WELDING RESEARCH
SUPPLEMENT TO THE WELDING JOURNAL, MAY 1996
Sponsored by the American Welding Society and the Welding Research Council
Corrosion Behavior of Welded Stainless Steel
Corrosion resistance of stainless steel weld metal depends on an
understanding of the nature of the protective passive film
that gives the steel its "stainless" characteristic
ABSTRACT. The corrosion resistance of
stainless steels depends on a protective,
passive film being fornled at the steel sur-
face on exposure to the service environ-
ment. The use of fusion welding for fab-
rication leads to local compositional
variations within the material, which
may significantly alter the stability of the
passive layer and hence the corrosion be-
havior. The paper reviews published
work and practical experience on such
effects of a weld thermal cycle.
Compositional heterogeneity and lo-
cally reduced passive film stability can
stem from three main causes. Attention is
given first to the consequences of alloy
element segregation during weld metal
solidification and to the formation of a fu-
sion boundary unmixed zone. Element
partitioning as a result of solid-state
phase change is then considered, with
particular reference to duplex
ferritic/austenitic materials. Finally, the
effects are described of precipitation,
both of carbide (or carbonitride) particles
and of intermetallic phases, with resul-
tant development of alloy depleted re-
gions. Throughout, recognition is made
of the different grades of stainless steel
employed by industry in terms of overall
composition and microstructure.
1 G. GOOCH is with T~/Vh Abin~4ton Hall,
Abington, Cambrid,~e, U.K. Paper presented
as the Comfort A. Adams Lecture at the AVVS
76th Annual Meetin,G April 3-7, 1995, Cleve-
land, Ohio.
BY T. G. G O O C H
Study remains necessary to ensure
that corrosion resistance of welded joints
is adequate for service in a range of
media. However, controlling factors
have in large part been defined for both
established and recently developed
steels, and quantitative recommenda-
tions on preferred welding procedures
can generally be given.
Introduction
There can be no doubt that the devel-
opment of stainless steel represents one
of the major technical achievements of
the 20th century. The demonstration and
understanding that the addition of
chromium to steels endowed thenl with
the property of passivity led to the devel-
opment of materials with remarkable
KEY WORDS
Stainless Steel
Austenitic
Martensitic
Ferritic
Duplex
Welding
Corrosion
WELDING RESEARCH SUPPLEMENT I 135-s
corrosion resistance, coupled with ex-
cellent mechanical properties (Ref. 1).
Hence, "stainless steels" have reached a
dominant position for a very wide range
of applications. They give resistance to
aggressive media, provide an inert sur-
face such that a product stream is not
contaminated, and can offer high
strength and toughness for service at ex-
tremes of temperature. The alloys are em-
ployed in chemical all([ process plants,
for power generation and other energy
industry equipment, for the food industry,
and for medical duties.
The fact that passivity can be induced
in an iron-based system is extrenlely for-
tunate, since, by appropriate adjustment
of elements other than chronlium, fer-
ritic, martensitic or austenitic structures
can be produced singly or in any combi-
nation. The result is that alloys can be tai-
lored to produce specific properties, de-
pending on practical requirements and
costs of alternative materials.
Welding, especially by a fusion
process, plays an essential role in fabrica-
tion of stainless steel products because of
the economy and flexibility afforded to
design and manufacturing. A continuous
item is produced, facilitating direct trans-
mission of stresses through the stru(ture,
and avoiding through-wall perforations
and potential leakage resultant on other
methods of joining. However, welding
necessarily involves a thermal cycle with
localized heating and cooling, and ex-
pansion and contraction. Regardless of
 the grade of stainless This situation can stem from segregation
! 1 I I steel, and whether it be of alloy elements during solidification,
wrought or cast, the base from element partitioning during phase
0.50 m

material will be supplied changes, or from precipitation of second

30~ ~ 0 MO
following careful pro- phase particles. These aspects are con-
'ZII cessing to achieve opti- sidered below.
lie
mum properties. The ad-
ditional welding cycle Passivity of Stainless Steels
~.-0.25 will differ appreciably
I I I I from that imposed dur- Passive Film Formation
10 10z 10 ~ 10 ~ 105 ing material manufac-
Currenf densify, p.A/cm z ture, and can markedly The nature of the passive film formed
change the properties on stainless steels has been researched
I

