by other means.
1B
Heat to 1040 C (1900 F) minimum, hold for sufficient time to heat casting
uniformly to temperature, quench in water or rapid cool by other means.
29
Figure 3-10. Modified Ternary Section of Fe-Cr-Ni Phase Diagram Plotted Using the
WRC-1992 Equivalent Relationships
30
become smoother with an increase of the solution annealing temperature. Kuroda and
Mastsuda [27] also noted that grain size increases with increasing peak temperature.
In summary, increasing the solution annealing temperature increases the ferrite
content and thus lowers the impact toughness, ductility and corrosion resistance, which
indicates the high solution annealing temperature may not be beneficial. However,
depending on the alloy composition, particularly the nickel and nitrogen content, solution
annealing temperature may have to be raised to ensure a complete dissolution of sigma
phase and obtain a certain ferrite level. Therefore, solution annealing temperature should
be chosen on the basis of specific heat chemistry rather than selecting a temperature
based on the ASTM required minimum in Table 3-3.
31
32
Equation 2.*
33
optimum conditions; that is, the material is well heat treated, the composition is well balanced
and surface is well prepared. Realistically, materials in service may not achieve the CPT obtained
in laboratory experiments.
To achieve the best pitting corrosion resistance, the physical metallurgy and
welding metallurgy of duplex stainless steels must be understood since the pitting
resistance performance is a reflection of the microstructural integrity. The following
areas that need to be addressed are:
1) Balance ferrite and austenite: too much ferrite can cause the formation of Cr2N or
other intermetallic phases and too much austenite will not only reduce the nitrogen
concentration in austenite but also will result in greater segregation of Cr and Mo in the
austenite [56].
Figure 3-13. Theoretical Calculations Based on Alloys with 25% Cr and 4% Mo. Ni was
varied to keep Constant Ferrite Content
34
2) Control Ni content: Ni only should be used for controlling phase balance. High Ni
will result in too much austenite and not enough Ni will promote the formation of too
much ferrite. Higher Ni content also stabilizes sigma phase.
3) Select proper heat treatment temperature: unlike the solution heat treatment of
fully austenitic stainless steels, solution annealing temperature has a significant effect on
the balance of ferrite/austenite in duplex materials. For a given nitrogen content, the
higher the solution annealing temperature, the higher the ferrite content will become.
4) Select proper welding procedures: this includes selection of welding parameters,
joint geometry, heat input, filler metal and shielding/backing gases as needed. Excessive
dilution and extremely fast or slow cooling rates should all be avoided.
35
stainless steels are resistant to intergranular attack. Thus, microstructure control is again
of paramount importance.
4. Welding of DSS
4.1. Welding Metallurgy
As welding is an important method in castings upgrading and fabrication, to weld
DSS, it is important to understand how duplex stainless steels transform at different
cooling rates, the effect of peak temperature in the HAZ and filler metal dilution.
36
Ogawa and Koseki [38] conducted similar investigations. These authors found
that among Cr, Mo and Ni, the microsegregation of Ni and Mo is more pronounced than
that of Cr, and Ni is more pronounced than Mo. However, the reason was not clear. It
was also found that partitioning of Cr, Mo and Ni during ferrite solidification is not as
great as in austenite solidification. Furthermore, it is indicated that the partitioning of Cr,
Mo and Ni between the ferrite and the austenite was not significant in welds. However
an increase in Ni and/or nitrogen promoted partitioning by raising the austenite
transformation temperature. Again, indicate nitrogen has a dominant effect on the
formation of weld metal austenite.
37
it is important to realize that the welding heat input cannot be considered alone.
However, for the sake of the following discussion, the plate thickness and joint
configuration is assumed to be the same.
For duplex stainless steels, it has been found that ferrite content is a function of
heat input/cooling rate. The lower the heat input, the higher the ferrite content and the
lower the impact toughness [32, 61-72]. A simple explanation for the phenomenon is that
the higher cooling rates suppress the diffusion-controlled processes in austenite
reformation, hence, the original phase ratio of ferrite to austenite is shifted toward higher
ferrite content [32] (Figure 3-14). The transformation rate is the fastest at approximately
850 C (1562 F) in Fe-C-Cr-Ni alloys. The nose is shifted upwards and also towards the
left on the TTT axes with increasing levels of austenite stabilizing elements such as
nickel and nitrogen. For super duplex stainless steels, the nose of the C-curve is at about
1050 C (1922 F) and the transformation to g starts within a few seconds at this
temperature.
High cooling rates do reduce the tendency of sigma and chi precipitation.
But Lippold et al. [69] and Kirineva and Hannerz [70] showed the presence of chromiumrich nitrides (Cr2N) is observed over a wide range of cooling rates and the effect is
particularly evident for microstructures with a high proportion of ferrite (usually the
result of a fast cooling rate). Increased ferrite content and increased nitrogen levels cause
a risk of chromium nitride formation in ferrite; due to the lower solubility of nitrogen in
ferrite.
38
Figure 3-14. Schematic TTT Diagram showing the C-Curve Kinetics and the Effect of
Increasing Nitrogen on the Austenite and Cr2N [32]
Excessively high heat input may reduce the ferrite content but the risk of
intermetallic precipitation significantly increases. In addition, high heat input usually
results in the material being at peak temperatures for longer times and thus substantial
grain growth may occur (at least for wrought alloys), which consequently, lowers the
impact toughness [32, 69, 70, 73, 74].
As mentioned previously, alloying elements, particular nickel and nitrogen, can
raise the temperature range in which ferrite transforms to austenite upon cooling. Thus,
studies that compare sensitivity with respect to cooling rate for different grades of duplex
stainless steels have been conducted.
Research indicated that ferrite level in the HAZ of 2205 alloy is higher than 2507.
This is believed due to the greater temperature range between the solidus and ferrite
solvus temperature of 2507 [69, 71, 67]. Figure 3-10 and 3-15 [70] illustrates the results.
39
Figure 3-15. Micrographs Showing Microstructures of SAF 2205 and 2507 after Gleeble
simulation at Dt = 93.0 s
40
Lippold et al. [75] compared the effect of cooling rate on Alloy SAF 2205 and Ferralium
255, which has higher chromium content but similar nickel and nitrogen content. The
results show that for cooling rates ranging from 2C(3.6F)/min. to 50C(90F)/min., the
ferrite content in the HAZ is nearly identical for both alloys, which again demonstrates
that nickel and nitrogen are dominant elements in controlling ferrite content.
Hoffmeister and Lothongkum [71] investigated the effect of nitrogen by varying
the nitrogen content in super duplex stainless steels and found that increasing the nitrogen
content not only raised the A4 temperature but also accelerated the ferrite to austenite
transformation, which is consistent with the previous discussion. In addition, the authors
indicated that a medium nitrogen content, such as ~0.10%, can be detrimental due to
precipitation of Cr2N when the cooling rate is high.
Nickel and nitrogen also stabilize austenite and delay austenite transformation to
ferrite to higher temperatures upon heating. This particular aspect was of interest in a
study of the effect of peak temperature and time at peak temperature for different grades
of duplex stainless steels.
The welding thermal cycle peak temperature most often studied by researchers is
1350 C (2462 F), at which ferritization occurs even for super duplex stainless steels. In
general, for a given cooling rate, the higher the peak temperature the higher the ferrite
content. However, heating rate and base metal structure also affect the final ferrite and
austenite balance [32, 69]. Fast heating rates retard the dissolution of the austenite and
thus may prevent a high ferrite content in the HAZ [32, 69]. In addition, for wrought
materials the interphase spacing may also affect the ferrite and austenite content in the
HAZ [32].
41
High peak temperatures also may cause grain growth problems in wrought
materials; lower impact toughness [32, 69, 70, 73, 74]. However, peak temperature is not
the only factor that influences grain growth in the HAZ. Ferrite grain growth highly
depends on the heat input and cooling rate. Furthermore, grain growth is controlled by
dissolution of austenite. Atamert and King [32] indicated that when the spacing between
austenite particles is large, grain growth is extensive. Interestingly enough, according to
Ferreira and Hertzman [74], the ferrite grain size had a strong influence on the austenite
reformation rate. That is, the larger the ferrite grain size, the lower the austenite content,
which is another reason why higher peak temperature lowered the austenite content in the
HAZ.
Draugelates et al. [65, 66] investigated the effect of peak temperature and cooling
time on the HAZ structure in cast duplex stainless steels. No significant differences were
found compared to the above discussion. However, the authors did not discuss the grain
growth issue for cast duplex stainless steels, which already exhibit a larger grain size than
wrought materials. Unfortunately, this subject was not discussed elsewhere either.
All the above discussion concerning the HAZ was limited to single pass welding.
It is important to understand the effect of reheating on the HAZ structure since multipass
welding is a requirement in industrial practice.
In multipass weld deposits, the HAZ from the first cycle can be reheated by
subsequent passes, to a degree dependent on the position of the HAZ relative to the heat
source. Figure 3-16, from Atamert and King [32] schematically shows six regions that
experience different thermal cycles. It is evident that not all HAZs (regions 1 and 2) are
affected by the second cycle. However, regions that are affected by the second thermal
42
Figure 3-16. Schematic Showing HAZs Experience Different Thermal Cycles [32]
43
Region 1
Region 2
Region 3
Region 4
Figure 3-17. Schematic Diagram Illustrating the Relative Positions of the Different
Thermal Cycles in a Two Pass Weld Deposit [70]
44
sensitization and for duplex stainless steel may cause precipitation of various undesirable
secondary phases. Since no systematic research has been conducted on this subject,
contradictory speculation exists on which type of duplex stainless steel can tolerate
higher interpass temperature without forming intermetallics.
45
contain at least a 2% higher nickel content than the base metal. However, if the filler
composition is biased to austenite by adding nickel, an adverse weldment performance
may result due to the following reasons [79]:
1) Increasing the nickel content promote austenite formation and dilution of nitrogen
content in the austenite and thus lower the corrosion resistance of the austenite and
therefore the weld metal.
2) High Ni promotes austenite formation but also promotes a greater concentration of
ferrite stabilizing elements (Cr, Mo) in the remaining ferrite. This results in more
susceptible to the precipitation of sigma phase at temperatures in the range from 650-950
C (1202-1742 F). Consequently, higher postweld solution heat treatment temperatures
(1100 to 1150 C/2010 to 2100 F) must be utilized to dissolve all sigma phase. [22].
3) If the dilution from the parent steel is low, ferrite levels can be too low to even
satisfy the weld metal strength requirements.
4.2. Weldability
For this discussion, weldability means the relative ease of producing a defect-free
weld with adequate mechanical properties and corrosion resistance. The principal defects
of interest are hot cracks (fusion zone or heat affected zone hot cracking) and cold cracks
(hydrogen assisted cracking). Welding considerations and proper welding procedures, to
not only avoid defects, but also to achieve the desirable level of performance is
important.
46
47
Not many research results regarding fusion zone solidification cracking have been
published for duplex stainless steels. The main reason is that fabrication experience with
a number of commercial duplex stainless steels had suggested the weld solidification
cracking is not a significant problem [80]. It has been suggested that duplex stainless
alloys solidify as ferrite as the primary phase and thus are less susceptible to cracking
than those that solidify solely to austenite. The difference in cracking susceptibility as
a function of primary solidification product is generally ascribed to the greater affinity of the
ferrite phase for the impurity elements such as sulfur and phosphorus and the reduced tendency
for liquid films to wet ferrite/ferrite boundaries[81].
