Effect of Composition Profiles on
Metallurgy and Corrosion Behavior of
Duplex Stainless Steel Weld Metals
Diluting the nitrogen content of the austenite with increased nickel
appears to degrade the weld pitting corrosion property
ABSTRACT. The weld solidification of
duplex stainless steel is entirely ferritic,
and the austenite is formed through a
solid-state phase transformation during
postsolidification cooling. According to
the computer-aided microanalysis, the
ferritic weld solidification was found to
cause the microsegregation of Ni and
Mo, that of Ni being more pronounced
than that of M o , although its extent was
not so great as compared with the case
of austenitic solidification. The partition-
ing of Cr, Ni and M o between the ferrite
and the austenite was not significant in
the welds, while an increase in an austen-
itizer such as Ni and nitrogen promoted
the partitioning by raising the tempera-
ture of the transformation to austenite.
Nitrogen was found to dominate the
formation of the weld austenite by rapid
diffusion during post-solidification cool-
ing, being more enriched in the austenite
than in that of the base metal.
Preferential occurrence of pitting cor-
rosion within the ferrite in current nitro-
gen-bearing duplex stainless steel welds is
due to the compositionally inferior corro-
sion resistance of the ferrite and the
detrimental effect of precipitates within
the ferrite. An increase of nitrogen
improves the weld pitting corrosion
property by ameliorating the pitting resis-
tance of the austenite of the weld, while
an increase of austenite with Ni instead of
nitrogen degrades the weld pitting prop-
erty through the dilution of the nitrogen
content in the austenite.
Background and Objectives
Current duplex stainless steels with low
carbon and high nitrogen exhibit a good
combination of stress corrosion cracking
(SCC) resistance, pitting and crevice cor-
T. OCAWA and T. KOSEKI are with the Joining
Technology Laboratory, Nippon Steel Corp.,
Kanagawa, Japan.
BY T. O G A W A A N D T. KOSEKI
rosion resistance, strength, and tough-
ness in comparison with commonly uti-
lized austenitic and ferritic stainless steels
(Refs. 1, 2). Therefore, they are being
applied increasingly in a variety of fields
that contain corrosive, chloride environ-
ments, such as oil and gas exploration
and gathering systems, pulp and paper
plants and chemical processing plants.
The microstructure of wrought duplex
stainless steels is established by hot work-
ing and subsequent annealing in a t w o -
phase region, and typified by elongated
austenite grains in a ferrite matrix. Gener-
ally, the proportions of austenite and
ferrite are approximately equal in the
annealed condition. The above-men-
tioned property combination of duplex
stainless steels mainly results from such a
microduplex structure. However, fusion
welding processes, which are common
methods of fabrication, give rise to quite
different microstructures in the fusion
and heat-affected zone from that of the
base metal, modifying the weld proper-
ties adversely (Refs. 3-5).
The solidification of duplex stainless
steels is entirely ferritic, with an austenitic
phase formed through a solid-state phase
transformation during postsolidification
cooling (Refs. 3, 6, 7). Thus, the as-
solidified microstructure of the fusion
zone consists of coarse, epitaxial ferrite
KEY W O R D S
Duplex Stainless Steel
Composition Profiles
Effect on Metallurgy
Corrosion Behavior
Profile Effects
Weld Microchemistry
C r / N i / N 2 Profiles
Weld Transformation
N2 Transform Control
N 2 Diffusion Effect
WELDING RESEARCH SUPPLEMENT 1181-s
grains with inter- and intragranular aus-
tenite, though the formation, morpholo-
gy and resultant content of austenite are
justly affected by the weld compositions
and welding parameters (Refs. 3, 4, 8, 9).
Since the transformation occurs preferen-
tially at prior ferrite grain boundaries, the
intergranular austenite generally results in
continuous networks and possesses Wid-
manstatten morphology and/or allotrio-
morphs, while intragranular austenite, if
any, exhibits fine acicular morphology.
The adverse effect of such weld micro-
structures has been particularly pointed
out on the localized corrosion resistance
in chloride environments (Refs. 4, 5, 9-
12). Hence, strong attention has been
paid to the localized corrosion behavior
of the welds, related to their microstruc-
tural characteristics. Pitting corrosion
attacks were found predominantly within
ferrite in the weld metals, as shown in Fig.
1, which was a striking contrast to the
case of base metals where austenite was
susceptible to pitting attacks (Refs. 5, 9,
13). The selective pitting corrosion
attacks within the weld ferrite were con-
sidered to be associated with chromium
depletion arising from the precipitation of
chromium carbide, carbonitride and
nitride within ferrite. The detrimental
effect of chromium nitride on pitting
corrosion resistance was indicated in
weld metals by Sridhar, et al. (Ref. 9), in
weld heat-affected zones by Ume, ef al.
(Ref. 14), and in cast duplex stainless
steels by Poznansky, ef al. (Ref. 15).
However, increased nitrogen certainly
exerted a considerable beneficial influ-
ence on the weld pitting corrosion resis-
tance (Refs. 4, 11, 16). Furthermore, inter-
granular austenite was often observed to
impede the pit.propagation within ferrite
in nitrogen-enriched welds, whereas it
served as a preferential site of pitting in
low-nitrogen welds (Refs. 4, 5, 13).
Increased austenite with higher nitrogen
improved the weld pitting corrosion
resistance, while increased austenite with
 *sr'iFlrijfi .
jM*rl