around the joint. Specif- for many years (Refs. 1,4, 5). Although
Fig. I - - Potentiostatic polarization curves for 12% Cr (410), 17% commonly, and conveniently, regarded
E I ically, this is the case
Cr (430) and 18% Cr (304) stainless steels in 1N H2SO 4 + 1N NaCI
at room temperature (Ref. 2). with corrosion resis- as an oxide layer, it is in fact considerably
WI
] tance, and the present more complex. Simple application of a
WI paper is intended to re- Pourbaix diagram, for example, would
El not predict the observed fact of passiva-
i
view the effects of weld-
-0.1 ~ Z Effect of chromium: Cr.8%Ni steel- I ing as a method of fabri- tion in acid media on the basis of a ther-
I cation on the service modynamically stable oxide (or hydrox-
behavior of stainless ide) layer. The constitution of the passive
LI film has not been precisely defined, but
01 steels in aggressive
-Ok the development of x-ray photoelectron
media.
It is generally consid- spectroscopy (XPS) has enabled study to
I
Effect of nickeh 18%Cr-Ni steel ered that the develop- be carried out on stainless steels surfaces
al -~ - o . 2 1 ~ ment of passivity in exposed to various environmental condi-
iron-chromium alloys tions. The approach is in principle more
iilUiii!iI occurs virtually as a step direct than interpretation of electro-
~iEi!i!ill -OI,
change as chromium chemical data or examination of film
level is increased: stripped by aggressive etchants, although
-0.I Effect of molybdenum: 18%Cr-lO%Ni steel I
below some 10% Cr, the the possibility of some change between
material remains active removal from the test environment and
-03 o Mo
in normal aqueous XPS analysis must be recognized.
-04 ' , media, while above Accepting this limitation, Asami, e t a l .
0 1 2 3 (Ref. 4), working with a range of Fe-Cr al-
12% Cr, a passive film
Currenf densih/,mA/cm z
develops and corrosion loys, found that the surface film formed
: I rate is greatly decreased after exposure to 1M H2SO 4 in the pas-
Fig. 2 - - Effects o f varying Cr, N i and M e on active range o f stain- (Ref. 1). While this is es- sive range became chromium-rich im-
11 less steels in 10% H2SO 4 at 2 0 ° C (Ref. 3).
| sentially true, the influ- mediately after the substrate chromium
:) ence of the environment content exceeded 12%, the minimum
must be clearly recog- level commonly associated with passiv-
nized in terms of redox ity and hence "stainless" steels-- Fig. 3.
potential and content of Despite the high chromium content in
1.0 specific anions such as
, , ' r=j...~~-~/~ the film, the composition of the metal
chlorides (Ref. 2). Under
surface corresponded to that of the bulk
aggressive conditions, a
0.8 alloy, indicating that the film resulted
chromium level well in
from preferential dissolution of iron.
|
excess of 12% will be
w I Chromium enrichment in the surface
needed to maintain a
film has been shown (Ref. 5) for a range
~s 0,6 stable passive film - - of potential, and in both chloride-free
Fig. 1. There are, there- and chloride-containing media, but only
:):?: ,/t0: I fore, varying degrees of
J;:l under passive conditions. Below the pas-
: U,i; I ~ o,4 "stainlessness" (Fig. 2) sive/active transition, the surface film an-
(Ref. 3), and a major ef- alyzed reflected the Cr and Fe contents of
fect of welding is that the the base metal. Hashimoto, e t a l . (Ref. 5),
associated metallurgical concluded that the passive film was es-
02
÷lOOmVsce • • changes may lead to sentially a hydrated chromium oxy-hy-
some parts of the mater- droxide (CrOx(OH)3_2x-nH20), with a
ial having lower levels of small amount of hexavalent molybde-
O, I I I I
I 0 20 40 50 80 100 chromium (or other ele- num if the substrate steel contained this
Steel Cr content, af % ments which enhance element. Molybdenum was found to be
corrosion resistance, pri- beneficial primarily by suppressing ac-
marily molybdenum and tive sites via formation of an oxy-hydrox-
Fig. 3 - - Relationship between Cr content and Fe-Cr base metal. A
- - Cr cation fraction in surface film; B - - atomic fraction in un- nitrogen) than elsewhere ide or molybdate, and this was further in-
derlying material: I M H2SO 4. on the metal surface. dicated by Halada, et al. (Ref. 6).

136-s I MAY 1996

 200 1[ I I , ,
b.t 2" i~.;l'z " , ,~,,
I
r
?°

0 . ,'o '

A lime sec

Fig. 4 - - Current transients on austenitic stainless steel in chloride media (Ref. 11). A - - Metastable pitting; B - - stable pitting.

The beneficial effect of nitrogen has
also been explored (Refs. 6, 7). Available
evidence has indicated that surface en-
richment of nitrogen takes place at breaks
in the passive film, thereby blocking ac-
tive dissolution. This view is consistent
with the observed synergistic effect be-
tween molybdenum and nitrogen (Ref. 6).
It has also been suggested that nitrogen
encourages iron dissolution, thus en-
hancing repassivation by the resultant
chromium enrichment (Ref. 8), and the
two mechanisms may be complementary.
ble hexavalent chromium ions. Neverthe-
less, the passive region is sufficiently ex-
tensive for the materials to be employed in
a wide variety of service media.
However, stainless steels are sensitive
to local passive film breakdown and at-
tack, most notably by chloride ions (Ref.
1). This limitation is well recognized, and
has led to significant developments in
material composition to achieve resis-
tance to chloride pitting (and crevice at-
tack), exemplified by the increased Mo
and N levels in high-alloy "super-
austenitic" and "superduplex" grades
marketed over the last decade or so. Pit-
ting occurs at potentials corresponding to
general passivity, becoming more pro-
nounced at higher chloride levels and
applied potential. The formation of a pit
is preceded by electrochemical noise,
and, from measurement of small corro-
sion current transients (typically less than
l n A to over 101aA), the concept has
emerged of the passive layer being fre-
quently penetrated by chlorides (or other
sufficiently mobile anions), but with re-

Passive Film Breakdown

Stainless steels display passivity only

i|O l l I I w ! I
over a certain range of potential (Ref. 1).
At low potentials, the passive film cannot
form and the material corrodes in the ac-

[.
tive state (Fig. 1), whereas under high po-
ou ,
tential conditions (in chloride-free media),
the passive film is oxidized to form solu-

Fig. 5 - - Segregation and pitting in fully austenitic weld metal Fig. 6 - - Critical pitting temperature data from ferric chloride tests on stainless
(125X). steel base metal and weld metals (Ref. 17).