48
49
processes. The presence of these phases definitely, to some extend, lead to degradation
of the corrosion resistance of the weldment. According to Karlsson [90], pitting and
crevice corrosion is decreased by presence of intermetallic phases; general corrosion and
intergranular corrosion is not affected significantly unless the presence of intermetallic
phases reach a certain level; stress corrosion cracking is significantly decreases by the
presence of these phases. P. Woollin did quantitative research on superduplex welds with
intermetallic in Sour Media show that the strain to failure of all-weld superduplex
decreases with the increasing of the amount of local intermetallic phase, also it suggested
that the size of intermatallic particles is more important than volume fraction [91].
50
properties and better corrosion resistance and to allow for the loss of particular elements
in the arc [3]. To accomplish the above goals, filler metals are higher in nickel and
contain nitrogen.
As discussed previously, weld metal toughness is affected by not only the ferrite
content but also the oxygen content. Covered electrodes with high silicon content such as
rutile electrodes also give a high oxygen content in the weld metal. Basic covered
electrodes give lower silicon and oxygen contents [92]. Flux core arc welding is usually
known for its difficulty in control of the oxygen content in the weld. Atamert et al. [93]
claimed that flux-cored wires with low oxygen concentration and optimum nitrogen
solubility display excellent corrosion resistance and the required mechanical properties
have been developed (composition was not available). Pak and Rigdal [94], on the other
hand, used readily available consumable wires OK Tubrod 14.27 and OK Tubrod 14.37
and found that these wires can produce weld metals that fulfill the common requirements
for duplex stainless steel welding.
Ni-base filler metals are often used for better corrosion resistance, especially for
root passes where the dilution is the highest. However, Holmberg [92] stated that the
combination of Ni-base fillers in the root and duplex fillers in the intermediate passes and
cap passes may result in brittle microstructures. degrd and Fager [95] found that
welding super duplex stainless steel using high Ni filler metal produced Cr2N in the
reheated regions and resulted in lower toughness. Although the development of
welding filler electrodes/wires for duplex and super duplex stainless steels has been
rapid, the standardization of welding consumables is limited [96]. Below are the national
and international standards or working documents for covered electrode [96]:
51
1) AWS A 5.4-92
2) AWS A 5.9-93
3) CEN (TC121 PREN)
4) IIW (Subcommittee IIE. Doc. II-E-118-91)
52
Nitrogen is known to have a beneficial effect on duplex stainless steels and the
above work has quantified the effect of nitrogen additions to both the shielding and
backing gases using manual GTAW. It was shown that nitrogen additions to both the
shielding gases and backing gases significantly improves the pitting corrosion resistance
compared to normal pure argon shielding and backing gases. Figure 3-19 [100]
illustrates the effect of various shielding gas composition on critical pitting temperature
(CPT). While backing gases are encouraged to be 100% N2, the nitrogen content in
shielding gas has to be limited to below 5% due to weldability problems. Besides adding
nitrogen to argon, helium and hydrogen can also be added to achieve more penetration.
However, if hydrogen is used in the shielding gas, ferrite content must be properly
53
controlled to prevent hydrogen cracking. Also, noted that H2 enhances nitrogen loss in
the weld pool [86].
GMAW is another process that requires attention to the shielding and backing
gases [104, 105]. However, oxygen additions may result in lower weld metal toughness
for duplex stainless steels. In addition, carbon pick-up in the weld metal due to CO2
addition in the shielding gas may occur. A quaternary gas mixture containing Ar, 5% He,
2% CO2 and 2% N2, which is called Arcal 129 and commercially available, has shown
good results and has not shown carbon pickup [139].
4.4.Welding Processes
Depending on the process and economy-related conditions, many welding
processes can be applied to duplex stainless steels [96, 107-114]:
a. SMAW Shielded Metal Arc Welding (stick electrode welding)
b. GTAW Gas Tungsten Arc Welding
54
4.4.1. SMAW
SMAW has the advantage of being a very versatile method that can be used for all
position welding. In addition, for repair welding of castings and other structures, SMAW
is usually selected [107].
Either rutile or basic covered electrodes can be used for welding duplex stainless
steels. While welders prefer rutile coated welding consumables for good slag
detachability (beneficial for root pass welding) and smooth weld bead appearance, welds
made with rutile coated electrodes generally have low impact toughness due to high
silicon and oxygen content [107-110]. Basic electrodes, on the other hand, result in a
55
poor appearance and difficult slag detachability but exhibit good impact values at low
temperatures. It was shown that basic welding consumables have a lower oxygen and
silicon content in the deposited weld metal.
Moisture control is important not only to prevent hydrogen cracking, but also
porosity [107, 109, 111, 115]. One method is to re-dry electrodes for about two hours at
250 to 350 C (480 - 660 F) before welding. Another alternative is to use extramoisture-resistant (EMR) electrodes, which have a guaranteed low coating moisture
content.
In SMAW, the weld pool is protected by gases and slag from the electrode
covering. To maximize this protection, Holmberg [111] recommended that an arc as
short as possible should be maintained. A long arc can produce weld porosity, excessive
oxides, excessive heat input and reduced mechanical properties.
The control of heat input, as discussed previously, affects the ferrite content of the
weld metal and heat affected zone. Too low a heat input will result in a fast cooling rate
and consequently brittle weld metal due to high ferrite and Cr2N precipitates. On the
other hand, too high heat input will result in precipitation of intermetallic phases such as
sigma due to a slow cooling rate. Thus, heat input for welding duplex stainless steels
must fall within a certain range. Holmberg [111] recommended 0.2-1.5 KJ/mm (5-38
KJ/in.) heat input for welding SAF 2507; for 22Cr duplex stainless steels, 0.5-2.5 KJ/mm
(12.7-63.5 KJ/in.) heat input has been considered suitable for a fairly broad thickness
range. The metal should be deposited in a straight bead with the width of weave not
exceeding twice the electrode diameter to ensure a proper heat input. For detailed
56
57
58
5. Toughness
Charpy impact test is a supplementary requirement for duplex stainless steel castings
specified in ASTM A890-99. The supplementary requirement S9 included in ASTM
A781M-00 states that:
Charpy impact test properties shall be determined on each heat from a set of
three Charpy V-notch specimens made from a test coupon in accordance with Test
Methods and Definitions A 370, and tested at a test temperature agreed upon between the
manufacturer and purchasers. Test specimens shall be prepared as Type A and tested in
accordance with Test Methods and Definitions A370.
Druce et al. [116] studied the effects of notch geometry on the impact toughness
using cast duplex stainless steel and concluded that the best notch geometry is the Vnotch specified by ASTM.
No guidelines regarding the extraction of Charpy impact test specimens have been
issued by ASTM. Gossett [117] indicated that the orientation of the sample is very
important. Unfortunately, no definitive suggestions were given.
It has been mentioned several times that a high ferrite content and the presence of
intermetallic compounds deteriorates impact toughness. The factors that control the
formation of ferrite and intermetallic phases have been discussed in detail.
Another well-known factor that affects the toughness of a material is the
oxygen/oxide content and other inclusions content. While there is not an extensive data
base illustrating the effect of oxygen on impact toughness of cast duplex stainless steels,
sufficient data have shown that duplex weld metal toughness may vary significantly when
59
deposited by different welding processes and that the coating of the electrode, namely,
rutile vs. basic is critical.
Overall, duplex stainless steels have excellent impact toughness. However, weld
metal toughness is generally lower than base metal. Many variables, such as alloy
content, solution annealing temperature, cooling rate, weld heat input, HAZ peak
temperature will affect the toughness. ASTM standards do not specify any minimum
impact toughness for duplex stainless steel castings.
6.1. Diagrams
The earliest work on this complex and important issue was accomplished by
Schaeffler [118] in 1949 on weld metals. Schaeffler's work was modified by Delong
[119], whose work was again modified several times by a host of researchers, led by
Kotecki [43, 120, 121], who also has accomplished significant work on ferrite
measurement.
60
The basic idea of ferrite content prediction has not changed since 1949. A
diagram contains phase fields and iso-ferrite lines that permit prediction of the weld
structure from composition. Figure 3-21 is the Schoefer diagram, Figure 3-18; the 1992
WRC Diagram. The procedure involves calculating a "chromium equivalent" (Creq) and
a "nickel equivalent" (Nieq) for each base metal and for the proposed filler metal, plotting
each equivalent on the diagram, drawing tie lines between the plotted points,
proportioning according to expected dilution, to obtain an estimate of the weld metals
ferrite content.
61
Equation 3
Equation 4
For the WRC-1992 Diagram [43], the Creq and Nieq are calculated as:
Creq = Cr + Mo + 0.7 Nb
Equation 5
Equation 6
Mn
Si
Cr
Ni
Mo
Co
0.20 max
2.00 max
2.00 max
17.0 ~ 28.0
4.0 ~ 13.0
4.00 max
1.00 max
0.20 max
Thus, it is evident that for modern duplex stainless steels, especially super DSS
can easily exceed the Schoefer diagram maximum limitations, which raises concerns
about the accuracy of the estimation. However, at the present time, there are no alternate
quick methods for estimating ferrite content in cast duplex stainless steels. At the same
time, there is always a degree of variance in the chemical analysis of an alloy. Accuracy
62
of the prediction of ferrite in this manner will depend on the accuracy of chemical
analysis.
In addition, as discussed previously, cooling rate is a dominant factor affecting the
ferrite content. Thus, ferrite content at different locations in individual castings can vary
considerably, depending on section size.
63
moreover, it may not be accurate due to individual bias, improper magnification and
improper grid size employed.
64
(a)
(b)
Figure 3-23. Ferrite Measurement with Single and Two-Pole Probes (a), and
Feritscope (b) [123]
65
Equation 7
Note that the Extended Ferrite Number is used in the equation, thus, Ferrite Numbers in
the range of 0-28 are not applicable for this equation.
66
Casting Production
Melting of duplex cast alloys may be done either in the electric arc or the
induction furnace [3, 36, 127, 128]. During the melting process, control of chemical
composition and removal of tramp elements are the most important aspects.
Argon-Oxygen-Decarburization (AOD) refining is highly recommended. Taylor [3] and
SCRATA [36] have more recommendations regarding melting.
67
ASTM A 890-99
ASTM A890-94a is the only standard for duplex stainless steel castings.
However the standard, requires attention and optimization in the following areas:
1) Lack of ferrite/austenite balance requirement.
2) Lack of minimum Charpy impact toughness requirement.
3) Lack of minimum corrosion resistance requirement (the PREN > 40 requirement
for Grades 5A and 6A is meaningless, because a material can have a satisfactory
PREN, but not satisfactory corrosion performance).
4) Lack of upper solution annealing temperature limit.
68
69
70
71
72
ASTM A890-5A and 6A are super duplex stainless steels of the type
25 Cr-7Ni-3.5Mo-0.27N. Alloy 2507 and Zeron 100 are the wrought counterparts of
the ASTM A890-5A and 6A, respectively. Three ASTM A890-5A heats, from three
different foundries, were tested. The chemical composition is presented in Table 4-2-2.
Heat 1 was tested in the as-cast and SA static cast condition. Heat 2 was tested only in
the SA static cast condition. Heat 3 was tested in the SA static cast and SA centrifugal
cast condition.
Three ASTM A890-6A heats, from three foundries, were tested. The chemical
composition of the three heats is presented in Table 4-2-3. All three 6A heats were tested
in the static cast form. Heat 1 was tested in both the as-cast and SA condition and Heats
2 and 3 were only evaluated in the SA condition.