^ #
^
#
|
- a
5 &
j
lOOym
A
F/g. 7 Typical pitting corrosion of: A weld metal and; B base metal of 22Cr-6Ni-3Mo-0.12N duplex stainless steel. Selective attacks were found
ferrite of the weld metal and in austenite of the base metal

higher Ni content deteriorated when it
became too much, though both were
effective to diminish the deleterious pre-
cipitates within ferrite (Refs. 4, 5, 9).
Accordingly, in addition to the detrimen-
tal effect of the precipitates, there must
be compositional effects on the pitting
corrosion behavior in the welds.
As for austenitic stainless steel weld
metals, composition profiles in the solidi-
fication microstructure have been exten-
sively investigated to understand the
solidification sequence (Refs. 17-21), hot
cracking (Refs. 22, 23), pitting corrosion
(Refs. 24, 25) and fracture (Refs. 26, 27) in
the weld fusion zone. On the other hand,
only a few studies have been made on
the composition profiles in current duplex
stainless steel welds, presumably due to
their complicated microstructures. Suu-
tala, ef al. (Ref. 28), indicated that the
ferritic solidification was not accompa-
nied by significant segregation, but the
solid-state phase transformation to aus-
tenite imparted the partitioning of ele-
ments between the phases in conven-
tional Cr-Ni-Mo stainless steel welds.
Their findings are suggestive, but present
no information concerning nitrogen alloy-
ing which is essential in currently focused
duplex stainless steels. Liljas and Qvarfort
(Ref. 16) recently reported the partition-
ing of major alloying elements, including
nitrogen, between the phases in the
nitrogen-containing duplex welds by the
point-counting technique, using electron
probe microanalysis (EPMA). The data
showed that the partitioning of Cr, Ni and
M o was, if it occurred, insignificant in the
Table 1Chemical Compositions of Duplex Stainless Steel Weld Metals Studied
C Si
22Cr-6Ni-3Mo-0.12N 0.013 0.17
22Cr-10Ni-3Mo 0.005 0.32
22Cr-6Ni-3Mo-0.18N 0.004 0.28
22Cr-10Ni-3Mo-0.12N 0.006 0.31
weld metals, while weld nitrogen was
partitioned and enriched in austenite to a
greater extent than in the case of the
base metals. However, since the point-
counting measurement gives a limited
aspect of composition profiles, full com-
positional variations relating to weld
microstructures remain poorly under-
stood. Nelson, etal. (Ref. 29), applied the
three-step etching technique to a duplex
stainless steel weldment, and successfully
obtained the color metallography with
regard to the segregation and distribution
of Cr throughout the microstructure, but
not to those of other elements.
In the present study, the concentration
profiles of Cr, Ni, M o and nitrogen were
evaluated in the duplex stainless steel
weld metals by using a computer-aided
microanalyzer (hereafter referred to as
CMA) (Refs. 30, 31). Emphasis was placed
on the as-solidified (not heat-affected)
fusion zone. The CMA is an EPMA highly
computerized in its operation, data acqui-
sition and data analysis. As compared
with conventional EPMA, the analytical
sensitivity of the CMA is improved by
approximately eight times, which facili-
tated high-speed quantitative analysis of
alloying elements in a relatively large
area, even as to nitrogen. Moreover, the
computerized data acquisition made it
possible to analyze and display the data
by color graphic images. Based on the
composition profiles obtained, the segre-
gation and partitioning behavior of the
elements was correlated to the micro-
structural changes during weld solidifica-
tion and phase transformation. In addi-
current of 5 fiA at an accelerating voltage
Mn P S Cr Ni Mo N markedly increased in CMA as compared
1.49 0.013 0.0026 22.52 6.12 3.14 0.127
1.49 0.012 0.0063 22.34 9.54 2.98 0.003
1.50 0.014 0.0065 22.48 6.24 3.01 0.184
1.46 0.012 0.0064 22.02 9.98 2.91 0.110
tion, the effect of composition profiles on
the weld pitting corrosion behavior was
discussed.
Experimental
In order to study the weld microchem-
istry, four experimental duplex stainless
steels containing different amounts of Ni
and nitrogen were prepared. The main
compositions of the steels were 22Cr-
6Ni-3Mo-0.12N, 22Cr-10Ni-3Mo, 22Cr-
6Ni-3Mo-0.18N and 22Cr-10Ni-3Mo-
0.12N. Those steels were made by vacu-
um induction melting and hot rolling to
5-mm (0.2-in.) thick plates, and finally
annealed at 1050C (1922F), followed
by water quenching.
Two-pass autogenous (no filler metal
added) welding was performed on the
plates by the gas tungsten arc welding
(GTAW) process. The welding conditions
were 200 A and 13 V with a travel speed
of 15cm/min (38 ipm). Pure Ar was
employed as a shielding gas at a flow rate
of 15 L/min (7 cfh). The chemical analyses
of the weld metals are given in Table 1.
The welded samples were sectioned
transverse to the welding direction, and
the metallographic examination and
microanalysis by CMA were carried out
on the surfaces.
The samples were polished and elec-
trolytically etched in a 50% nitric acid
aqueous solution for optical microscopy.
An area of 200 X 200 ixm that exhibited
typical microstructure was selected for
each sample and marked by microhard-
ness identification. Then the samples
were repolished flat prior to microanaly-
sis. The CMA was operated with a beam
of 15 kV. Note that the beam current is
with that in conventional EPMA, which is
generally in the order of 0.01 to 0.1 fiA.
The size of an analysis spot was 1 ^m, i.e.,
200- X 200-MITI spots were analyzed
step-by-step in each sample. Electron