WELDING RESEARCH SUPPLEMENT I 137-s

 pair rapidly taking place after dissolution weak points. Mattin associated rupture
Table 1 - - EDX Analyses (wt-%) on GTA events with inclusions in the steel surface
of a small volume of metal (Refs. 9-11).
Root Passes in $31254 Pipe Butt Joint Welds
As chloride activity or applied potential (Ref. 9), but in principle any local alloy
Dendrite inter- is increased, the volume of metal dis- element depletion would be expected to
Filler Element Bulk Core dendritic solved is sufficient that local hydrolysis constitute a weak point and thus a pit ini-
and acidification prevent repassivation, tiation site.
Autogenous Mo 6.1 4.2 6.9 and a stable pit is formed which will then
Cr 20.2 19.3 20.5
Ni 17.6 17.6 19.2 propagate - - Fig. 4. The critical volume Solidification
ERNiCrMo-3 Mo 7.6 5.8 10.5 of metal constituting the pit nucleus de-
Cr 21.4 20.7 20.9 pends on the environmental conditions, Alloy Element Segregation
Ni 47.2 47.7 43.6 but has been estimated as a hemisphere
ERNiCrMo-4 Mo 11.3 9.8 14.4 from about 10 nm to 11Jm diameter (Ref. A weld metal effectively constitutes a
Cr 17.3 17.2 18.1 chill casting and is subject to the normal
Ni 40.7 43.1 39.2 9). In this model, the initial passive film
rupture is considered to take place at segregation of alloy elements during so-
lidification of the molten weld pool (Fig.
5) (Refs. 12, 13) in the first instance, the
degree of segregation will depend upon
I I I
the equilibrium partition coefficient of
individual elements between the solid
and liquid states, and this can vary con-
siderably depending on the element and
the primary solidification phase.
Chromium and molybdenum are re-
jected from the solid to a greater extent

/
with primary austenite solidification than
in weld metals freezing to ferrite (Ref.
14), whilst the reverse is true for nickel.
Nitrogen displays a somewhat unusual
behavior in that, thermodynamically, it is

Fig. 7 - - Depen-
dence of stainless
steel weld metal
.!
passivation on in-
terclendritic Mo
segregation: 30%
H2SO4 with 0.1 ~.
g/L NH4CNS at
25°C (Ref. 15).
2.S "
¢3
1.0
more soluble in solid austenite than in
liquid steel, and thus tends to segregate
in the reverse sense to other elements
(Ref. 1 5).
Because of segregation, the corrosion
resistance of weld metal is inferior to that
of base metal of identical bulk composi-
I I ! tion (Refs. 15-17), In effect, the behavior
0
0.5 1.0 1.5 20 2.5 of the weld deposit is determined by the
minimum content of "passivating" ele-
Molybdenum segmc~hon ratio
ments at a point w i t h i n the solidified
weld metal, generally the dendrite cen-
ters since these are the first to solidify.
The consequences of segregation have
long been recognized, and consumable
I I I I I specifications for common grades of
.~lid i fication mode stainless steel are generally slightly over-
Pffmary [ Mixed Primary ousfenife alloyed primarily in Cr and Mo, so that
even depleted regions retain sufficient
~~ I levels of these elements for satisfactory
I corrosion resistance to be obtained.
Segregation is not commonly seen as
a practical problem with ferritic alloys.
The liquid/solid partition coefficients for
chromium and molybdenum approach
unity under solidification to ferrite, while
high-temperature diffusion in the bcc fer-
rite lattice is very rapid, so that some ho-
b-----o~ ~, 8 o-o"--o---o
mogenization takes place in the solid

Fig. 8 - - Relation-
1- ii state during the weld cooling cycle. Ni-
trogen might segregate strongly, but this
ship between ele- element is usually held at a very low level
ment segregation, in ferritic stainless steels. In contrast, seg-
partitioning and 0 l , I, ~',.~1 I I , ~ I regation becomes much more significant
bulk composition
and solidification
0,4 0.5 0.6 0.7 0.8 0,9 1.0 1.1 1.6 in high-alloy superaustenitic grades. The
mode (Ref. 15).
' w /P
cr~
# materials typically contain 20-25%Cr,
20-25%Ni, 6%Mo and 0.2%N, and seg-

1 3 8 - s l M A Y 1996
regation of molybdenum can be suffi-

'j"
ciently marked that some regions of the I I I I I I I
weld metal contain only about 4% (Ref.
15), leading to an appreciable loss in cor- 800 n

rosion resistance - - Table 1. This has

most frequently been highlighted with
reference to chloride pitting attack, and 600
indeed any reduction in passive film sta-
bility would be expected to have a pro-
nounced effect on pitting behavior; given
passive film breakdown at alloy-depleted 400
regions and stable pit initiation, local hy-
drolysis and acidification will render
subsequent pit growth autocatalytic - - 200 Fig. 9 - - Relation-
Fig. 5. Over the last decade, it has be- ship between weld
metal pitting resis-
come common practice to describe the
tance and modified
pitting resistance of stainless steels by an
0 I / I - I I J I I pitting index (MPI)
empirical compositional parameter (Ref. (Re£ 15). Potentio-
17), variously termed a "pitting index" or 0 20 4O 50 8O dynamic passive
"pitting resistance equivalent" (PRE), flint in 3% NaCI at
Cr+ 3,SMo- 14N÷ (1.TMo, 23N) 50°C.
such as (Ref. 18)
- -

PRE = %Cr + 3.3%Cr + 16%N (1)

A direct equivalence in pitting behav-

ior can be drawn between the minimum
alloy level in the weld metal solidifica- D IQ! i N # H # O ~
tion structure and a base metal of similar 60
"lean" bulk composition - - Fig. 6. At the
same time, the adverse influence of seg- .4r/3Nz
regation on passive film stability has L.j
been demonstrated also in other media, 0 40
notably sulphuric acid (Ref. 15) in which
Ar
general rather than pitting corrosion will
Fig. 10 - - Effect o f
occur Fig.7. 20 arc energy and
Various factors for nitrogen in Equa-
shielding gas on
tion 1 have been proposed. While Suu-
FeCI 3 pitting resis-
tala and Kurkela used 13 (Ref. 17), 16 is I I I tance o f GTA welds
most commonly employed (Ref. 18), al- 0.5 20 1.5 in $31254 steel
though a higher value of 30 has been rec- (Ref. 24).
Arc ene~jy, k J / ~
ommended for high-alloy superduplex
and superaustenitic steels (Refs. 18, 19).
Recognizing that the PRE concept is em-
pirical, Walker and Gooch showed that
the "optimum" compositional relation-
ship, in fact, depends on the environ- o,24 I i J I t .
mental conditions causing attack (Ref.
20).
o z2
Effect of Composition
0.20
The degree of segregation is influ-
enced by the total composition of the ma- 0"18
terial, and tends to be more pronounced
in iron-based than in nickel-based sys-
tems (Refs. 15, 21 ). As illustrated in Fig.
8, segregation is likely to be most marked
.•E 0.16