73
ASTM A890-1B, whose wrought counterpart is Ferralium 255, and its variant,
CD7MCuN, belong to the 25% Cr variety. Four ASTM A890-1B heats were tested.
Table 4-2-4 shows the chemical composition of these heats. Heat 1 was tested in the
as-cast and SA static cast condition. The other three heats were only tested in the SA
static cast condition. Two CD7MCuN heats were tested. Their chemical compositions
are presented in Table 4-2-5. One CD7MCuN heat was tested in the SA static cast
condition. The other was tested in the SA static cast and SA centrifugal cast condition.
74
75
2. Test Methods
2.1. Critical Pitting Temperature (CPT) Test
2.1.1 Specimen Preparation
1)
Extract 1" X 1" X 1/8" test coupons from the casting (see Figure 4-1 for typical
extraction example)
2)
Affix the coupon on a specimen holder using double stick tape. Grind the coupon
on 120-grit abrasive paper and then on 600-grit abrasive paper, to obtain a
uniform 600-grit surface finish on all surfaces (including the edges). Sharp edges
should be rounded.
3)
4)
Note: Autogenously welded specimens are prepared using an automatic GTA welder.
Specimens are welded in a copper fixture to maintain suitable cooling rates and to
prevent distortion. The welding parameters (100A, 12V, 10in (25.4cm) / min. travel
speed) were chosen to provide a suitably sized weld on the coupon specified above.
Argon shielding gas is used. It is to be noted that welding must be conducted before
grinding to a 600 grit surface finish.
Figure 4-1. Corrosion Test Specimen Machinery Sketch (a). Production Casting
(b). Schematic Drawing Showing the Extraction of Corrosion Test Specimens
77
Note: For ASTM G48-97, the standard test solution for CPT testing is 6% FeCl3 + 1%
HCl. To make this standard solution, 24mL of reagent grade concentrated (36.5-38.0%)
hydrochloric acid (HCl) is added to 1000mL 6% FeCl3 solution to obtain a solution that
contains 6% FeCl3 and 1% HCl by weight. The purpose of using this acidified solution is
to obtain a pH-controlled environment over the test temperature range and to minimize
precipitation in the solution.
78
2.1.4 Procedure
1)
Transfer the flask that contains test solution to the bath and allow the system to
come to equilibrium at the temperature of interest.
2)
Place the specimen in a glass holder and immerse in the test solution, after the
solution has reached the desired temperature. No more than one specimen should
be placed in a test container. The total test period is 24 hours.
Note: According to ASTM G48-97, the starting temperature may be estimated by
the following equation:
CPT (C) = (2.5 x % Cr) + (7.6 x % Mo) + (31.9 x %N) - 41.0
Testing shall begin at the nearest increment of 5C estimated by the above
equation. The minimum temperature of test is 0C and the maximum temperature
of test is 85C. Testing may be done at a higher temperature (85C was the
highest temperature of testing in an ASTM CPT round-robin).
3)
At the end of the test period, remove the specimen, rinse with water, and scrub
with a nylon brush under running water and place in methanol with ultrasonic
agitation to remove corrosion products and dry.
2)
If pitting attack is defined, lower the bath temperature 5C and, using a new
specimen and fresh solution, repeat testing.
3)
If no pitting attack is defined, raise the bath temperature 10C using a new
specimen and fresh solution, repeat testing.
4)
Extract 3 1/8" X 3/4" X 1/8" coupons. (See Figure 4-1 for typical example)
2)
All surfaces of the test specimen shall be ground, to a uniform surface finish of
120-grit. Sharp specimen edges should be rounded.
3)
Determine the dimensions of the test specimen exposed surfaces and weigh the
specimen to the nearest 0.001g.
4)
80
Argon shielding is used. The weld face must be re-ground to a uniform 120 grit
finish before ICT.
The standard test solution for ICT is the Ferric Sulfate-Sulfuric Acid Test Solution
(ASTM A262 B)
Caution: Protect the eyes and use rubber gloves for handling acid. Mix
solution under a hood.
2)
3)
Measure 354.0mL of reagent grade sulfuric acid (concentration range from 95.0 to
98.0 % by weight), and add the acid slowly to the Erlenmeyer flask containing
distilled water avoiding excessive heating.
4)
Weigh 37.50g of reagent grade ferric sulfate (contains 75% Fe2(SO4)3) and add
to the sulfuric acid solution.
81
5)
6)
7)
2.2.4 Procedure
1)
2)
Mark liquid level on flask to provide a check on vapor loss (which would result in
increased concentration). If there is an appreciable change in the level, the test
must be repeated with a fresh solution and a re-ground specimen.
82
3)
Continue immersion testing of the specimen for a total of 120 hours, remove
specimen, rinse in water and use ultrasonic agitation to remove the corrosion
products, and dry.
4)
Weigh the tested specimen to the nearest 0.001g, and determine the weight loss of
the specimen.
A typical bend test fixture is shown in Figure 4-4. The fixture is constructed so as
to provide a 2t radius of bend, where t is the specimen thickness.
2)
The specimen shall be forced into the die by applying load on the plunger until
the specimen touches the bottom of the die.
Note: A test specimen with an autogenous weld, shall be placed with the weld
surface in tension.
83
84
3)
4)
2)
85
Set the energy indicator of the Charpy machine at the maximum reading.
2)
Use self-centering tong to take the Charpy bar from its cooling/heating
medium if test temperature is not ambient temperature, to place the
Charpy bar in the proper position on the specimen anvils.
86
Figure 4-5 Standard Dimension of Charpy Test Specimen (Type A) Used in this Study.
87
3)
Release the pendulum smoothly. Read the value of indicator on the scale.
Note: It shall not take more than 5 seconds if cooling/heating is applied.
4)
Gather the broken specimen and dip the pieces into acetone.
5)
If any specimen fails to break, no repeat test shall be given, record the fact.
6)
If specimen jams in the machine, disregard the result and check the test machine.
Information that shall obtain from the test including: Energy absorbed, lateral
Cracks, as tears in the casting in the fusion zone or heat-affected zone of the
macro-specimen shall be cause for rejection. Cracks originating at the weld bead
undercuts, at weld slag inclusions, or at casting defects shall not be cause for
rejection.
2.
Cracks or other open defects exceeding 1/8-in (3.2mm) measured in any direction
on the convex surface of the bent specimens shall be cause for rejection, except
that cracks occurring on the corners while testing and cracks origination at weld
bead undercuts shall not be considered.
89
91
Table 4-3. Duplex Stainless Steel Casting Heat Treatment Study Schedule
Note 1:
Thermal Arrest (Per ASTM A890-4A) requires that the castings be cooled
to 1850F (1010C) minimum for a duration of 15 minutes (minimum)
prior to quenching. Total arrest time will be 1 hour.
Note 2:
92
Unaffected Structure (Figure 4-9-1) - The ferrite has been etched without revelation of
intermetallic phase. The interphase boundaries are smooth.
Possibly Affected Structure (Figure 4-9-2) - The ferrite has been etched with isolated
indications of possible intermetallic phase. The interphase boundaries may show a fine
waviness.
93
Affected Structure (Figure 4-9-3) - The indications of an intermetallic phase are readily
revealed before or simultaneously with the staining of the ferrite during etching.
Centerline Structure (Figure 4-9-4) - An intermetallic phase is observed as a continuous
or semi-continuous phase in the mid-thickness region of the product, with or without the
affected structure out side of the mid-thickness region, indicative of segregation.
preparation and test solution preparation for this test method follow the same procedures
for the CPT test (see section 2.1). The corrosion rate is calculated in accordance with the
weight loss and total surface area, using the formula below:
Corrosion rate (mdd*) = weight loss (mg) / [specimen area (dm2) x time (days)]
* mdd; mg/ dm2/day
The acceptance criterion is that the corrosion rate shall not exceed 10mdd.
The method detects a loss of corrosion resistance associated with a local depletion
of chromium and molybdenum as a result of the precipitation of chromium-rich and
possibly molybdenum-rich phases, but not limited to intermetallic phases. An affected
structure should be associated with significant weight loss in the corrosion test.
2.9. OLM
Microstructural relationships can provide improved understanding of material
behavior and assist in defining changes necessary to improve performance. An
explanation of experimental variation can usually be found when microstructures are
defined.
Samples for metallographic evaluation are to be extracted from the castings and
wrought plates, mounted with epoxy. Metallographic samples then are ground to
600-grit. Polishing of the sample including coarse polishing and fine polishing. The
finished sample shall have a surface finish of 0.05mm then etched with solute sensitive
etchants. Electrolytic etching in 10% oxalic acid or 40% sodium hydroxide and
Glycerigia (HNO3, HCl, Glycerol) were selected for this study. Moreover, in order to
identify sigma phase, a stain-etching technique employing a 10% sodium cyanide
electrolyte (current density: 1A/in2, etching time: 5s) maybe used in addition to 10%
oxalic acid etching.
97
ASTM A890-4A
Four ASTM A890-4A heats and one heat of Alloy 2205 were CPT tested. Heat 1
was tested in four conditions; the as-cast, as-cast + autogenously welded, SA and SA +
autogenously welded condition. Heats 2, 3 and 4 were tested in the SA and SA +
autogenously welded condition. Centrifugal casting from Heat 4 was also tested in SA
and SA + Autogenous welded condition. The CPT results are summarized in Table 5-1-1
for ASTM A890-4A and wrought Alloy 2205. The CPT of Heat 1 in the as-cast
condition is 25C. The CPT of autogenously welded as-cast Heat 1 decreased to 15C.
The CPTs of Heats 1 through 4 SA static cast materials, vary from 35C to 50C, and the
CPTs in the SA + autogenously welded condition are in the range of from below 0C to
30C. It is to be noted that Heat 2, in the SA condition, exhibits the lowest SA base
98
Table 5-1-1. Duplex Stainless Steel CPT Test Results, ASTM A890-4A
(ASTM G48, 6 % FeCl3, 24 hrs.)
* CC - centrifugal cast
99
casting CPT (35C), while Heat 3 has the highest (50C). This result indicates that the
difference in the CPT, between heats of the same material, can be significant.
For Heat 4, the CPT of the SA centrifugal casting is 50C. It is 5 C higher than
the CPT of the SA static casting (45C). Thus, it appears that there is little difference in
pitting resistance between these casting methods. The CPT of the SA + autogenously
welded centrifugal casting is 15C. In addition, the wrought counterpart alloy 2205
shows a lower CPT (40C) than most of the 4A cast materials in the SA condition. The
CPT of autogenously welded Alloy 2205 is 25C. Thus, it is evident that autogenous
welding has a significant negative effect on the CPT, regardless of the material condition.
The CPT test results can be summarized as follows:
1.
The pitting corrosion resistance is the worst in the as-cast condition (ASTM A890
requires a SA for all grades). After solution annealing, it is significantly improved.
There is a variation in CPT between SA cast heats and casting procedures (SA
static casting and SA centrifugal casting). However, regarding the 5C increment,
these maybe simply scatter of the data.
2.
3.
100
ASTM A890-5A
Three ASTM A890-5A heats and one heat of Alloy 2507 were tested for the
determination of the CPTs. Heat 1 was tested in the as-cast, SA and
SA + autogenously welded condition. Heats 2 & 3 were tested in the SA and
SA + autogenously welded condition. Additionally, Heat 3 was also tested in the SA
centrifugal cast condition. The CPT results are summarized in Table 5-1-2 for ASTM
A890-5A and wrought Alloy 2507. The CPT of Heat 1 in the as-cast condition is < 0C.