1 8 2 - s l M A Y 1989
beam irradiation time for each analysis ly separated into two maximum peaks culated nickel equivalent of the weld was
spot was 200 ms, and during the whole due to partitioning between ferrite and almost the same as that of the 22Cr-
measurement, the variation of beam cur- austenite, whereas, for the weld metal, 6Ni-3Mo-0.12N weld, ferrite content was r-
rent was kept within 1%. the distribution of Cr, Ni and M o cen- markedly increased to 97% in the as- Z
Ui
Ferrite content was measured using a tered on the nominal value with a con- welded condition. Ferrite/ferrite inter-
permeability meter (Fischer Feritscope fined width. Distribution of nitrogen in faces without any formation of austenite o.
M10). the weld metal, however, extended to a were observed at some grain bound- o
_l
higher concentration range than that of aries. Composition profiles obviously UJ
the base metal. indicated that partitioning occurred >
Results
between ferrite and austenite during the
Composition Profiles of the austenite formation. Cr and M o were X
22Cr-6Ni-3Mo-0.12N Base and Weld Metal Composition Profiles of the 22Cr-10Ni-3Mo depleted and Ni was enriched in austen- o
Weld Metal cx
Figures 2 and 3 show the microstruc- ite as is the case of the base metal shown <
Figure 6 shows the microstructure and in Fig. 2. Note that the segregation pat- ui
ture and the related CMA images of
composition profiles of the 22Cr-6Ni- the composition profiles of the 22Cr- terns of Ni and M o were still retained
3Mo-0.12N base metal and its autoge- 10Ni-3Mo weld metal. Although the cal- within the ferrite.
nous weld metal, respectively. The z
microstructure of the base metal con- UJ
sisted of austenite (white) and ferrite ICrS 1 2
(relatively dark), each preferentially elon-
*flPW!^^WBfl8 SP a
gated to rolling direction, and propor-
O
_i
tions of the t w o phases were approxi- UJ
>
mately equal (ferrite: 49%). Ferritizers UJ

such as Cr and M o were significantly

a
^ ^ ^ ^ -^
enriched in ferrite, while austenitizers ^\*-^- i
o
such as Ni and nitrogen were enriched in tr
austenite, as generally accepted. The <
UJ
concentration of nitrogen in austenite v>
was approximately 0.2 wt-% on average. ui
cc
O n the other hand, the microstructure of >
I-
the as-solidified fusion zone exhibited
JfiHr - *
zUJ
coarse ferrite grains with continuous net-
E
works of Widmanstatten intergranular a.
austenite. Since the rapid cooling of Cr im_ 21 ' ZZ 23 ' k 'iS Z6 (wtZ)
O
welding retarded the transformation of
ferrite to austenite, the resultant ferrite
>
UJ
content was remarkably increased (fer-
rite: 74%) as compared to that of the a
x
base metal. The partitioning of Cr, Ni and o
M o was not clear between the two oc
<
phases, but some locally enriched traces Ul
CO
of Ni and M o were observed in the Ul
manner of a periodically arranged net- oc
work throughout the microstructure of z
interest. The manner and spacing sug- Ul
gested that such local compositional vari- S
ation resulted from the segregation of Ni a.
O
and M o during cellular/dendritic solidifi-
cation. Nitrogen was significantly en-
riched in austenite, more than the case
of the base metal, up to 0.3 wt-% on x
average. Within ferrite, nitrogen was o
tr
depleted in the vicinity of austenite, while <
slightly enriched in the region far away Ul
u>
from austenite, which was correlated -s --^ r- Fig. 2 A Microstructure, ui
tr
:::;:
... 5 ;-

with the nitride precipitation within fer- and composition profile of

rite, as shown in Fig. 4. It should be noted B - Cr; C - Ni; D - Mo; and
that the ferrite matrix could contain very Enitrogen of the z
low nitrogen content (<0.05 wt-%), as 22Cr-6Ni-3Mo-0.12N base ui
seen in the vicinity of austenite. Figures metal S
a.
5 A - D give the distributions of Cr, Ni, M o O
and nitrogen within the area examined. -i
ui
The fraction of area, the concentration of >
which was within a range of interest, was Ul
a
plotted against the mean value of the ->.
range, where the increment of the range x
u
was selected as 1.0, 0.5, 0.25 and 0.05 CE
wt-% for Cr, Ni, M o and nitrogen, respec-
<
Ul
tively. As for the base metal, the distribu- , r ~ ; " - ... :' (/>
Ul
tion of all the elements exhibited definite- CE
N 0.0 0.1 0.2 0.3 0.4 0.5 0.6 (wtZ)

WELDING RESEARCH SUPPLEMENT 1183-s

 / . rl

Fig. 3 A Microstructure,
and composition profile of
B - Cr; C - Ni; D - Mo; and
Enitrogen of the
22Cr-6Ni-3Mo-0.12N weld ; 20um
metal

N 0.0 0.1 0.2 0-3 0.4 0.5 0.6 (wg:

Composition Profiles of the phases due to partitioning was rather Composition Profiles of the
22Cr-6Ni-3Mo-0.18N Weld Metal limited as compared with the case of 22Cr-10Ni-3Mo-0.12N Weld Metal
near-equilibrium partitioning found in the
The microstructure and composition
The microstructure and composition base metal. Furthermore, nitrogen was
profiles of the 22Cr-10Ni-3Mo-0.12N
profiles of the 22Cr-6Ni-3Mo-0.18N weld strongly enriched in austenite, up to 0.3
weld metal are displayed in Fig. 8. The
metal are given in Fig. 7. Because of wt-% on average. Also, it should be
weld ferrite content was fairly decreased
increased nitrogen, the ferrite content of noted that the nitrogen concentration in
with Ni content to 25%. The austenite
the weld was decreased to 49%, and austenite of the 22Cr-6Ni-3Mo-0.18N
developed with more thickened lath-like
austenite had a weli-developed Widman- weld was almost the same level as that of
morphology rather than the Widmanstat-
statten structure. There was some parti- the 22Cr-6Ni-3Mo-0.12N weld, though
ten one into ferrite. Partitioning of Cr and
tioning of Cr, Ni and Mo, but the concen- the nominal nitrogen content was
M o was evident between the t w o
tration difference between the t w o increased.
phases, while that of Ni was masked with
the -segregation pattern, and the correla-
Fig. 4-SEM tion of the profile to the microstructure
micrograph of the was not well identified. Nitrogen was
22Cr-6Ni-3Mo-0.12N enriched in austenite, but being diluted
weld metal, showing with increased austenite; and the concen-
austenite at prior tration (0.2 wt-% on average) was lower
ferrite grain than that of the 22Cr-6Ni-3Mo-0.12N
boundary and fine, weld.
copious precipitates
within ferrite. Note
the precipitation-free Discussion
region in the vicinity
of austenite Solidification and Transformation of the
Weld Metals
The CMA images of composition pro-
files obtained were quite helpful in under-
standing the solidification and transfor-
mation of the duplex stainless steel weld
metals studied.
It is generally accepted that ferritic
solidification is not accompanied by