0.11,
in high-alloy austenitic steels containing
around 20-25%Ni, decreasing at higher
and lower Ni levels. Figure 9 shows the 0.12
correlation between weld metal pitting Fig. 11 - - Effect o f
resistance and a PRE parameter incorpo- 0.~ I I I I I nitrogen level in Ar
rating an empirical factor to recognize 2 4 6 8 10 shielding gas on
the overall composition (Ref. 15), de- 22% Cr duplex
Nitrogen in A r shield,%
rived from studies of stainless steel solid- weld metal nitrogen
content (Ref. 25).
ification. From Figs. 8 and 9, it appears

W E L D I N G RESEARCH SUPPLEMENT I 139-s

 that segregation and the effect on passive
film stability is greatest in weld metals of
composition such that the primary solid-
ification phase is austenite, but in which
! the Cr and Mo rejection is sufficient for
the interdendritic regions to approach
final solidification to ferrite.
Experience with plant made from

c.I 316L-type steels and producing urea or

some organic acids, such as pteraph-
thalic acid, has indicated that preferen-
tial corrosion can occur in weld metals
z containing a small amount of ferrite
(Refs. 22, 23). Consequently, it is normal
Fig. 12 - - Variation o f CO to specify low or zero ferrite contents,
c o m p o s i t i o n across an with attendant sensitivity to solidification
interdendritic volume
cracking and microfissuring. Almost cer-
element allowing com-
plete mixing in the tainly, these media result in a metal/envi-
liquid (Re£ 13). Distance - - - ~ . ronment potential close to the active/pas-
sive transition, depending on the oxygen
level of the process stream. Passive film

I I I I I I I I EE

f=O.18 sec ~

f~
•~ 20 &
m

Ni ~3 CO

A
b~ 10

0
0
I I
0.2
I I
0.4
i i
0.6
i

NOrl~lised d~-h~nce,r/R
i
08
,1 tO
kco
D m ~ n ~ ~

Fig. 13 - - Calculated interdendritic microsegregation patterns for GTA welds in stainless steel (Ref. 28). A 21% Cr, 14% Ni, 65% Fe alloy, solid-
ifying to primary austenite; B - - 23% Cr, 12% Ni, 65% Fe alloy, solidifying to primary ferrite.

,/
1.0 , , /I-~......--~ , 80 I I I

0.9 Base
70 O - -
~Itzl
0.8

0.7

O6

0.5
cont,
~Z
6O

50

40
/" • QO

04 --.~ Aziz ,/.

m ~ Wood
I , | .........
0310.~ 10"1 I 10 102 I0 100 I000 10000
Dimensionless velocify Laser veloc#y,mm /min

Fig. 14 - - Calculated variation of partition coefficient with velocity Fig. 15 - - Effect of laser travel speed on ferric chloride critical pitting
using various models (Rei~ 13). temperature of surface melted UNS $31254 steel (Ref. 31).

140-s MAY1996
 stability is therefore marginal, and it is
probable that the observed corrosion, I I I

which tends to be initiated at ferrite-

Fig. 16 - - Relationship be-
austenite interfaces, is due not to the I
presence of ferrite per se, but rather to the
associated segregation and alloy deple-
/ tween FeCI3 pitting
resistance o f welded joints
in UNS $31254 steel and
I
tion. Interfacial effects, such as residual composition (Ref. 32).
50 !I
element segregation, may also be con- A - - Weld metal bulk com-
I
tributory. Comparable restriction on
weld metal ferrite content has seldom " position: O@ = GTA weld
metal; O~D = SMA weld

been found necessary in other environ- q !

metal. H o l l o w symbols =
15% M o filler metal; solid
ments, and is apparently a consequence
of the specific cathodic corrosion reac- 50 ~lIlr~ /60 ........................................................
45
symbols = autogenous or
9% M o filler metal;
tions in the organic media concerned. It numbers = % dilution;
seems that improved behavior could B - - minimum alloying
level in solidification struc-
equally well be obtained with weld met-
4# i I I
ture: A = base metal; 17 =
als of composition giving either fully autogenous weld metal; Ci =
austenitic or primary ferritic solidifica- 30 40 50 60
Pl = % E r ÷ 93°/ot.fo+16°/oN GTA unmixed zone; ll =
tion. In the latter regard, satisfactory ser- SMA unmixed zone.
vice has been reported to TWl of materi-
als such as 309LMo or 22% Cr duplex
steel which solidify initially to ferrite, al-
though these are also somewhat more
highly alloyed than the 316L base metals
generally used.
A further point regarding weld metal
corrosion behavior is that the possibility
must be recognized of compositional
changes during welding. With flux
processes, factors such as element trans- -
• 7T-).
J f ' L
%
~-
" "~'~
:~.'.>'
"'" ~.~x;-
/7). _
- -.
..... .
• <~
.-,~_
' > >~>.," .,/.,
. • ,

fer efficiencies, alloying addition particle V >r-';.-<<-.<,-d-.:~-,<I~J,4tD>.Q t \ ' ~ , . ~ : ~ ' ~ t ,.1~I~!