The CPTs of Heats 1, 2 & 3, SA static cast materials rank from 50C to 65C, and the
CPT of SA + autogenously welded materials from these three heats range from 40C or
45C. Heat 2, in the SA condition, has the lowest SA CPT (50C), while Heat 1 and Heat
3 have the same CPT (65C) in SA condition. A difference in the CPT, between heats of
the same material is evident, as with ASTM A890-4A.
The CPT of Heat 3, SA centrifugal casting, is 50C. This is 15 C lower than the
CPT of the SA static casting of the same material (65C). No evidence was found to
explain this difference in pitting resistance between the two different casting methods.
The CPT of the SA + autogenously welded centrifugal casting was 30C.
The wrought counterpart, Alloy 2507, showed a CPT of 80C, higher than any of
the 5A cast materials, in the SA condition. The CPT of autogenously welded Alloy 2507
is 45C.
101
Table 5-1-2 Duplex Stainless Steel CPT Test Results, ASTM A890-5A
(ASTM G48, 6 % FeCl3, 24 hrs.)
* CC - centrifugal cast
ASTM A890-6A
The CPT of three ASTM A890-6A heats and one heat of wrought
Zeron 100, were determined in the SA and SA + autogenouslly welded condition.
Results are shown in Table 5-1-3. The highest CPT of the three 6A SA static cast
materials is 70C, the lowest, is 55C. SA + autogenously welded CPTs rank from 40C
to 55C. The CPT of base metal of wrought counterpart Zeron 100 is 65C. When
autogenously welded, the CPT is reduced to 30C.
102
Table 5-1-3 Duplex Stainless Steel CPT Test Results, ASTM A890-6A
(ASTM G48, 6 % FeCl3, 24 hrs.)
Material
Heat No.
Condition
CPT (C)
ASTM A 890-6A
Heat 1
Solution annealed
65
ASTM A 890-6A
Heat 1
SA
55
ASTM A 890-6A
Heat 2
Autogenous welded
Solution annealed
70
ASTM A 890-6A
Heat 2
SA
45
ASTM A 890-6A
Heat 3
Autogenous welded
Solution annealed
55
ASTM A 890-6A
Heat 3
SA
40
Zeron 100
Zeron 100
Autogenous welded
Wrought
65
Zeron 100
Zeron 100
Wrought
30
Autogenous welded
ASTM A890-1B
Four ASTM A890-1B heats and one heat of wrought Ferralium 255 were CPT
tested. Heat 1 was tested in the as-cast, as-cast + autogenously welded, SA and SA +
autogenously welded condition. Heats 2, 3 and 4 were tested in the SA and SA +
autogenously welded condition. The CPT results are summarized in Table 5-1-4 for
ASTM A890-1B and wrought alloy Ferralium 255. The CPT of Heat 1, in the as-cast
condition, is 15C. The CPTs of autogenously welded as-cast 1B remains the same
(15C). The CPT of the 1B, SA static cast materials, fall into the range of 30C to 40C.
In the SA + autogenously welded condition, the CPTs of these materials range from
10C to 25C. Wrought counterpart Ferralium 255 has a CPT of 45C, and 25C for the
103
Table 5-1-4 Duplex Stainless Steel CPT Test Results, ASTM A890-1B
(ASTM G48, 6 % FeCl3, 24 hrs.)
Material
Heat No.
Condition
CPT (C)
ASTM A 890-1B
Heat 1
As-cast
15
ASTM A 890-1B
Heat 1
As-cast
15
Autogenous welded
ASTM A 890-1B
Heat 1
Solution annealed
35
ASTM A 890-1B
Heat 1
SA
25
Autogenous welded
ASTM A 890-1B
Heat 2
Solution annealed
40
ASTM A 890-1B
Heat 2
SA
15
Autogenous welded
ASTM A 890-1B
Heat 3
Solution annealed
30
ASTM A 890-1B
Heat 3
SA
15
Autogenous welded
ASTM A 890-1B
Heat 4
Solution annealed
35
ASTM A 890-1B
Heat 4
SA
10
Autogenous welded
Ferralium 255
Ferr. 255
Wrought
45
Ferralium 255
Ferr. 255
Wrought
25
Ferr. 255
Wrought
Autogenous welded
(Ar + 5%N2)
104
30
CD7MCuN
Two CD7MCuN heats were tested for the determination of CPTs. Heat 1 was
tested in the SA static cast condition. Heat 2 was tested in both the SA static cast and SA
centrifugal cast condition. Autogenous welding was applied to both heats. Heat 1 SA
static cast revealed a CPT of 45C, and the CPT of the SA + autogenously welded
coupon is 5C. The CPTs of Heat 2 in the SA static cast and SA centrifugal cast
condition are 40C and 50C, respectively. The CPTs of the SA + autogenously welded
static cast and centrifugal cast are 15C. The results are presented in Table 5-1-5.
Heat No.
Condition
CPT (C)
CD7MCuN
Heat 1
Solution Annealed
45
CD7MCuN
Heat 1
SA
Autogenous Welded
CD7MCuN
Heat 2
Solution Annealed
40
CD7MCuN
Heat 2
SA
15
Autogenous Welded
CD7MCuN-CC
Heat 2
Solution Annealed
50
Heat 2
SA
15
CC*
Autogenous Welded
CC*
CD7MCuN-CC
* CC - centrifugal cast
105
1.2. IGC
The intergranular corrosion resistance evaluation was conducted according to
ASTM A262 Practice B with an ancillary adopted Bend Test. Samples, in the form of a
3 1/8" X 3/4" X 1/8" coupon, were prepared to a uniform 120-grit surface finish.
Intergranular corrosion tests (ICT) were conducted in a boiling Ferric Sulfate-Sulfuric
Acid (Fe(SO4)3 - 50% H2SO4) solution for a 120-hour test period. After ICT testing,
samples were 2t bend tested to assist in the revelation of the extent of intergranular
corrosion.
ASTM A890-4A
Four ASTM A890-4A heats and one heat of Alloy 2205 were ICT tested. Heat 1
was tested in the as-cast, as-cast + autogenously welded, SA and SA + autogenously
welded condition. Heats 2, 3 and 4 were tested in the SA and SA + autogenously welded
static cast condition. Heats 1, 2 and 3 were tested only in the SA static cast condition and
Heat 4 was tested in both the SA static and centrifugal cast conditions. The ICT results
for ASTM A890-4A are presented in Table 5-2-1. The IGC rate of Heat 1 in the as-cast
condition is the highest of the materials tested (62.23mpy). The as-cast Heat 1 ICT
samples showed intergranular separations after bending. The Heat 1 autogenously
welded as-cast samples, showed an average of 47.00mpy. The autogenously welded ascast ICT samples also showed intergranular separations (in the base metal, not in the
welded region) after bending. IGC rates and bend test behavior of SA Heats 1, 2, 3 & 4
are very similar, regardless of casting method (static or centrifugal). In general,
autogenous welding increased the IGC rate of SA materials to a minor extent with the
106
Table 5-2-1. Intergranular Corrosion Test and Bend Test Results, ASTM A890-4A
(ASTM A262 Practice B, Ferric Sulfate-Sulfuric Acid, Boiling, 120 hrs.)
Material
Code
Condition
Corrosion
Bending Results
Rate
(After ICT)
(mpy)
ASTM
Heat 1
As-cast
61.26
A890-4A
ASTM
63.29
Heat 1
A890-4A
ASTM
Heat 1
A890-4A
ASTM
Heat 1
A890-4A
ASTM
Heat 2
A890-4A
ASTM
Heat 2
A890-4A
ASTM
Heat 3
A890A-4A
ASTM
Heat 3
A890-4A
ASTM
Heat 4
A890-4A
ASTM
Intergranular Separations
Heat 4
A890-4A
As-cast
49.76
Intergranular Separations
(A-W)
44.23
in the BM
Solution
12.93
No Separations
Annealed
12.43
SA
15.25
Interdendritic Separations
(A-W)
15.18
Solution
10.84
No separations
Annealed
15.51
Minor separation
SA
11.73
No separations
(A-W)
17.59
Minor separation
Solution
11.21
No separations
Annealed
11.08
SA
21.13
Interdendritic separations
(A-W)
21.72
in the weld
Solution
10.81
No separations
Annealed
10.50
SA
10.90
Separations
(A-W)
11.21
in the HAZ
ASTM
Heat 4
Solution
11.17
Minor separation
A890A-4A
CC*
Annealed
10.86
No separations
ASTM
Heat 4
SA
11.18
Separations
A890-4A
CC*
(A-W)
10.75
Alloy 2205
Alloy 2205
Wrought
16.60
No Separations
16.11
Alloy 2205
Alloy 2205
Wrought
20.72
Interdendritic Separations
(A-W)
19.90
in the WM
* CC - centrifugal cast
107
corrosion taking place in the weld fusion zone. The ICT results also showed heat-to-heat
behavioral differences. For example, Heat 3 SA static cast base metal show an average
of 11.15mpy, with no grain boundary separations observed after bending. The average
IGC rate for SA + autogeously welded is 21.43mpy, with interdendritic separations
observed in the weld fusion zone. For Heat 4, the SA static cast base metal has an
average of 10.65mpy, with no separations observed after bending. The average of its SA
+ autogeously welded is 11.05mpy, with separations observed in the HAZ. Wrought
Alloy 2205 shows a higher IGC rate than the SA castings even when they are
autogenously welded. No separations were observed on the SA casting base metal bent
samples, but interdendritic separations appeared in the fusion zone of autogenous welds.
The IGC test results are summarized as follows:
1.
The as-cast condition shows the highest intergranular corrosion rate, and the most
extensive separations (some intergranular fractures) upon bending.
2.
Solution annealing reveals a significant decrease in the IGC rate compared to the
as-cast materials.
3.
The wrought counterpart alloys showed higher IGC rates but similar bending
behavior when compared to the SA cast materials.
4.
Welding decreases the IGC rates in the as-cast condition, but for the SA cast
materials and wrought counterparts, welding increased the IGC rates to a minor
extent.
108
ASTM A890-5A
Three ASTM A890-5A heats and one heat of Alloy 2507 were evaluated by ICT.
Heat 1 was tested in the as-cast, as-cast + autogenously welded, SA and SA +
autogenously welded condition. Heats 2 & 3 were tested in the SA static cast and SA +
autogenously welded conditions. In addition, Heat 3 was tested in the SA centrifugal cast
condition. Table 5-2-2 shows the ICT results for ASTM A890-5A materials. Compared
to ASTM A890-4A materials, the same trends on ICT behavior were observed for the
ASTM A890-5A materials. However, the IGC rates of ASTM A890-5A, solution
annealed cast (Avg. 7.58mpy) and wrought materials (Avg. 8.29mpy), were lower than
ASTM A890-4A materials in the corresponding conditions (Avg. 11.74mpy for SA static
cast and centrifugal cast / Avg. 16.36mpy for wrought Alloy 2507). SA + autogenous
welding increased IGC rate. Maximum increment of SA + autogenous welding on IGC
rate is 1.0mpy).
ASTM A890-6A
ICT of three ASTM A890-6A heats and one heat of wrought counterpart Zeron
100, were conducted in the as-cast, as-cast + autogenously welded, SA and SA +
autogenously welded condition. The IGC rates of ASTM A890-6A materials and wrought
Zeron 100 and their autogenously welded condition are approximately the same as that of
ASTM A890-5A materials. The results are presented in Table 5-2-3.