1 8 4 - s l M A Y 1989
either significant segregation of alloying ' I ' I
elements or clearly visible solidification Ni 54.6
_-; 698
/\ r^
O ubase
substructures in final weld microstructure l\ O-base
T-T --weld -weld Z
due to rapid diffusion and homogeniza- ^ sn 30
tion in ferrite (Ref. 28). However, in the * / \ T nominal UJ
c 5
oa_l
present study, the CMA images showed
the evidence of microsegregation of o ?n o 20
alloying elements resulting from cellular/
to * / \ * ui
dendritic solidification. In the 22Cr-6Ni-
U_ >
3Mo-0.12N weld metals, for example,
CD

< 10
/ f \ \ < 10
Ul
a
the measured segregation ratios (C m a x / / /1 \ \ x
Cmin) of Cr, Ni and M o were 1.05, 1.16
and 1.1 on average, respectively.
Although the extent was much lower
compared with that in austenitic stainless
0 LO // 20
#
22
, L ^
24
\v LO-
26
.O^L
4.0
-L-i
5.0 6.0 7.0 8.0
o
cx
<
UJ
V)
Cr content (wt%) Ni content (wt%)
steel weld metals, it is interesting to note
that the segregation certainly remained i . , . i
-I'Ir
Mo 72.8
along the solidification substructures and
*V O base O- base
that of Ni was the most pronounced in S
the ferritic solidified weld metal. A similar / \ --wold. weld_ a
30 30
| nominal
O
tendency was also ascertained in the / 1 * nominal _i
Ui
22Cr-10Ni-3Mo and 22Cr-10Ni-3Mo- >
0.12N weld metals. Fredriksson (Ref. 32) Ul
20 20 a
/
reported the partition coefficient of Ni at
0 A
the solid/liquid interface during ferritic
solidification as 0.84, which is relatively W , \/ "\ o.-Q' o
IX
closer to unity than that of M o (0.80) and
thereby indicates less segregation of Ni
during solidification (Ref. 33). Thus, the
reason for the more pronounced segre-
< 10

: / hf :
2.0
2.5
/ /
3.0
*v
3.5 4.0
) 0.1 0.2
0.2
_l L Q^
O Jn^T*-T-4-->
0.3 "0.4
J
0.4 0.5
< 10
\ \
<
UJ
tn
Ul
CK

gation of Ni rather than in M o should be o-t-o,

II i . n. i
associated with slower homogenization Mo content (wt%) N content (wt%)
S
of Ni during postsolidification cooling. Fig. 5 - Distribution of alloy content of: A-Cr; B Ni; C-Mo; and D nitrogen within the a.
However, because of the great scatters examined area of the 22Cr-6Ni-3Mo-0.12N base and weld metal O
_i
of the reported data on the diffusion of ui
>
Ni and M o and the lack of data on the
'i Ul
interaction between elements during
homogenization in ferrite, the reason still
remains uncertain. Nitrogen may be com-
pletely homogenized in ferrite just after
4fc a Q
X
o
CE
<
Ul
solidification due to the very rapid diffu- u>
sion rate. Ul
J*" - - - - , CE
Just after the solidification, duplex I-
Z
stainless steel attains a ferritic single phase fl ui
which then undergoes a solid-state trans- S
a.
formation to austenite (Refs. 3, 6, 7). O
According to the delato metric measure- _i
ui
ment, the transformation of the 22Cr- >
6Ni-3Mo-0.12N weld occurred approxi- Ul
20um
mately at the temperature range of a
1250 to 1150C (2282 to 2102F) on o
weld cooling. The diffusion rate of Cr, Ni CE
and M o would be fairly decreased at that Ni <
Ul
stage, resulting in insignificant partitioning m
of those elements between the phases.
" ' * k '
Note that the retained segregation pat- t-
Z
terns did not affect the austenite forma- ui
tion. Nitrogen, on the contrary, possesses
J**1
S
a diffusion rate rapid enough to acceler- a.
ate the transformation still at the temper- "
o
ature range, resulting in a remarkable >
increase of nitrogen in the austenite, as ui
"yf^ '' ;" . '. Q
shown in Fig. 3E. Therefore, it should be
concluded that nitrogen plays the most X
o
important role for the austenite forma- CE
tion in nitrogen-containing duplex stain- <
UJ
less steel weld metals. This was support- tn
ed by the fact that the nitrogen-contain- Ni' 9.0 IB lolO
n'.o ' 1
(yen
ui
CE
ing weld metal (22Cr-6Ni-3Mo-0.12N)
exhibited more increased austenite con- Fig. 6 A - Microstructure, and composition profile of B-Cr; CNi; and D Mo of the
22Cr-10Ni-3Mo weld metal

WELDING RESEARCH SUPPLEMENT 1185-s

 frr^r^

Fig. 7 A Microstructure,
and composition profile of
B - Cr; C - Ni; D - Mo; and
Enitrogen of the
22Cr-6Ni-3Mo-0.18N weld
metal ^ ^ S ^ C r ' 2 1 2 2 Z 3 - 4 2 5 i 6 (wg)

1% 2.5 iO 3.5 4.0 (wlZ)