sizing, etc., are well understood by con-
sumable manufacturers, and the required Fig. 1 7 - Unmixed
deposit composition can normally be ob- zone at weld interface
, ~ ~ - z :<.',.,~., ..-J ~.. ' W ' " R ~ E V Z : z : o f welds in 531254
tained for a wide range of welding condi-
steel: N i - 2 0 C r - 9 M o
tions. However, recent years have seen filler metal. A - - SMA,
increased use of nitrogen as an alloying ', ~ ,-t . . . . /~ O01xm .<t ~- ' "..'. . . . ,
50)0
addition to enhance corrosion resistance,
and, when GTA welding high nitrogen
"\ L
steels with a conventional inert gas
shield, this element tends to be lost from
the molten pool because of the relatively +t
low partial pressure in the surrounding at-
mosphere. In consequence, shielding
gases are finding favor that contain a few
percent nitrogen to counter the nitrogen
loss, and even to promote pickup by the
weld metal and improve corrosion be-
havior (Fig. 10) (Refs. 24, 25). The per-
missible nitrogen content in the shielding
gas depends on the solubility in the
molten pool, and hence on the composi-
(_b) ~ . ~ B - - center o f A, 320X;
tion, especially Cr and Mn levels. Exces-
sive shielding gas nitrogen levels may
lead to porosity, and to evolution during
solidification, causing "spitting" and
degradation of the tungsten electrode. At
least for duplex ferritic-austenitic grades,
up to some 2% N 2 in the gas shield is nor-
mally acceptable for a 22%Cr steel, and
possibly 3% for a 25%Cr alloy - - Fig. 11.
Higher nitrogen levels may be tolerable
with the plasma arc process, used in key-
hole mode (Ref. 26).

Effect of Welding Conditions

c - - GTA root toe,
The residual segregation in a weld 160X.