109
Table 5-2-2. Intergranular Corrosion Test and Bend Test Results, ASTM A890-5A
(ASTM A262 Practice B, Ferric Sulfate-Sulfuric Acid, Boiling,120 hrs.)
Material
Code
Condition
Corrosion
Bending Results
Rate
(After ICT)
(mpy)
ASTM
Heat 1
As-cast
24.22
Intergranular Separations
25.46
(Fractured)
As-cast
23.98
Intergranular Separations
(A-W)
23.91
(Fractured)
Solution
8.12
No Separations
Annealed
8.33
SA
7.89
Interdendritic Separations
(A-W)
7.80
in the WM
Solution
6.73
No separations
Annealed
6.85
Minor separation
SA
6.25
Separations
(A-W)
7.29
in the HAZ
Solution
6.96
No separations
Annealed
6.81
SA
7.74
Minor separations in WM
(A-W)
7.33
No separations
A890-5A
ASTM
Heat 1
A890-5A
ASTM
Heat 1
A890-5A
ASTM
Heat 1
A890-5A
ASTM
Heat 2
A890-5A
ASTM
Heat 2
A890-5A
ASTM
Heat 3
A890-5A
ASTM
Heat 3
A890-5A
ASTM
Heat 3
Solution
7.59
Minor separations
A890-5A
CC*
Annealed
7.91
No separations
ASTM
Heat 3
SA
8.70
Minor separations
A890-5A
CC*
(A-W)
8.16
Alloy 2507
Alloy 2507
Wrought
8.17
No Separations
8.41
Alloy2507
Alloy2507
Wrought
8.74
Minor separations
(A-W)
9.83
in the HAZ
* CC - centrifugal cast
110
Table 5-2-3. Intergranular Corrosion Test and Bend Test Results, ASTM A890-6A
(ASTM A262 Practice B, Ferric Sulfate-Sulfuric Acid, Boiling,120 hrs.)
Material
Code
Condition
Corrosion
Bending Results
Rate
(After ICT)
(mpy)
ASTM
Heat 1
As-cast
33.22
Intergranular separations
32.50
(Fractured)
As-cast
31.03
Intergranular separations
(A-W)
30.75
(Fractured)
Solution
7.99
No Separation
Annealed
7.83
SA
8.25
No Separation
(A-W)
7.73
Solution
7.77
No Separations
Annealed
7.83
Minor Separations
SA
7.63
(A-W)
7.63
Solution
7.21
Annealed
7.12
SA
7.28
Minor separations
(A-W)
7.43
in the HAZ
Wrought
6.81
No Separation
A890-6A
ASTM
Heat 1
A890-6A
ASTM
Heat 1
A890-6A
ASTM
Heat 1
A890-6A
ASTM
Heat 2
A890-6A
ASTM
Heat 2
A890-6A
ASTM
Heat 3
A890-6A
ASTM
Heat 3
A890-6A
Zeron 100
Zeron100
No separations
7.12
Zeron 100
Zeron100
Wrought
7.96
(A-W)
7.75
111
Table 5-2-4. Intergranular Corrosion Test and Bend Test Results, ASTM A890-1B
(ASTM A262 Practice B, Ferric Sulfate-Sulfuric Acid, Boiling,120 hrs.)
Material
Code
Condition
Corrosion
Bending Results
Rate
(After ICT)
(mpy)
ASTM
Heat 1
As-cast
31.04
Intergranular Separations
30.76
(Fractured)
As-cast
28.02
Separations
(A-W)
28.81
in the WM & BM
Solution
11.39
Minor
Annealed
11.83
Intergranular Separations
SA
12.22
Minor Interdendritic
(A-W)
12.22
Separations in the WM
Solution
10.43
Minor
Annealed
10.76
intergranular separations
SA
18.71
Serious separations
(A-W)
19.08
Solution
9.18
Minor
Annealed
9.02
Intergranular Separations
SA
9.95
Separations
(A-W)
11.13
Solution
8.82
Minor
Annealed
9.09
Intergranular Separations
SA
9.28
Interdendritic Separations
(A-W)
8.99
in the WM
Wrought
8.49
No Separations
A890-1B
ASTM
Heat 1
A890-1B
ASTM
Heat 1
A890-1B
ASTM
Heat 1
A890-1B
ASTM
Heat 2
A890-1B
ASTM
Heat 2
A890-1B
ASTM
Heat 3
A890-1B
ASTM
Heat 3
A890-1B
ASTM
Heat 4
A890-1B
ASTM
Heat 4
A890-1B
Ferralium 255
Ferr.255
9.49
Ferralium 255
Ferr.255
Wrought
10.30
Separations
(A-W)
9.77
113
Table 5-2-5. Intergranular Corrosion Test and Bend Test Results, CD7MCuN
(ASTM A262 Practice B, Ferric Sulfate-Sulfuric Acid, Boiling,120 hrs.)
Material
Code
Condition
Corrosion
Bending Results
Rate
(After ICT)
(mpy)
CD7MCuN
CD7MCuN
CD7MCuN
CD7MCuN
CD7MCuN-CC
CD7MCuN-CC
Heat 1
Solution
9.15
Annealed
8.83
SA
14.78
Serious interdendritic
(A-W)
14.48
separations in the WM
Solution
12.40
Intergranular Separations
Annealed
12.37
SA
13.67
Separations
(A-W)
14.07
in the WM & BM
Heat 2
Solution
10.01
No Separations
CC*
Annealed
10.37
Heat 2
SA
10.73
Serious separations
CC*
(A-W)
10.78
Heat 1
Heat 2
Heat 2
No separations
* CC - centrifugal cast
cast or SA. It is to be recalled, that the entire fusion zone of an autogenous weld is an
unmixed zone, in which depletion of alloy elements through segregation may occur
during solidification and subsequent transformation, and thus egregiously result in the
degradation of corrosion resistance.
In addition, nitrogen has a significant effect on pitting corrosion behavior of DSS.
In general, an increase in nitrogen content in the shielding gas, improves the pitting
corrosion resistance. The loss of nitrogen during welding may result in a decrease in
corrosion resistance. The study on adding 5% nitrogen into the shielding gas, during
autogenous welding, reveals that the corrosion resistance (CPT) was improved or
partially restored (Table 5-1-4). However, the extent of CPT improvement, through
adding nitrogen into the shielding gas, is not as significant as anticipated. It is to be
noted that the dramatic decrease in CPT upon autogenous welding is consistent with what
was reported in the literature. Thus, welding DSS without a filler metal is not a
recommended practice.
A similar effect of autogenous welding on IGC resistance was also determined for
SA cast materials and the wrought counterparts. The bending results of ICG test samples
show that IGC preferentially occurred in the fusion zone and/or HAZ. However, for the
castings in the as-cast condition, autogenous welding slightly improves the IGC behavior
in terms of a decrease in the IGC rate. It is believed that this positive effect of
autogenous welding on IGC of as-cast materials is attributed to a refined grain structure
in the fusion zone.
115
Filler Metal
Electrode Diameter
Welding
Welding
(inches)
Current (A)
Voltage (V)
ASTM 890-4A
Alloy 2209
1/8
93
26
ASTM 890-5A
Alloy 2507
1/8
94
25
ASTM 890-6A
Zeron 100
5/32
152
26
ASTM 890-1B
Ferralium 255
1/8
113
26
CN7MCuN
Ferralium 255
1/8
113
26
Figure 5-1. Cutting Plan for Corrosion Test Samples for Preliminary Study of Pitting
Performance of Composite Welds
117
Figure 5-2. ASTM A890-4A, Sample 1, 60C, 6 min, Pits in the HAZ, 200X
Figure 5-3. ASTM A890-5A, Sample 1, 65oC, 6 min, Pits on FL, 200X
119
Figure 5-4. ASTM A890-5A, Sample 3, 65oC, 2 min, Pits on HAZ, 200X
Figure 5-5. ASTM A890-6A, Sample 1, 65oC, 6 min, Pits on WM, 200X
120
Preliminary conclusions, based on the results of corrosion testing conducted on the SMA
welded samples, can be drawn as follows:
1).
2).
Surface condition (roughness) of a corrosion test sample will influence the base
metal CPT. In general, the finer the surface finish, the higher the CPT.
These preliminary results of the trial pitting corrosion test on DSS castings
clearly define the necessity for an additional detailed study on the corrosion performance
of the DSS composite welds.
The heat treatment requirements for ASTM A890-6A mandate is that, castings shall be
heated to 2010F (1100C) minimum, held for sufficient time to heat casting uniformly to
temperature, quenched in water or cooled rapidly by other means.
A carefully planed heat treatment schedule, based on the specification and
metallurgy of the alloys, was applied to as-cast 4A and 6A materials. This heat treatment
schedule is presented in Table 5-4.
Table 5-4. Duplex Stainless Steel Casting Heat Treatment Study Schedule
HT No.
HT Temperature
Treatment Time
Arrest Method
Quench Method
(F, C)
1
2000F (1090C)
4 Hours
N/A
Water Quench
2000F (1090C)
4 Hours
N/A
Air Cool
2050F (1120C)
4 Hours
N/A
Water Quench
2050F (1120C)
4 Hours
N/A
Air Cool
2050F (1120C)
4 Hours
See Note 1
Water Quench
2050F (1120C)
4 Hours
See Note 1
Air Cool
2050F (1120C)
4 Hours
See Note 2
Water Quench
2050F (1120C)
4 Hours
See Note 2
Air Cool
2100F (1150C)
4 Hours
N/A
Water Quench
10
2100F (1150C)
4 Hours
N/A
Air Cool
Note 1: Thermal Arrest (Per ASTM A890-4A) requires that the castings be cooled to
1850F (1010C) minimum for a duration of 15 minutes (minimum) prior to quenching.
Total arrest time will be 1 hour.
Note 2: Thermal Arrest will be conducted at 1950F (1065C) for a duration of 1 hour
prior to quenching.
122
In the schedule, three heat treatment temperatures were selected (2000F, 2050F
& 2100F) followed by different cooling methods (air cool and water quench). Two
thermal arrest procedures were applied with the 2050F heat treatment temperature. One
thermal arrest method required castings be cooled to 1850F (1010C) minimum for a
duration of 15 minutes prior to quenching. The other was conducted at 1950F (1065C)
for a duration of one hour prior to the final quench. Totally, there were ten different heat
treatment conditions for each alloy, making a total of twenty tested lots.
CPT testing, ICG testing results of all the heat treated 4A and 6A materials are as
follow.
3.1. CPT
The CPT test results of the heat treatment study samples are presented in Tables
5-5-1 and 5-5-2 for ASTM A890-4A and 6A.
All the ASTM A890-4A water quenched materials in this study reveal the same
CPT as foundry SA materials (40C), except when an 1850F (1010C) thermal arrest is
applied (35C). All the air cooled materials exhibit a CPT of 35C, with the exception of
the 1950F (1065C) thermal arrest with a CPT of 40C.
For ASTM A890-6A (Heat 3), the CPT of the foundry SA material is 55C. 6A
does not require a thermal hold in accordance with ASTM A890. The same thermal
holds as for 4A were evaluated to determine if thermal holds were detrimental. All the
water quenched heat treated materials (CPT 45-55C) exhibit higher CPTs than the air
cooled (CPT 5-50C) for the same heat treatment temperature and thermal arrest
123
Table 5-5-1. CPT & IGC Test Results of Heat Treatment Study Materials, ASTM A890-4A, Heat 1
(ASTM G48, 6% FeCl3, 24 hrs.)