Cr
r_^3- V*
'/9%?:s <M>" fc->rt

Ml^jf9bb\*'V

; . . : 20um
Cr' 21 22 23 ' 24 ' _ 26~(wtZ)
_L_

F/g. 8 A Microstructure,
and composition profile of
Ito
B - Cr; C - Ni; D-Mo and
E nitrogen of the
22Cr-10Ni-3Mo-0 12N weld
metal

ft) 2.5 4.0 (wtZ)

186-s|MAY 1989
tent as compared to the weld metal of
the same Ni equivalent without nitrogen
addition (22Cr-10Ni-3Mo). Because of
less contribution of Ni to austenite forma-
tion, nitrogen is required to be more
enriched in austenite for the phase stabil-
ity in the nitrogen-containing weld as
compared with the case of the base
metal, and this was certainly attained due
to the rapid diffusion of nitrogen. O n the
other hand, in the case of the no-
nitrogen-added weld, the partitioning of
Cr, Ni and M o is indispensable to form
and stabilize austenite. Thus, if it occurs,
the transformation to austenite is sup-
pressed, as shown in Fig. 6A, due to the
slower diffusion rates of those substitu-
tional elements.
Calculated Distribution of Nitrogen in the
22Cr-6Ni-3Mo-0.12N Weld
It is quite important to note that the
transformation process of the weld was
predominantly controlled by the diffusion
of nitrogen. When the transformation
occurs preferentially at prior ferrite grain
boundaries, nitrogen diffuses into and
stabilizes the intergranular austenite with
a rapid diffusion rate, which will lead to
the depletion of nitrogen in a ferrite
matrix. But, according to the nitrogen
profile of the 22Cr-6Ni-3Mo-0.l2N weld,
the depleted regions existed only in the
vicinity of austenite. Limited nitrogen-
depleted regions were presumably due
to a higher weld cooling rate and larger
prior ferrite grain size, which was sug-
gested by the simple calculation model
on the nitrogen distribution, taking into
account the movement of a/y interface
during transformation. The calculation
assumed 1) cylindrical prior ferrite grain,
2) transformation from the grain bound-
ary toward the center with a concentric,
planar interface, and 3) the completely
diffusion-controlled process of nitrogen.
The third assumption means that the
system considered was sufficiently
undercooled to make the ferrite thermo-
dynamically unstable, and that the diffu-
sion of nitrogen into austenite was the
only, and sufficient, requirement for the
austenite growth. The governing equa-
tions and the initial and boundary condi-
tions are given in the appendix. The
moving-grid method of Murray and Lan-
dis (Ref. 34) was applied for the numerical
solution by the finite difference method
(FDM). Regarding the temperature-
dependent diffusion coefficient of nitro-
gen, data in pure a and y iron (Ref. 35)
were used for simplicity. A transforma-
tion temperature range of 1250 to
1150C, a grain size (diameter of cylin-
der) of 200 /im, and a weld cooling rate
of 200C/s (360F/s) were employed to
fit the conditions to actual ones. The
result obtained is depicted in Fig. 9. As the
interface moved to the inside of the
0.5
Transformation : 1523K- 1423K
Cooling Rate : 200K/sec
9
H
2
0.2
Distance ('<m)
ferrite grain, the nitrogen-depleted region
was found to expand in front of the
interface into the ferrite. However, due
to the large grain size, the very short time
for the transformation, and the de-
creased diffusion rate with lowered tem-
perature, the central region of the grain
was still enriched in nitrogen. Although
the model contained some assumptions,
the result was consistent with the actual
profile of nitrogen. The nitrogen-de-
pleted region seen in Fig. 3E was the
result of the migration of nitrogen during
the transformation into the adjacent aus-
tenite, which behaved as a sink for nitro-
gen. Enriched nitrogen at the central
region of the ferrite grain would result in
nitride precipitation below the transfor-
mation temperature range. From the cal-
culations with different conditions of
grain size and cooling rate, it was indi-
cated that a decrease in grain size and/or
cooling rate was effective to decrease
the nitrogen content at the central region
of the ferrite grain, i.e., to reduce the
nitride precipitation within ferrite.
Effect of Increased Ni and Nitrogen on
Composition Profiles
In the 22Cr-6Ni-3Mo-0.18N weld met-
al, nitrogen was highly enriched in austen-
ite, and thus, the postsolidification trans-
formation of ferrite to austenite was
supposed to be strongly affected by the
diffusion of nitrogen, as in the case of the
22Cr-6Ni-3Mo-0.12N weld metal. But the
composition profiles revealed the parti-
down to 0.18 wt-%. Since an increase in
tioning of Cr, Ni and Mo between ferrite
and austenite in this weld. Owing to
increased nitrogen, intergranular austen-
ite nucleated and developed with smaller
spacings by the Widmanstatten mecha-
nism, which facilitated the partitioning of
the substitutional elements, despite the
WELDING RESEARCH SUPPLEMENT 1187-s
Fig. 9-
Redistribution of
nitrogen during
ferrite to austenite
transformation in the
high-N duplex
stainless steel weld
metal, obtained by
numerical calculation
slower diffusion rate. Moreover, based
on the delato metric measurement,
increased nitrogen to 0.18 wt-% led to
raising the transformation temperature
range by approximately 80C (144F). A
higher transformation temperature also
gave rise to the partitioning of substitu-
tional elements by increasing the diffusion
rate, though the extent was not so large
due to the rapid weld cooling.Thermody-
namically, increased nitrogen was stated
to suppress the partitioning of Cr, Ni and
M o between the phases in duplex stain-
less steels (Ref. 36). It is interesting to note
that the result obtained in the weld met-
als was in contrast with the thermody-
namical prediction. Kinetic factors such as
diffusion and austenite growth are more
influential to the partitioning of the ele-
ments in the as-solidified weld metals.
On the other hand, in the 22Cr-l0Ni-
3Mo-0.12N weld metal, the enriched lev-
el of nitrogen in the austenite was found
to be relatively reduced. The average
nitrogen concentration of 0.18 wt-% in
the austenite was certainly higher than
the nominal concentration of 0.12 wt-%,
but not so significant as compared with
that of 0.3 wt-% measured in the austen-
ite of other nitrogen-containing weld
metals. Because of increased Ni to 10
wt-% in the matrix, the formation and the
stability of the austenite on weld cooling
should be affected not only by nitrogen,
but by Ni. Therefore, with the aid of Ni,
nitrogen was not required to be enriched
up to a level of 0.3 wt-% for the austenite
stability, and was consequently diluted
Ni content raised the transformation tem-
perature in the same manner as nitrogen,
the partitioning of Cr and M o could
readily occur. However, the partitioning
of Ni was indefinitely masked with the
segregation pattern, because an increase
 in the content accompanied more pro-
r+3.3Mo+13N nounced segregation. Note that the aus-
tenite formation and growth was not
justly associated with the segregation of
2 Ni.
Q.