WELDING RESEARCH SUPPLEMENT I 141-s


Fig. 18 - - Pitting attack initi-
tared at U M Z in GTA weld in
$31254 steel: ERNiCrMo-3
filler metal, 25X.
metal at room temperature will depend
on element rejection during solidifica-
tion, on the extent of intermixing in the
liquid phase ahead of the liquid/solid in-
terface, and on the degree of diffusion and
homogenization in the solid phase during
cooling and any reheating by further weld
runs. The last few years have seen con-
siderable advances in understanding the
dependence of the solidification se-
quence in stainless steels on the bulk
composition (Ref. 27). This has been as-
sociated with evaluation of element seg-
regation behavior, as reviewed by David
Fig. 19 - - EDX
scans across weld
interface o f SMA
weld in UNS
531254 steel using
ENiCrMo-3 elec-
trodes (Ref. 32).
Fig. 20 - - H A Z microstructures in duplex ferritic-austenitic stainless steels, 40X. A - - Predominantly ferritic; B - - austen-
ite reformation.
142-s I MAY 1996
allow for solid state diffusion after solid-
ification, and found (Ref. 28) to give good
qualitative prediction of final segregation
gradients in stainless steels - - Fig. 13. A
problem arises, however, in that no direct
allowance is made for a time factor dur-
ing the solidification process, with the re-
sultant implication that the degree of seg-
regation is unaffected by welding
procedure. From studies on castings, seg-
regation is known to depend upon solid-
ification rate because this influences ele-
ment redistribution apart from diffusion
and intermixing in liquid and solid
phases. Most alloy weld metals in which
and Vitek (Ref. 13). In large part, the the effects of segregation are greatest so-
Scheil hypothesis has been followed, viz. lidify primarily by dendritic growth, and
various models for solute redistribution
during such solidification have been de-
C s = k C o ( 1 - f s ) k-1 (2)
rived (Ref. 13). These have been based
mainly on the assumption of segregation
where Cs = composition of solid; Co = ini- under equilibrium conditions, and this is
tial alloy composition; fs = volume frac- unlikely to be the case over the range of
tion of solid; k = partition coefficient. solidification rates normally encom-
This assumes that pool stirring by con- passed by fusion welding.
vection and electromagnetic and surface Accordingly, models have been de-
tension forces is sufficient to give com- veloped in which the segregation coeffi-
plete mixing in the liquid phase - - Fig: cient varies between the equilibrium
12. The approach has been modified to value and unity as growth rate is in-
creased from low to high velocities
(Fig.14) (Refs. 13, 29). On this basis, ele-
ment segregation will be reduced and
weld metal corrosion resistance im-
proved as solidification rate is increased.
This has been experimentally demon-
strated by Nakao and Nishimoto (Ref. 30)
and by Woollin (Ref. 31), for the laser
process - - Fig. 15. With laser welding,
the solidification rate will be high, al-
though rather lower than the travel speed
since solidification will occur epitaxially
from the base metal, with preferential
growth parallel to the maximum temper-
ature gradient, and perpendicular to the
travel direction. For travel speeds associ-
ated with more common arc welding
procedures, growth rate will be relatively
low, and will vary around the periphery
Oisfonce,~m of the weld pool, so that a lesser effect of
solidification rate might be anticipated.
Nonetheless, im-
provement in corro-
sion resistance has
been found at low
arc energy (Ref. 24),
with the rider that,
unfortunately, the
necessary arc energy
limits to achieve
practical benefit for
high-alloy austenitic
deposits may be so
low as to be unac-
ceptable from the
productivity view-
p o i n t - - Fig. 10.
Unmixed Zone
Because of the problem of segregation
in high-alloy austenitic steels, it is normal
industrial practice to weld these materi-
als using nonmatching nickel-based filler
metals such as ENiCrMo-3 (Ref. 19).
These were selected originally simply by
virtue of their high molybdenum content,
and although segregation still occurred,
even the dendrite cores had an alloy con-
tent and corrosion resistance equivalent
to that of the base metal (Table 1). The ap-
proach is now almost invariably em-
ployed for fabrication. Seam welded tube
may be welded autogenously (at, it may
be noted, high speed), but this product
form will be given a high-temperature
homogenization treatment by the tube-
maker prior to delivery. Use of non-
matching consumables requires close at-
tention to welding procedure to obtain
adequate filler metal addition (Ref. 32).
Dilution by base metal can be tolerated,
up to perhaps 60% (illustrated by the
hatched area in Fig. 16), but this still
means that a root opening is preferable,
to ensure that filler metal addition takes
place during welding.
The application of "overalloyed" con-
sumables has enabled satisfactory ser-
vice to be obtained from high-alloy
austenitic types in a range of media, but
does not give weldment corrosion resis-
tance completely matching the base
metal. It has been known for many years
that, during arc welding, a stagnant zone
can exist at the weld interface (Fig. 17),
constituted by melted base metal that has
not mixed into the bulk weld metal (Ref.
33, 34). Following solidification, the re-
gion displays segregation analogous to
that in an autogenous weld metal and is
thus sensitive to localized attack in ap-
propriately aggressive media (Refs. 32,
34, 35). This effect was identified origi-
nally in welds of ordinary 300 series
stainless steels (Ref. 36), causing a minor
increase in the active/passive transition
potential, but it
becomes much .~.'-..,~
more significant ~,~ ~
with high-alloy
grades to the ex-
tent that it is lim- ~ ' - ~ i
iting on corrosion
resistance of
joints made with
overalloyed con-
sumables. With ~ ~
increasing envi-
ronmental corro-
sivity, for exam-
ple higher (a) a ~ ' ~ ~ ~ ' 4 ' ~
exposure temper-
Fig. 22 Preterential weM metal attack in FeCI3. A - - Austenite, 70X; B - - ferrite, 250X.
atures in an ASTM
~o, I o
G48 ferric chloride pitting test, attack
generally takes place first on the unmixed
zone (Fig. 18), resulting in a weldment
critical pitting temperature (CPT) some
15-20°C (27°-36°F) below that of the
base metal. In fact, it is the presence of
the unmixed zone (UMZ) that renders
fairly high dilution levels acceptable in
joints made with nickel-based filler met-
als (Fig. 16), and further means that there
is no practical advantage in employing
even more highly alloyed filler metal
types for improved weldment corrosion
behavior (Ref. 32)
Available corrosion test data indicate
that the UMZ is not as detrimental as
conventional autogenous weld metal.
This is indicated by the dotted line in
Fig.16 (Ref. 32). Solidification in the
UMZ may be by cellular as opposed to
dendritic growth, but microanalyses
have not shown any marked difference in
minimum Cr and Mo levels from segre-
gation in the UMZ (Fig. 19) and those in
bulk autogenous weld metal• The reason
for the disparate corrosion behavior has
not been established, but it may be that
nitrogen loss from the UMZ is less than
from an autogenous weld bead. Cer-
tainly, pitting resistance of autogenous
GTA weld metal can be increased by use
of an Ar/5% N 2 shielding gas to promote
' ~,?
0Y875
WELDING RESEARCH SUPPLEMENT I 143-s
Fig. 21 - - Calcu-
lated PRE values o f
ferrite and austen-
ite in alloys with
25%Cr and
4%Mo. Ni was
varied to keep a
constant ferrite
content. PRE = Cr
+ 3.3%Mo +
16%N (Ref. 18)•
net nitrogen pickup in the bulk weld
metal (Fig. 10), and weldment pit initia-
tion then takes place preferentially at the
UMZ (Ref. 24).
The unmixed zone may be essentially
stagnant when molten, or may display re-
stricted laminar flow (Ref. 33). In either
case, its thickness is not uniform around
the weld. This is partly because fluid flow
in the molten pool can lead to swirls of
base metal becoming detached but not
fully mixed into the bulk weld deposit,
but in addition there will be an effect of
the drag induced by the surface adjacent
to the molten metal. This drag is less at
the pool/gas interface than at the
pool/base metal junction, and in general
the stagnant zone tends to be thinner to-
ward the surface of the material as op-
posed to the mid-depth of the weld pool
(Fig. 17A)(Ref. 32).
This may not be the case actually at
the toe of a root run, where a more pro-
nounced UMZ has been noted for GTA
than SMA welds, presumably reflecting a
local stagnant region - - Fig. 17C. Un-
derstanding of weld pool flow and the
relative effects of buoyancy, electromag-
netic and surface tension forces has in-
creased substantially (Reg. 37, 38), but
modeling remains a complex problem
 [~~. 10 ' z ' I

, /~ • ~ • ,; ?- Is

Ferri~ content, %
Fig. 23 - - Secondary austenite in superduplex weld metal, Fig. 24 - - Effect of ferrite-austenite balance on pitting resistance of 22%Cr-
1000X. 0.12%N GTA weld metal (Ref. 49).