Treatment Time
Arrest Method
Quench Method
CPT
(C)
Heat Treatment
Temperature
(F, C)
2000F (1090C)
4 Hours
N/A
Water Quench
40
2000F (1090C)
4 Hours
N/A
Air Cool
35
2050F (1120C)
4 Hours
N/A
Water Quench
40
2050F (1120C)
4 Hours
N/A
Air Cool
35
2050F (1120C)
4 Hours
Water Quench
35
2050F (1120C)
4 Hours
Air Cool
35
2050F (1120C)
4 Hours
Water Quench
40
2050F (1120C)
4 Hours
Air Cool
40
2100F (1150C)
4 Hours
See Table11
Note 1
See Table11
Note 1
See Table11
Note 2
See Table11
Note 2
N/A
Water Quench
40
10
2100F (1150C)
4 Hours
N/A
Air Cool
35
124
Intergranular
Corrosion
Rate (mpy)*
12.35
11.61
10.15
9.15
11.87
12.11
9.58
10.14
10.50
10.78
11.26
11.36
11.27
10.62
11.29
10.81
12.85
11.95
11.62
11.81
Table 5-5-2. CPT & IGC Test Results of Heat Treatment Study Materials, ASTM A890-6A, Heat 3
(ASTM G48, 6% FeCl3, 24 hrs.)
Treatment Time
Arrest Method
Quench Method
CPT
(C)
Heat Treatment
Temperature
(F, C)
2000F (1090C)
4 Hours
N/A
Water Quench
45
2000F (1090C)
4 Hours
N/A
Air Cool
40
2050F (1120C)
4 Hours
N/A
Water Quench
55
2050F (1120C)
4 Hours
N/A
Air Cool
50
2050F (1120C)
4 Hours
Water Quench
45
2050F (1120C)
4 Hours
Air Cool
2050F (1120C)
4 Hours
Water Quench
55
2050F (1120C)
4 Hours
Air Cool
50
2100F (1150C)
4 Hours
See Table11
Note 1
See Table11
Note 1
See Table11
Note 2
See Table11
Note 2
N/A
Water Quench
55
10
2100F (1150C)
4 Hours
N/A
Air Cool
45
125
Intergranular
Corrosion
Rate (mpy)*
7.27
6.85
6.72
6.58
7.65
8.02
7.30
6.93
7.25
7.52
8.50
8.43
6.88
7.25
8.33
8.13
7.82
7.87
8.68
8.82
method. In general, the air cooled coupons had CPTs of 5-10C lower than the water
quenched materials. An exception for the CPT response is found for the 1850F
(1010C) thermal arrested and followed by air cool, with which shows a CPT of 5C.
The heat treatment produced a secondary phase (s) as etched with 40% NaOH per ASTM
A923 Method A. Thus, thermal holds at 1850F followed by air cooling should not be
applied for 6A materials. In general, the thermal arrests applied in this study revealed no
significant influence on the CPT. The heat treated materials have similar CPTs,
regardless of heat treatment temperature and cooling method.
3.2. IGC
The ICT was conducted on the ASTM A890-4A & 6A heat treated materials. The
results are presented in Table 5-5-1 for ASTM A890-4A and Table 5-5-2 for 6A. It is
evident that the water quenched materials (10.50-12.85mpy) show a slightly lower IGC
rate than the air cooled materials (9.15-11.81mpy), for the same heat treatment
temperature and thermal arrest method. The difference between water quenched and air
cooled materials is approximately 0.5 to 2.0 mpy. The study indicates that the IGC rates
will not be influenced significantly by different heat treatment conditions.
Ferralium 255. The CD7MCuN heat was tested with both the static and centrifugal
casting. Totally, eleven lots were tested.
The Charpy tests were conducted according to ASTM A370 and ASTM E23 in
the temperature range of 80 C to 20C. Duplicate samples were tested at each test
temperature. The energy absorbed, lateral expansion and percent shear of the tested
Charpy bars, were recorded for each sample. The Charpy results are presented in Figure
5-6, as a function of test temperature.
The Charpy results (Figure 5-6) show that the toughness of the majority of the
heats, over the test temperature interval, falls in the same range. However, ASTM A8904A Heat 1 and wrought Zeron 100 exhibit outstanding toughness, compared to the other
tested materials. Wrought Ferralium 255 possesses the worst toughness at low test
temperatures (-40 to -10C). In addition, the two heats of ASTM A890-4A revealed
significant differences in their toughness, as indicated in Figure 5-6.
The toughness was found to be similar for the SA CD7MCuN castings in the
static and centrifugal cast conditions. This indicates that the two casting methods may not
significantly affect the mechanical properties, however, just one heat was tested in the
centrifugal cast condition.
Based on the Charpy impact test results, it can be concluded that most of the cast
materials have better toughness than their wrought counterparts in the temperature range
of 80C to 20C, and a heat-to-heat variation in toughness can exist.
127
Figure 5-6. Toughness of Solution Annealed Duplex Stainless Steel Castings and Companion Wrought Alloys
128
Material
Heat No.
Filler Metal
Pass/Fail
ASTM A890-4A
Heat 4
Alloy 2209
Pass
ASTM A890-5A
Heat 3
Alloy 2507
Pass
ASTM A890-6A
Heat 1
Zeron 100
Pass
ASTM A890-1B
Heat 1
Ferralium 255
Pass
CD7MCuN
Heat 2
Ferralium 255
Pass
129
Figure 5-7. ASTM A890-5A Weldability Bend Test Sample (a) with
Discontinues Marked on Cross Section Prior to Bending, (b) After Bending
130
131
The NaOH etched microstructure of these samples are presented in Figures 5-8-2 through
5-8-4.
In contrast with foundry SA sample in Figure 5-8-1, where smooth
ferrite/austenite boundaries are observed, the other trial samples all show distinctive
secondary phase microconstituents at the austenite/ferrite boundaries, but at different
levels due to various holding times at 1550F (845C).
In Figure 5-8-2 (10 minutes at 1550F), most interphase (F/A) boundaries are
clear and unprecipitated. However, waviness can be observed for some boundaries,
which indicates that precipitation has started. According to ASTM A923, the structure
may be classified as Possible Affected Structure.
As holding time increased, secondary phase(s) began to readily visible along
interphase boundaries (Figures 5-8-3) as darker etching secondary particles. Comparing
20 minutes 30 minutes holding, there is no significant morphology change except the
growth of the secondary particles. According to ASTM A923, the structures are
classified to be Affected Structure.
Figure 5-8-4 shows the interphase (F/A) boundaries of the 30 minutes hold sample at
1000X. The dark etched secondary phase(s) particles grew at the phase boundaries and
into the ferrite matrix.
132
Figure 5-8-1. Sodium Hydroxide Etched Structure of ASTM A890-4A (a) As-cast,
(b) SA Casting, (c) Wrought Alloy 2205, 400X
133
Figure 5-8-2. Sodium Hydroxide Etched Possible Affected Structure (Sample #1,
1950oF + WQ, 1550oF for 10 minutes + WQ), 400X
Figure 5-8-3. Sodium Hydroxide Etched Affected Structure (Sample #3, 1950oF + WQ,
1550oF for 30 minutes + WQ), 400X
134
135
Method B
P/F**
P
P
P
P
P
P
P
P
P
P
F
* Charpy Impact test conducted according to ASTM A370 and E23 utilizing
V-notched Charpy test samples
** Acceptance criterion of method B of base metal is 40 ft-lbs (54J) at 40F/C)
136
Table 5-8-1 Duplex Stainless Steel ASTM A923 Method C Ferric Test Results,
ASTM A890-4A (6% FeCl3, Base Metal@25C & Weld Metal@22C, 24 hrs.)
Material
Heat #
Condition
Corrosion Rate
P/F***
(mdd**)
ASTM
CPT
(C)
Heat 1
Solution annealed
0.73
40
Heat 1
SA
65.93
30
A890-4A
ASTM
A890-4A
ASTM
Autogenous welded
Heat 2
Solution annealed
2.19
35
Heat 2
SA
65.93
<0
0.00
50
415.20
<0
A890-4A
ASTM
A890-4A
ASTM
Autogenous welded
Heat 3
Solution annealed
Heat 3
SA
A890-4A
ASTM
A890-4A
ASTM
Autogenous welded
Heat 4
Solution annealed
0.00
45
Heat 4
SA
15.10
20
Solution annealed
2.12
50
33.34
15
A890-4A
ASTM
A890-4A
Autogenous welded
ASTM
Heat 4
A890-4A
CC*
ASTM
Heat 4
SA
A890-4A
CC*
Autogenous welded
Alloy 2205
Wrought
0.00
40
Alloy 2205
Wrought
7.92
25
Autogenous welded
* CC - centrifugal cast
**mdd - mg/dm2/day
*** The acceptance criterion is no corrosion rate shall excess 10mdd.
137
Table 5-8-2 Duplex Stainless Steel ASTM A923 Method C Test Results,
ASTM A890-5A (6% FeCl3, Base Metal@25C & Weld Metal@22C,24 hrs.)
Material
Heat #
Condition
Corrosion Rate
P/F***
(mdd**)
ASTM
CPT
(C)
Heat 1
Solution annealed
2.64
65
Heat 1
SA
3.05
45
A890-5A
ASTM
A890-5A
ASTM
Autogenous welded
Heat 2
Solution annealed
0.00
50
Heat 2
SA
4.41
40
A890-5A
ASTM
A890-5A
ASTM
Autogenous welded
Heat 3
Solution annealed
0.00
65
Heat 3
SA
0.00
45
Solution annealed
0.00
50
3.78
30
A890-5A
ASTM
A890-5A
Autogenous welded
ASTM
Heat 3
A890-5A
CC*
ASTM
Heat 3
SA
A890-5A
CC*
Autogenous welded
Alloy 2507
Wrought
0.00
80
Alloy 2507
Wrought
0.00
45
Autogenous welded
* CC - centrifugal cast
**mdd - mg/dm2/day
*** The acceptance criterion is no corrosion rate shall excess 10mdd.
138
Table 5-8-3. Duplex Stainless Steel ASTM A923 Method C Test Results,
ASTM A890-6A (6% FeCl3, Base Metal@25C & Weld Metal@22C,24 hrs.)
Material
Heat #
Condition
Corrosion Rate
P/F***
(mdd**)
ASTM
CPT
(C)
Heat 1
Solution annealed
0.00
65
Heat 1
SA
4.47
55
A890-6A
ASTM
A890-6A
ASTM
Autogenous welded
Heat 2
Solution annealed
0.00
70
Heat 2
SA
0.00
45
A890-6A
ASTM
A890-6A
ASTM
Autogenous welded
Heat 3
Solution annealed
0.67
55
Heat 3
SA
2.70
40
A890-6A
ASTM
A890-6A
Autogenous welded
Zeron 100
Wrought
0.00
65
Zeron 100
Wrought
0.00
30
Autogenous welded
2
139
Table 5-8-4 Duplex Stainless Steel ASTM A923 Method C Test Results,
ASTM A890-1B (6% FeCl3, Base Metal@25C & Weld Metal@22C,24 hrs.)