o Effect of Composition Profiles on Weld

_J Pitting Corrosion Behavior in Chloride
ui Solution
>
X It is generally accepted that Cr and M o
o are the major elements that improve the
(X pitting corrosion resistance of stainless
<
ui steels in a chloride environment. As for
tn austenitic stainless steel, the beneficial
ui
CE effect of nitrogen is also documented
H-" (Refs. 37, 38). The pitting corrosion resis-
Z tance of solution-annealed stainless steels
ui
5 has been well-correlated with the nomi-
OL nal content of those elements by using an
o equivalent, i.e., so-called pitting index,
-1 such as Cr+3.3Mo+13N (Ref. 39). In
ui
> Cr+3. 3Mo+13N austenitic stainless steel weld metals, the
occurrence of pitting corrosion is associ-
- v ated with the minimum levels of those
o
- /

W r
St< '/'
V :. 7 elements at the dendrite cores, which

1
CE result from the microsegregation during
<
Ul **^ solidification (Refs. 24, 25). Therefore, the
tn ^ compositional effect on the pitting corro-
ui E
sion in duplex stainless steels and their
IE
I-
Z
/ "
1
^^l weld metals, which possess composition
variation due to segregation and parti-
ui tion, could be understood by considering
5 !" 4 i? * the microdistribution of the pitting index
a. .A5 .<** ,5f
* value (Cr+3.3Mo+13N) throughout the
o
r.>. * fe tllhi;
microstructure of interest.

T*
M*

f-M
ixll t j * " Figures 10A and B give the profile of
> the pitting index value in the microstruc-
ui
Ci A4 *?. > / *.
ture of the 22Cr-6Ni-3Mo-0.12N base
X and weld metal, respectively. These
o 21
20um
r w ? *WI3N z> 34 3fi
\w\ n
38 40
images were graphically synthesized on
CX the basis of the composition profiles of
< Fig. 10 Profile of the pitting index value (Cr+3.3Mo+ 13N) in Abase metal and Bweld
Ul Cr, M o and nitrogen. In the base metal,
tn metal of the 22Cr-6Ni-3Mo-0.12N duplex stainless steel the ferrite exhibits a higher index value
ui
cx than the austenite because of enriched
i-
Z Cr and M o by partitioning. Although the
ui austenite is substantially enriched in nitro-
E
a. gen, the depletion of Cr and M o leads to
O
-i
ui
>
X
o
cx
<
Ul
tn
ui
a:
tV-

z
UJ

s
OL
o
-J
UJ
;*
Ul
a
X
a
K
<
UJ
tn
Ul
ce Fig. 11 A Pitting corrosion and Bprofile of the pitting index value (Cr+3.3Mo+13N) in the 22Cr-10Ni-3Mo weld metal

188-s I M A Y 1989
a lower index value, which indicates that 10
the austenite is more susceptible to pit- F e - 2 2 C r - N i - 3 M o - N weld
ting corrosion. Actually, the austenite was
selectively attacked in a chloride solution, O 0.10-0.12 N z
as shown in Fig. 1B. On the contrary, the 0.18-0.20N
UJ
austenite exhibited a higher pitting index

Q.
value than the ferrite in the weld metal, 0.27-0.29 N o
I
owing to less partitioned Cr and M o UJ
between the phases and to significantly 6%FeCI 3 + ^20 N NaCI solution >
UJ
enriched nitrogen in the austenite. Result- ra 50C, 24 hr immersion Q
CC -v.
ing from Cr nitride precipitation, the cen- X
c
tral regions of the ferrite exhibit a little o o
higher pitting index value compared with co
o
cx
the other ferrite regions, but strictly <
o
speaking, those regions would be more O Ul
tn
susceptible to pitting corrosion than the o ui
other ferrite regions because of the pre- c cx
cipitates. Thus, in the weld metal, pitting z
2 UJ
corrosion would occur preferentially in CL

the ferrite associated with either the pre- \ y S

~.Q.o' Fig. 12-Effect of
cipitation or low pitting index value, as ferrite and nitrogen o
shown in Fig. 1A, while, being composi- content on pitting -I
tionally noble, the austenite is more resis- Ul
20 40 60 80 corrosion resistance >
tant to pitting and behaves as an impedi- of duplex stainless ui
F e r r i t e Content (%) Q
ent for the pit propagation. The change steel weld metals -\
of corrosion mode between the base X
and weld metal can be explained compo-
o
cx
sitionally by the change of the profile of l/WWP* Cr+3.3Mo+13N <
UJ
the pitting index value arising from differ- tn
UJ
ent partitioning behaviors of Cr, M o and cx
, * i
nitrogen between the base and weld >' 13P^ y-

metal. Note that such change of corro- z

Ul
sion mode is characteristic of nitrogen-
bearing duplex stainless steels, and this is
wS" 5
Q.
ascertained by the pitting corrosion *%,
behavior of the 22Cr-lONi-3Mo weld. As o
shown in Fig. 11, pitting corrosion
occurred preferentially in the austenite, X
even in the weld, when the weld does o
cx
not contain a substantial amount of nitro- <
gen. The preferable effect of nitrogen on UJ

the pitting corrosion resistance of austen- tn

ite should be noted again.