especially when filler metal additions are
made. In this respect, there will be some
disruption with GTA welding, as filler
metal is added, but the resultant stirring
will normally be low compared to gas
metal arc processes, whether metal trans-
fer takes place by short circuiting or
under droplet spray conditions. The situ-
ation thus exists that, although GTA
welding may be preferred for control of
bead shape in root runs, this is the
process in which the unmixed zone is
likely to be most marked. In principle, the
width of the UMZ may be reduced via
welding conditions giving steep thermal
gradients (Refs. 33, 39). There may also
be benefit from use of electromagnetic
stirring, either from external induction
coils, or perhaps by high current, high
travel speed conditions to increase the
Lorentz force in the pool. Further work is
I I
80
necessary, and this should recognize also
the possible influence of relative base
steel and weld metal melting points.
Solid State Transformation
Given the possible coexistence of fer-
rite, martensite and austenite, considera-
tion must be given to the effects of ele-
mental partitioning between the phases.
Since martensite formation is essentially
diffusionless, concern attaches primarily
to the ferrite and austenite phases, and
particularly to recently produced ferritic/
austenitic grades.
These alloys were developed primar-
ily to avoid the problem of chloride stress
corrosion cracking associated with fully
austenitic steels. Originally, the compo-
sition was designed to achieve a two-
phase structure that could be accommo-
dated by minimum
I
changes to existing rolling
schedules to produce a
-
reduction in corrosion resistance and
mechanical properties (Ref. 40). Hence,
it is now normal for welding consum-
ables to be slightly overalloyed in nickel
to promote austenite reformation, while
nitrogen levels have been increased in
base and weld metals to promote trans-
formation to austenite and obtain a more
equal ferrite/austenite balance, apart
from a beneficial effect on corrosion re-
sistance (Refs. 8, 41 ).
The two phases in duplex steels can
differ appreciably in composition, Cr and
Mo partitioning to ferrite and nitrogen
and nickel to austenite. Accordingly, a
thermodynamic approach to alloy design
has been pursued by Berhardsson, so
that, by appropriate control ofCr, Mo and
N levels, the compositions of both phases
following conventional annealing are
likely to lead to similar corrosion resis-
tance (Fig. 21) (Ref. 15). This does not,
however, avoid problems at welded
joints. Equilibrium partitioning of ele-

wrought product. This ap- ments between the phases during weld-
JI Illlf
proach did not adequately ing is most unlikely to be achieved, and,
.,drl I 1%1 allow for subsequent trans- even under the range of welding condi-
.~rl i i IJF _/
6O formation during a welding tions appropriate to normal industrial
~ l l l ~
cycle. The annealed base practice, the compositions of ferrite and
P metal might have a 50/50 austenite can differ markedly.
The ferrite-austenite transformation
i ' ~ I// . phase balance, but weld
metals displayed primary
ferritic solidification, while
during welding has been modeled by
Hertzman, et al. (Ref. 42), using a ther-
q -.- / modynamic approach based on the Ther-
the high-temperature heat-
20
---/
f affected zone (HAZ) trans- mocalc system, with diffusional growth.
formed to ferrite close to Viewed more simply, the mean diffusion
the solidus. Under the distance, x, of any element from random
0 I I I I fairly rapid cooling associ- walk theory is roughly (Ref. 43)
30 34 38 42
PI= %Cr+~3(% Mo+OSx% W ~ 16x% N /'6 ated with welding, trans-
formation to austenite was x = 2~/Dt (3)
suppressed, leading to a
Fig. 25 - - Relationship between duplex steel and weld metal predominantly ferritic weld where D is the diffusion coefficient and t
composition and critical pitting temperature in EeCI3 (Ref 46). is the time. Integrating the diffusion dis-
area structure (Fig. 20) with

144-s MAY 1996

 /200 I I I I I

------ 17%Cr: 0.05%C

-.,-~ 18%Cr: 8%Ni: 0 . 0 5 % C
1000 .-.--. 18%Cr: 9%Ni: 0.06%C: 0 . 6 4 % N b
..... 18%Cr: 8%Ni: 0.02%C

J .,
,q
6OO

"4/ 400
0 0,01 0.1 1,0 10 100 1000
Ageing time,hrs

Fig. 2 7 - - Effect of steel composition on sensitization behavior. Strauss testing, sen-

sitized within bounding lines (Ref. 54).

lOOp, m { •0 T 2 5 8 2
I
Table 2 - - E D X Phase Analysis (wt-%) on SMA Welds in $31803 Steel Made with Overalloyed
Fig. 26 - - Intergranu/ar po/ythionic acid Filler Metal under Varying Arc Energy Conditions
cracking in sensitized 304 stainless steel,
125X. Element, wt-%
Weld region Phase Cr Mo Ni
tance (Ref. 43) over a cooling cycle, for
say a 1kJ/mm (25 kJ/in.) GTA weld run in As-deposited ferrite 23.9 3.0 7.5
10-mm plate (0.4 in.), substitutional ele- root(a) austenite 23.7 2.8 7.8
Reheated ferrite 23.7 3.0 7.2
ments Cr and Ni would diffuse in ferrite rootTM austenite 23.4 2.7 7.7
(Ref. 44) during cooling some 0.5 and 2 Reheated ferrite 25.1 3.7 6.2
pm, respectively. As an interstitial ele- root(b) austenite 22.7 2.5 8.6
ment, nitrogen would diffuse roughly Base ferrite 23.2 3.3 4.1
50-100 pm. The resultant austenite laths metal austenite 19.5 2.4 7.0
are perhaps 4 lam thick, and, in this ex- (a) Root and ill[ passes at 0.7 kJ/mm.
ample, austenite formation could be due (b) Root at 0.5 kJ/mm, fill passes at 3.2 kJ/mm.