Material
Heat #
Condition
Corrosion Rate
P/F***
(mdd**)
ASTM
CPT
(C)
Heat 1
Solution annealed
0.00
35
Heat 1
SA
16.79
25
0.00
40
198.02
15
3.45
30
133.92
15
2.87
35
184.31
10
A890-1B
ASTM
A890-1B
ASTM
Autogenous welded
Heat 2
Solution annealed
Heat 2
SA
A890-1B
ASTM
A890-1B
ASTM
Autogenous welded
Heat 3
Solution annealed
Heat 3
SA
A890-1B
ASTM
A890-1B
ASTM
Autogenous welded
Heat 4
Solution annealed
Heat 4
SA
A890-1B
ASTM
A890-1B
Autogenous welded
Ferralium
Wrought
1.96
45
255
Ferralium
Wrought
66.39
25
255
Autogenous welded
2
140
Table 5-8-5 Duplex Stainless Steel ASTM A923 Method C Test Results,
CD7MCuN (6% FeCl3, Base Metal@25C & Weld Metal@22C,24 hrs.)
Material
Heat #
Condition
CD7MCuN
Heat 1
Solution Annealed
CD7MCuN
Heat 1
SA
Corrosion Rate
P/F*
CPT
(mdd**)
**
(C)
0.00
45
427.03
0.00
40
142.64
15
0.00
50
116.40
Autogenous Welded
CD7MCuN
Heat 2
Solution Annealed
CD7MCuN
Heat 2
SA
Autogenous Welded
CD7MCuN-
Heat 2
CC
CC*
CD7MCuN-
Heat 2
SA
CC
CC*
Autogenous Welded
Solution Annealed
* CC - centrifugal cast
** mdd - mg/dm2/day
*** The acceptance criterion is no corrosion rate shall excess 10mdd.
141
15
7. Microstructure Characterization
The testings gave a significant database on characterizing the corrosion and
mechanical properties of the DSS castings. In general, the performance of a material is
controlled by its microstructure. In order to provide a better understanding of corrosion
behavior and mechanical properties of DSS castings, microstructural characterizations
were conducted using optical light metallography (OLM), color staining etching, SEM
and EDS analysis.
The materials selected for microstructural evaluations include:
1). As-cast, SA static cast, SA centrifugal castings and wrought materials.
2). Pitting corrosion tested samples with and without autogenous welds.
3). Intergranular corrosion tested samples.
4). Solution annealing heat treatment study samples.
In general, duplex stainless steel microstructures consist of approximately equal
proportions of austenite and ferrite, with ferrite comprising the matrix. During casting,
DSS solidify as essentially 100% ferrite. At elevated temperatures (1300-2370C),
austenite nucleates and grows first at ferrite grain boundaries and later along preferential
crystallographic directions within the ferrite grains. Diffusion/segregation of alloy
elements must occur as the transformation of ferrite to austenite proceeds. Normally,
austenite stabilizing elements (such as C, Ni, N, and Cu) concentrate in the austenite and
ferrite stabilizing elements (such as Cr, Mo and W) segregate to the ferrite. The extent of
the transformation depends not only on the balance between austenite stabilizing and
ferrite stabilizing elements, but also on the time available for diffusion and on the
diffusion rate of specific elements. Normally, both cast and wrought DSS exhibit a
142
ferrite matrix with austenite of varying morphologies, but the cast microstructure is
somewhat coarser and displays a different morphology (island-like) of austenite than that
observed in the wrought plate (rolling texture directionality). Typical structure are shown
in Figure 3-1.
ASTM A890-4A
ASTM A890-4A is an alloy containing approximately 22wt%Cr, 5wt%Ni,
3.0wt% Mo and 0.17wt%N. Three heats (Heat 1, Heat 2 and Heat 3) of ASTM A8904A,
from different foundries, were selected for this study in the as-cast, SA and SA +
autogenously welded condition. Pitting and IGC tested samples were also examined. For
comparison, the wrought counterpart alloy 2205 was included in the microstructure
study.
Figures 5-9 through 5-11 show the microstructure of Oxalic etched ASTM
A890-4A, Heats 1 & 2, in the as-cast and SA condition together with wrought counterpart
Alloy 2205. The microstructure of ASTM A890-4A Heat 1 in the as-cast and SA
conditions is shown in Figure 5-9. In the as-cast condition, austenite islands in a ferrite
matrix are evident, and fine precipitates are observed mainly along the ferrite/austenite
boundaries as shown in Figure 5-9a. In addition, some randomly distributed inclusions
are found in the matrix. Figure 5-9b reveals the microstructure of Heat 1 in the SA
condition. It is evident that the particles along the ferrite/austenite boundaries, observed
143
144
145
in the as-cast condition, are dissolved upon solution annealing. Austenite islands with
smooth boundaries (no precipitates) are obvious in the ferrite matrix. Inclusions in the
matrix remain unchanged after solution annealing. Figure 5-10 shows the microstructure
of ASTM A890-4A Heat 2 in the SA condition. It is clear that Heat 2 reveals a
microstructure identical to Heat 1 in the SA condition, in terms of austenite islands in a
ferrite matrix. However, larger inclusions were observed in the Heat 2 matrix as
compared to Heat 1. It is considered that these randomly distributed large inclusions may
have an influence the mechanical properties. The microstructure of wrought counterpart
Alloy 2205 is presented in Figure 5-11. A rolling texture structure directionality, from
hot working, followed by a solution annealing and quenching, is evident in comparison
with the cast material.
Figure 5-12 shows the OLM micrograph of ASTM A890-4A Heat 1 after pitting
testing in both the as-cast and SA condition. Figure 5-12a shows the microstructural
features of pitting on ASTM A890-4A Heat 1 in the as-cast condition. It is evident that
pits initiate at the precipitates along the ferrite/austenite boundaries and preferentially
grow into ferrite. In the SA condition, pits also initiate at the ferrite/austenite boundaries
and preferentially grow into austenite, as presented in Figure 5-12b. The OLM
characteristics of pitting in wrought Alloy 2205 base metal are shown in Figure 5-13.
The pitting behavior of wrought Alloy 2205, in terms of the initiation and growth, was
determined to be identical to the corresponding cast materials in the SA condition.
146
147
The optical features of the pitting behavior of autogenous welds on ASTM A8904A
castings and wrought Alloy 2205 are shown in Figures 5-14 through 5-18. In general,
a finer austenite structure in the ferrite matrix is evident in the fusion zone, as compared
to the cast base metal. This finer austenite microstructure shows the original
solidification pattern in the autogenous weld fusion zone and reflects the rapid cooling
upon welding. It should be recalled that all of the autogenous weld samples were tested
in the as-welded condition, and no filler was added. Thus, the fusion zone in these
autogenous welds is truly an Unmixed Zone. It is to be expected that segregation of
alloy elements in the fusion zone occurs during solidification. Generally, a greater extent
of element segregation occurs in the fusion zone adjacent to the fusion boundary, as
compared to the other fusion zone areas. The segregation of Cr and Mo in the
148
149
Figure 5-14. Pitting of Autogenous Weld on As-cast ASTM A890-4A, Heat 1, Oxalic
150
151
152
153
154
Figure 5-19. SEM Secondary (a) and Back-scattered (b) Electron Images of the Fusion
Line Area of the Autogenous weld on SA ASTM A890-4A Heat 1, Oxalic, 300X
155
Figure 5-20. Typical Secondary (a) and Back-scattered (b) Electron Images of SA ASTM
A890-4A Heat 1 Base Casting, Oxalic, 1000X
156
The EDS analysis of the base metal was conducted at the locations A, B and C, as
identified in Figure 5-20a. The EDS spectra are presented in Figure 5-21 for location A
and B in Figure 5-20a; and in Figure 5-22 for locations C. It is evident that the austenitic
region is slightly richer in Ni than the ferritic region, and the ferritic region is slightly
richer in Cr & Mo with some Si, than the austenitic region. The dark particles, shown at
Location C in Figure 5-20a, were determined to be rich in Fe, Mn, Cr, Si, Al and O with
some Ti and S present. This EDS result indicates that the dark particles in the casting
base metal are inclusions. Figure 5-22 shows an EDS spectrum of a dark particle.
Figure 5-21. EDS Spectrum of Location A (Austenite) and B (Ferrite) in Figure 5-20a
157
The SEM secondary and back-scattered electron images, of the Heat 1 autogenous
fusion zone, are presented in Figure 5-23. An acicular shaped austenite structure, in the
fusion zone, is evident and is much finer than that in the base casting. EDS analysis was
conducted at locations A and B as labeled in Figure 5-23a. The EDS spectra for locations
A & B, in the fusion zone, are presented in Figure 5-24 for the austenite (Location A) and
Figure 5-25 for the ferrite (Location B), respectively. It is evident that the austenite and
ferrite in the autogenous fusion zone have similar compositions.
In addition, EDS line scanning and mapping for Cr, Mo and Ni were conducted
across the fusion boundary area on the autogenous weld of Heat 1. Figure 5-26 shows
the digital image at the fusion boundary area for the EDS line scan study of Cr, Mo and
Ni distributions. The 73.9mm yellow colored line in Figure 5-26 indicates the scan
location. The Cr, Mo and Ni distributions across the fusion boundary are presented in
Figure 5-27. It is evident that a slight Mo depletion was determined at the
ferrite/austenite interfaces (Locations 1 and 2), as labeled in Figure 5-26. It is considered
that Mo depletion at the ferrite/austenite interfaces is responsible for a reduction in pitting
resistance of the fusion zone area, adjacent to the fusion boundary.
158
Figure 5-23. SEM Secondary (a) and Back-scattered (b) Electron images of ASTM
A890-4A Heat 1 Autogenous weld Fusion Zone, Oxalic, 1010X
159
160
Two element mappings (Cr, Mo and Ni) were conducted on the same sample across the
fusion boundary, as presented in Figures 5-28 and 5-29. It is clear that Cr and Mo are
rich in the ferrite region and Ni is rich in the austenite region, for the base casting and the
FZ area adjacent to the FL. A smaller extent of Cr, Mo and Ni segregation was detected
in the general fusion zone area in comparison with the fusion zone area adjacent to the
fusion line. The element mapping results are consistent with the spot EDS results in the
austenite and ferrite regions for both the casting base metal and fusion zone.
161
Figure 5-28. Element Mapping (Cr, Mo and Ni) Across Fusion Boundary
Figure 5-29. Element Mapping (Cr, Mo and Ni) Across Fusion Boundary
162
In addition, SEM and EDS analysis were also conducted on SA A890-4A Heat 2.
Figure 5-30 presents a SEM photomicrograph of the Heat 2 casting base metal. The
austenite islands in the ferrite matrix are evident, as well as some light gray particles
(marked A in Figure 5-30) and some dark gray particles (marked B in Figure 5-30).
EDS analysis was performed at locations A and B. The spectra of these EDS analysis
are presented in Figures 5-31 and 5-32. From Figure 5-31, the light gray particles
(Location A in Figure 5-30) are shown to be rich in Ti, Cr and Fe, with some Nb present.
It is considered that these light gray particles may be Ti and Cr carbides. Figure 5-32
reveals that the dark gray particles (Location B) are rich in Ti, Cr, Mn and O, with some
Al and Nb present. This EDS result indicates that these dark gray particles are
inclusions/oxides.
Three intergranular corrosion tested samples were also chosen for study. A8904A
Heat 1, in the as-cast and SA condition, and wrought counterpart Alloy 2205.
Figure 5-33 reveals the OLM micrographs of the transverse cross section of the
intergranular corrosion tested Heat 1, in the as-cast condition (Figure 5-33a) and SA
condition (Figure 5-33b), and Alloy 2205 (Figure 5-33c). Note that the transverse cross
section is through an intergranularly attacked region and represents the typical extent of
attack for each sample. It is evident that IGC is mainly associated with the
ferrite/austenite interface, regardless of the material condition (as-cast or solution
annealed or wrought). However, as-cast Heat 1 reveals the greatest extent of
intergranular attack (60mpy), and SA Heat 1 (12mpy) and wrought Alloy 2205 (16mpy)
show basically an identical level of corrosion. It is believed that precipitates, along the
ferrite/austenite interface, are responsible for the low IGC resistance of as-cast Heat 1.