Figure 12 shows the effect of ferrite ^ \ ^ :

<C5 1 20um
content on the chloride pitting corrosion
V\ V *?%&***&& Cr+3.3M*-13N 34 36 38 40
resistance of duplex stainless steel weld a.
Fig. 13-Profile of the pitting index value (Cr+3.3Mo+13N) in the 22Cr-6Ni-3Mo-0.18N weld O
metals having the composition of 22 _i
metal ui
wt-% Cr, 3 wt-% M o and various >
amounts of Ni and nitrogen, which was
previously reported by the authors (Ref. .**?*&* Cr+3.3Mo+13N X
5). Different weld ferrite contents were o
attained by varying the weld Ni content cx
<
for each nitrogen level. As for the weld Ul
metals with 0.12 wt-% nitrogen, the resis- tn
ui
tance was the most improved around a cx
ferrite content of 50%, and deteriorated
in both, more to the ferritic side with z
lower Ni, and more to the austenitic side ui

with higher Ni. Increased nitrogen, how- a.
ever, improved the resistance of more O
_i
austenitic weld metals. The decrease in ui
pitting corrosion resistance on the ferrite-
>
Ul
rich side is due to the enlarged precipita-
tion area with increased ferrite. In this J5>V >/ j ? h f I < )j a
x
case, the beneficial effect of an increase o
CK
in the austenite content on the weld <
pitting corrosion resistance is attributed Ul
(A
to reducing the detrimental precipitation Crf3.2K*-13N 32 34 36 38 40 Ul
CX
and increasing the corrosion-resistant
area with highly soluble nitrogen. How- Fig. 14-Profile of the pitting index value (Cr+3.3Mo+13N) in the 22Cr-10Ni-3Mo-0.12N weld
metal