163
Figure 5-30. SEM Photomicrograph of the Heat 2 Base Metal, Oxalic, 1000X
164
165
166
ASTM A890-5A
ASTM A890-5A is an alloy containing about 25wt% Cr, 7wt% Ni, 3.5wt% Mo
and 0.27wt% N. One heat (Heat 1) of ASTM A890-5A was selected for study in the
as-cast and SA condition, in addition to the wrought counterpart Alloy 2507.
Figure 5-34 shows the microstructure of ASTM A890-5A casting base metal in
the as-cast and SA condition. Figure 5-34a shows the microstructure of Heat 1 in as-cast
condition. A significant amount of irregularly shaped precipitates were observed in the
ferrite matrix. It is to be noted that a detailed study of these irregularly shaped
precipitates was conducted on ASTM A890-6A. The irregularly shaped precipitates were
determined to be Cr and Mo carbides based on the EDS results. Figure 5-34b reveals the
microstructure of Heat 1 in the SA condition. The irregularly shaped precipitates present
in the as-cast condition were completely dissolved upon solution annealing. A rolling
texture structure directionality, obtained by hot working and followed by solution
annealing, was observed in the wrought counterpart Alloy 2507, as shown in Figure 5-35.
Figure 5-36 shows the pitting behavior of ASTM A890-5A Heat 1 base casting in
both the as-cast and SA conditions. As shown in Figure 5-36a (in the as-cast condition),
pits preferentially initiate in the ferrite region and are mainly associated with the
irregularly shaped precipitates. However, in the SA condition, as shown in Figure 5-36b,
pits initiated at the ferrite/austenite interfaces and preferentially grew into the austenite
region, this behavior is similar to ASTM A890-4A in the SA condition.
167
168
169
170
ASTM A890-6A
ASTM A890-6A is a DSS of 25wt% Cr, 7wt% Ni, 3.5wt% Mo and
0.27wt% N. Two heats (Heats 2 & 3) of ASTM A890-6A heats were selected for the
microstructural evaluation in the as-cast and SA condition, as well as one heat of ASTM
A890-6A (Heat 1), for the ICT. It is to be noted that a Heat 3 sample from the heat
treatment study was also selected due to its low CPT value (5C). This material had been
SA at 2050F (1120C) followed by a 1850F (1010C) thermal arrest before air cooling.
Figure 5-37 shows the microstructure of Heat 2 in the SA condition, which
reveals a normal duplex casting microstructure. Figure 5-38 presents the microstructure
of Heat 3 in the as-cast and SA condition. Irregularly shaped precipitates in the ferrite
matrix are evident, in the as-cast condition (Figure 5-38a). Figure 5-38b reveals that the
irregular shaped precipitates in the ferrite matrix were dissolved during the solution
annealing treatment, which indicates a normal response of DSS castings to the solution
annealing heat treatment. In addition to austenite islands in a ferrite matrix, some
randomly distributed dark gray inclusions are also observed in the matrix.
Figure 5-39 shows the microstructure of a Heat 3 sample from the heat treatment
study (5C CPT). It is evident that the irregular shaped precipitates are present in the
ferrite matrix after the solution annealing treatment. It is considered that an improper
solution annealing heat treatment was applied to this sample. The corresponding pitting
corrosion behavior is presented in Figure 5-40. Pits preferentially initiated in the ferrite
region and were associated with the irregularly shaped precipitates. These irregular
shaped precipitates are responsible for the low CPT value of the SA Heat 3 sample.
Further evaluation of the irregular shaped precipitates in the ferrite region was performed
171
172
173
Figure 5-39. Microstructure of Improperly Heat Treated ASTM A890-6A Heat 3, Glyceragia
174
Figure 5-40. Pitting of Improperly Heat Treated ASTM A890-6A, Heat 3, Oxalic
175
using SEM and EDS. Figure 5-41 shows a SEM photomicrograph of the irregular shaped
precipitates in the ferrite region, in addition to the austenite islands and some gray
particles. Noted that the gray particles in Figure 5-41 were optically revealed as the dark
gray particles shown in Figures 5-39 and 5-40. The EDS analysis was conducted at
locations A, B, C & D (marked in Figure 5-41), and spectra are presented in Figures 5-42
to 5-45. Figure 5-42 reveals a normal EDS spectrum for the austenite region (Location
A). The gray particle (Location B) is considered to be an inclusion based on the
spectrum (rich in Cr, Mn, Al, Si & O, Figure 5-43). Figures 5-44 and 5-45 show the EDS
results of the irregular shaped precipitates in the ferrite region (Locations C & D). They
are rich in Cr, Fe and Mo. Based on the EDS spectra, these precipitates are considered to
be s-phase. Also it is believed that the presence of s-phase is responsible for the
preferential pit initiation in this area and caused the dramatic decrease in CPT for this HT
on 6A material. In addition, element mapping (Figure 5-46) for Cr, Mo and Ni was
performed in the same area s presented in Figure 5-41. Mo depletion in the ferrite region
was determined, as well as the segregation of Cr into the ferrite and Ni into the austenite.
Microstructural characterization was also carried out on the wrought counterpart
Zeron 100. Its base metal microstructure reveals a typical wrought DSS structure as
shown in Figure 5-47. Three ICT samples were chosen for study; A890-6A Heat 1 in the
as-cast, SA conditions and wrought counterpart Zeron 100. Figure 5-48 shows the OLM
micrographs of transverse cross sections of intergranular corrosion tested Heat 1, in the
as-cast (Figure 5-48a) and SA condition (Figure 5-48b) and Zeron 100 (Figure 5-48c).
176
177
178
179
Figure 5-46. Element Mapping (Cr, Mo and Ni) in the Area Presented in Figure 5-41
180
181
182
183
It is predicted that these fine precipitates are Cr or Mo carbides based on the morphology
and locations. No SEM or EDS analysis were conducted on this sample. In addition,
some dark gray inclusions were also found in the matrix. The fine precipitates were
completely dissolved upon solution annealing treatment as presented in Figure 5-49b.
The dark gray inclusions were un-changed after solution annealing treatment.
Figure 5-50 illustrates the microstructure of CD7MCuN Heat 2 in the SA static
cast (Figure 5-50a) and centrifugal cast (Figure 5-50b) condition. A normal DSS cast
microstructure, in the SA condition, was revealed for both static cast and centrifugal cast
samples. The centrifugal cast material shows a finer austenite structure than the static
casting. This finer austenite structure in the centrifugal casting may have a positive
influence on the mechanical properties, when compared to static casting. Figure 5-51
shows the microstructure of wrought alloy Ferralium 255. The structure is similar to all
other wrought alloys.
It has been established that nitrogen has a significantly positive influence on
pitting resistance of duplex castings. Thus, the loss of nitrogen from the fusion zone
during welding may cause a decrease in pitting resistance in the fusion zone. A trial
experiment, performed by adding 5% nitrogen into Ar shielding gas, was conducted on
Ferralium 255 autogenous welds. The CPT of the Ferralium 255 autogenous weld, with
5% nitrogen+95% Ar, was determined to be 30C compared to 25C for Ferralium 255
autogenous welds with 100% Ar. The OLM micrographs of the pitting behavior for both
Ferralium 255 autogenous welds with and without addition of 5% nitrogen are presented
in Figure 5-52. It is evident that pits preferentially initiated in the fusion zone and at the
fusion line of the autogenous weld with 100% Ar (without 5% nitrogen), as shown in
184
185
186
187
Figure 5-52a and b. Upon adding 5% nitrogen into shielding gas, no pits were found in
the fusion zone, as presented in Figure 5-52c. All of the pits preferentially initiated in the
HAZ of Ferralium 255 autogenous welds (with 5% nitrogen). The improvement in the
CPT is not significant because of the primarily HAZ pit initiation and the fact that the
nitrogen addition only affects the fusion zone. It should be recognized that there are
multiple potential pit initiation locations in the autogenous welds (fusion zone, fusion line
and HAZ). Pits will preferentially initiate at where the pitting resistance is the lowest.
Thus, an understanding of the effect of welding on the corrosion behavior of duplex
stainless steel castings is a necessary and extremely important subject for both foundry
and industry.
In order to identify whether there is precipitation of sigma phase in Ferralium
weld HAZ, a color staining etching technique, utilizing 10% NaCN, was applied to all the
samples evaluated above. No sigma phase was revealed by this color etching technique
in any of the samples.
188
VI. Conclusions
Over a thousand individual tests, including corrosion, impact toughness, weldability
and microstructure evaluation, were conducted in this program. A fairly useful database
for the corrosion performance of the duplex stainless steel castings has been established.
Heat-to-heat and duplex stainless steel alloy system-to-system comparisons were made
based on the obtained results. Some conclusions were drawn as follows:
Both the pitting and intergranular corrosion resistance of cast duplex stainless steels
are equal to or better than their wrought counterparts. Thus, cast and wrought
products can be produced to the same performance standards.
The corrosion test methods for wrought stainless materials are suitable for evaluation
of duplex stainless steel castings:
o
The solution annealing procedures in ASTM A890 are appropriate for placing cast
duplex stainless steel in the proper condition for service.
Despite the application of thermal arrests, corrosion performance was not degraded
when a rapid quench method (water) was applied.
189
materials. Cast duplex alloys can be added to this specification upon the inclusion of
appropriate photomicrographs.
Welding reduced the pitting and intergranular corrosion resistance for both the
wrought and cast duplex alloys of similar composition. The effect of welding should
be considered when selecting an alloy type for specific corrosion service. Thus, the
same fabrication considerations apply to the entire cast/wrought system.
The data obtained in this study suggests that ASTM A923 can be expanded in
coverage to include the cast duplex materials of ASTM A890. Thus, one
specification will cover both wrought and cast materials making selection
independent of product form.
Charpy impact test results show that castings generally have better toughness than
their wrought counterparts in the temperature range of 80C to +20C. Thus,
specification requirements are simplified for an entire system fabrication (both
wrought and cast).
Weldability bend tests (ASTM A494) were performed on castings with the
appropriate (matching) filler metals. All tested heats passed. Therefore, welding is
not a significant factor when considering duplex stainless steel applications.
190
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Specifications
207
1.
ASTM A890-94: Standard Specification for Castings, Iron-Chromium-NickelMolybdenum Corrosion Resistant, Duplex (Austenitic/Ferritic) for General
Application
2.
ASTM G48-92: Standard Test Methods for Pitting and Crevice Corrosion
Resistance of Stainless Steels and Related Alloys by Use of Ferric Chloride Solution
3.
ASTM G48-97: Standard Test Methods for Pitting and Crevice Corrosion
Resistance of Stainless Steels and Related Alloys by Use of Ferric Chloride Solution
4.
5.
6.
ASTM A 370: Standard Methods and Definitions for Mechanical Testing of Steel
Products
7.
ASTM E23: Standard Method for Notched Bar Impact testing of Metallic Materials
8.
ASTM A494-94: Standard Specification for Castings, Nickel and Nickel Alloy
9.
10.
ASTM A799/A 799 M -91: Standard Practice for Stainless Steel Castings,
Instrument Calibration, for Estimating Ferrite Content
208