WELDING RESEARCH SUPPLEMENT 1189-s

ever, the d e g r a d a t i o n o f t h e pitting c o r -
rosion resistance of austenite-enriched
w e l d m e t a l a n d the p r e f e r a b l e e f f e c t o f
increased n i t r o g e n in that case cannot be
explained in terms o f the p r e c i p i t a t i o n ,
because increased austenite significantly
suppresses t h e precipitation o f carbide
a n d nitride.
Figures 13 a n d 14 give t h e profile of
t h e pitting index value w i t h i n t h e 22Cr-
6Ni-3Mo-0.18N and 22Cr-10Ni-3Mo-
0 . 1 2 N w e l d microstructures, respectively.
T h e austenite o f b o t h w e l d s exhibits a
higher pitting index value t h a n the ferrite,
b u t the austenite of t h e 2 2 C r - 6 N i - 3 M o -
0.18N w e l d s h o w s m o r e increased value
c o m p a r e d w i t h that of t h e 2 2 C r - 1 0 N i -
3 M o - 0 . 1 2 N w e l d due t o a m o r e enriched
nitrogen content. In o t h e r words,
increased austenite w i t h higher Ni c o n -
tent results in a l o w e r pitting index value
w i t h diluted n i t r o g e n in the 2 2 C r - 1 0 N i -
3 M o - 0 . 1 2 N w e l d . Since the n i t r o g e n -
e n r i c h e d austenite w i t h a higher pitting
index value can o f f e r i m p r o v e d resis-
tance a n d b e h a v e as an i m p e d i m e n t t o
pitting c o r r o s i o n , the austenite of the
22Cr-10Ni-3Mo-0.12N w e l d offers a
d e g r a d e d resistance t o pit p r o p a g a t i o n
o n c e pitting occurs. Pitting c o r r o s i o n
resistance, s h o w n in Fig. 12, substantially
includes the e f f e c t of pit p r o p a g a t i o n ,
a n d thus, t h e d e g r a d a t i o n o f pitting cor-
rosion resistance in w e l d s w i t h higher Ni
can be compositionally explained b y the
dilution of n i t r o g e n in increased austenite.
It should b e c o n c l u d e d that the pitting
c o r r o s i o n resistance of austenite-en-
riched duplex w e l d metals is mainly d o m -
inated b y the n i t r o g e n c o n t e n t in austen-
ite.
Conclusions
C o m p o s i t i o n profiles of Cr, N i , M o and
n i t r o g e n w e r e investigated in d u p l e x
stainless steel w e l d metals having the
c o m p o s i t i o n o f 22 w t - % Cr, 3 w t - % M o
and different a m o u n t s of Ni a n d n i t r o g e n .
Based o n the results, the solidification a n d
the phase t r a n s f o r m a t i o n o n w e l d i n g and
t h e correlation w i t h the pitting c o r r o s i o n
b e h a v i o r of the w e l d s w e r e clarified. T h e
conclusions o b t a i n e d are as f o l l o w s :
1) T h e ferritic w e l d solidification w a s
f o u n d t o cause the m i c r o s e g r e g a t i o n of
Ni and M o , w i t h that of Ni being m o r e
p r o n o u n c e d than that of M o , although
t h e e x t e n t w a s n o t so great as c o m p a r e d
w i t h t h e case of austenitic solidification.
2) Partitioning of Cr, Ni and M o
b e t w e e n the ferrite a n d the austenite is
n o t significant in the n i t r o g e n - b e a r i n g
w e l d s , but an increase in an austenitizer
such as Ni a n d n i t r o g e n p r o m p t s it b y
raising t h e t e m p e r a t u r e of t h e transfor-
m a t i o n t o austenite.
3) N i t r o g e n is f o u n d t o d o m i n a t e the
f o r m a t i o n of w e l d austenite b y the rapid
diffusion d u r i n g postsolidification c o o l i n g ,
190-s | MAY 1989
being m o r e e n r i c h e d in the austenite than
that o f base metals.
4) Preferential o c c u r r e n c e o f pitting
w i t h i n the ferrite in t h e nitrogen-bearing
w e l d s is d u e t o the compositionally inferi-
o r c o r r o s i o n resistance o f t h e ferrite a n d
t h e d e t r i m e n t a l effect of precipitates
w i t h i n the ferrite.
5) A n increase of n i t r o g e n i m p r o v e s
t h e w e l d pitting c o r r o s i o n p r o p e r t y b y
ameliorating t h e pitting resistance of t h e
austenite of t h e w e l d , w h i l e an increase
of austenite w i t h Ni instead of n i t r o g e n
degrades t h e w e l d p i t t i n g c o r r o s i o n
p r o p e r t y b y diluting n i t r o g e n c o n t e n t in
the austenite.
Acknowledgments
The authors wish t o thank M r . Y a m a -
nishi f o r his skillful o p e r a t i o n of the C M A ,
a n d M r . H a m a d a f o r technical discussions
o n the C M A data analysis.
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225. (Cy*-Ca*) =0^
dt dr r = r* -E 0
30. Taguchi, I., and Hamada, H. 1985.
Development of new computer-aided micro- Appendix a ac,
-DN - (5)
analyzer and its application to iron and steel dr r = r* - 0
analysis. Analytical Sciences 1: pp. 119-121. It was assumed that a prior ferrite grain
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1985. Development and application of com- of R, and the transformation occurred tions of nitrogen in ferrite and austenite,
puter-aided micro analyzer (CMA) to analysis radially from the grain boundary toward respectively, at the interface, and com-
of iron and steel. Nippon Steel Technical the inside with a concentric, smooth bined by using the partition ratio, KM, as
Report No. 26:59-68. interface. follows:
32. Fredriksson, H. 1979. Transition from
When the a/y interface is located at D~* KM C (6)
peritectic to eutectic reaction in iron-base
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Metals Society pp. 131-138.
given by the following equations, respec- partition ratio of nitrogen (KN) between
33. Lippold, ). C, and Savage, W. F. 1979.
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inents: Part I A proposed mechanism. Weld- in ferrite 10, with reference to the work by Masu-
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= D N ( 1+ ),0<r<r* (1)
Numerical and machine solutions of transient 3t dr rdr
heat-conduction problems involving melting or = 0 (7)
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Japan Institute of Metals, pp. 25-26. 3C d2C dC I = 0 (8)
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denmo, M. 1986. Microstructure and proper- at dr rdr
ties of nitrogen alloyed duplex stainless steel The moving-grid method of Murray and
after welding treatment. Conf. Proc. Duplex Landis (Ref. 34) used in the present calcu-
where C is the concentration of nitrogen,
Stainless Steel '86, Hague, Netherlands Institute lation required the existence of both
of Welding, pp. 257-267, Paper 30. and D N and D N T are the diffusion coeffi-
phases, apriori. Thereby, the austenite
37. Streicher, M. A. 1956. Pitting corrosion cients of nitrogen in ferrite and austenite,
with thickness of 0.1 nm was assumed to
of 18Cr-8Ni stainless steels. /. Electrochem. respectively. For the sake of simplicity,
be at the grain boundary (i.e., r* = 199.9
Soc. Vol. 103, pp. 375-390. the data in pure a iron and y iron were
nm), and to impart the slight concentra-
38. Dundas, H. )., and Bond, A. P. 1975. employed, i.e.:
tion difference of nitrogen (0.001 wt-%)
Effect of delta ferrite and nitrogen content on
the resistance of austenitic stainless steels to D N a = 1.13X10"6 exp(-41800 at the a/y interface. The initial conditions
pitting corrosion. Corrosion Forum 75. Ontar- (1 - 14.03/T)/T) (m 2 /s) (3) are:
io, Canada, NACE. Paper No. 159. C = 0.12 0 < r < r * , r* (9)
39. Suutala, N and Kurkela, M. 1985. D N T = 3.6X10" 5 exp(-79000/T)
wt-%, < r < R, t = 0
Localized corrosion resistance of high alloy (m 2 /s) (4)
austenitic stainless steels and welds. Proc. C * = 0.119 r = r*, (10)
Conf. Stainless Steels '84, The Institute of where T is the absolute temperature wt-%, t= 0
Metals, pp. 240-247. (K). C 7 * = 0.121 r = r*, (11)
40. Masumoto, T., and Imai, Y. 1969. Struc- At the advancing a/y interface, the wt-%, t = 0

WRC Bulletin 332

April 1988
This Bulletin contains t w o reports t h a t characterize the mechanical properties of t w o different
structural shapes of constructional steels used in the pressure vessel industry.

( 1 ) Characteristics of Heavyweight Wide-Flange Structural Shapes

By J. M. Barsom and B. G. Reisdorf

This r e p o r t presents information concerning the chemical, m i c r o s t r u c t u r a l and mechanical (including

fracture toughness) properties for heavyweight wide-flange structural shapes of A36, A572 Grade 50 and
A588 Grade A steels.

( 2 ) Data Survey on Mechanical Property Characterization of A588 Steel Plates and Weldments
By A. W. Pense

This survey report summarizes, for the most part, unpublished data on the strength toughness and
weldability of A588 Grade A and Grade B steels as influenced by heat t r e a t m e n t and processing.
Publication of this Bulletin was sponsored by the Subcommittee on Thermal and Mechanical Effects
on Materials of the Pressure Vessel Research C o m m i t t e e of the Welding Research Council. The price of
WRC Bulletin 3 3 2 is $20.00 per copy, plus $5.00 for postage and handling. Orders should be sent with
payment to the Welding Research Council, Suite 1 3 0 1 , 345 E. 4 7 t h St., New York, NY 10017.

WELDING RESEARCH SUPPLEMENT 1191-s