to substitutional element diffusion. Cer-

tainly, at higher arc energy and slower
cooling, appreciable redistribution of Cr
and Ni between the ferrite and austenite
would be expected. Conversely, with
lower heat input, austenite reformation
would be controlled by nitrogen move-
ment, as was assumed by Hertzman (Ref.
42). Such differences in ferrite and
austenite composition have been ob-
served over the range of cooling rate ap-
propriate to normal welding practice
(Refs. 45, 46), and are illustrated in Table
2. Consequently, the relative corrosion
resistance of the two phases can vary
considerably, depending on the specific
steel and welding conditions entailed - -
Fig. 22.
The situation is further complicated in
that a single weld thermal cycle is most
unlikely to result in the equilibrium
austenite content being obtained, so that
additional transformation will occur on
deposition of subsequent weld runs. [n
part, this will involve growth of existing
transformed units, but it is possible also
for secondary austenite to be nucleated
and grow within the prior ferrite grains on
reheating (Fig. 23) (Ref. 47). The nitrogen
content of the ferrite matrix is fairly low
and, following diffusion of the nitrogen
and substitution elements, the final PRE
of the secondary austenite will be below
the surrounding material (Table 3), lead-
ing to appreciable reduction in corrosion
resistance (Ref. 48).
From the metallurgical viewpoint, the
prime objective in formulating a welding
procedure for duplex steels should be the
attainment of a satisfactory phase bal-
ance in the weld locale. It is generally ac-
cepted that austenite contents between
about 30 and 70% are preferred for opti-
mum overall properties. In particular,
high ferrite contents can lead to reduced
resistance to pitting corrosion (Fig. 24)
(Ref. 49), and to stresscorrosion, whether
in hot chloride media (Ref. 50) or under
sour, H2S conditions (Ref. 51). Such an
effect of high ferrite levels may be exac-
erbated by intragranular precipitation of
chromium nitrides, as a result of nitrogen
supersaturation in the ferrite at peak tem-
peratures during welding (Ref. 52).
However, even with control of mater-
ial composition and weld cooling rate to
obtain 50/50 phase balance, corrosion
resistance will not necessarily equal the
base metal - - Fig. 25. The adverse effects
of nonequilibrium partitioning tend to be
most marked in weld metal, and, since
they cannot yet be predicted reliably, the
use of overalloyed filler metals has been
propounded (Ref. 20). Commercial con-
sumables for the established 22%Cr
grades are commonly slightly enriched in
Cr, Mo or N relative to base metal, while
even more highly alloyed 25%Cr su-
perduplex filler metals may be used for
root runs exposed to the service environ-
ment. Experience has shown that analo-
gous overalloying is problematic with
superduplex base metal, because the
weld metal may be unacceptably sensi-
tive to precipitation of intermetallic
phases, which reduce corrosion resis-
tance and toughness (Ref. 53).
The last decade has seen considerable
attention paid to the chloride pitting re-
sistance of stainless steels, both
Table 3 - - EDX and WDX Analyses on
26Cr/9Ni/4Mo/0.26N Superduplex Weld
Metal (Ref. 47) (PRE = Cr + 3.3Mo + 16N)
Element, wt-%
Region Cr Mo N PRE
Primary austenite 26.6 3.3 0.52 45.8
Ferrite 27.4 4.0 0.07 41.7
Secondary austenite 24.3 3.4 0.24 39.4

WELDING RESEARCH SUPPLEMENT I 145-s

Table 4 - - PRE Relationships Derived from Polarization Tests on Duplex Weld Metals in
CO2-Saturated 3%NaCI: (FeCI3 data in brackets) (ref. 20)
Pitting Criterion Specific PRE Equation
Pitting potential at 80°C Cr + 1.9Mo + 0.55N - 0.27Ni
CPT at 700mVscE Cr + 2.9Mo + 21N - 0.25Ni
(CPT in FeCI3 Cr + 2.1Mo + 40N - 1.2Ni)
austenitic and duplex grades, for marine 500°-900°C (932°-1652°F), as in-
and oil and gas service. The PRE concept evitably experienced in part of the heat-
of Equation 1 was developed originally affected zone of a fusion weld. Because
from laboratory pitting tests, especially in the chromium diffusion rate is apprecia-
ferric chloride. Clearly, from Tables 2 and bly less than that of carbon, chromium is
3, the PRE values of ferrite and austenite removed from the surrounding matrix as
can differ relatively, and the net pitting the particles form, leaving a depleted
area of lower passivity than the grain cen-
resistance of a weld will depend on the
ters - - Fig. 26. Historically, the problem
minimum PRE in any one region. At the
was overcome (Refs. 1,54) by addition of
same time, studies on duplex steels have
"stabilizing" elements, principally nio-
shown that caution is necessary in ap- bium or titanium to the material to form
plying the PRE approach directly to prac-
stable carbides and getter the carbon
tice. As indicated in Table 4, the rela- from the matrix, or by reduction in mate-
tionship between resistance to chloride
rial carbon content via the use of low-
pitting and material composition de- carbon ferro-chrome in s t e e l m a k i n g -
pends critically on the environmental cri- Fig. 27. With the introduction of AOD or
terion adopted to describe corrosion be- VOD processing in steelmaking, carbon
havior (Ref. 20). levels in commercial products have
fallen dramatically, typically to 0.05% or
Precipitation of Second Phases below, so that the practical problem is
greatly reduced, and weld decay is now
Carbide Formation rarely encountered in plant used in the
as-welded condition (Ref. 55). This is the
Austenitic Steels case even without going to extra-low-
carbon grades (i.e., less than 0.03% car-
bon), although postweld heat treatment
All grades of stainless steel are subject
(PWHT) or service within the "sensitiz-
to precipitation of a range of second-
ing" temperature range can still induce
phase particles at intermediate tempera-
susceptibility to corrosion.
tures. The effect is particularly associated
Increasing time in the sensitizing tem-
with austenitic alloys, in which "weld
perature range leads to greater width of
decay" constitutes the classic case of the
corrosion resistance of a material being the depleted zone and lower local matrix
adversely affected by fusion welding chromium content. The situation is illus-
(Ref. 1). Grain boundary precipitation of trated by the unidirectional analysis of
chromium-rich M23C6 carbides takes Stawstr6m and Hillert (Ref. 56): assuming
place at temperatures between about a thin continuous carbide film,
I Kinetic parameters
diffusivities
Temperature (t)
Strain (t)
Input information Ef
Effective Cr
Alloy composition diffusivity
d monly recognized in welding procedures
Alloy condition
Initial DOS Nucleation
N
kinetics
Prior work
TM history
TA history Minimum Cr Cr depletion
Strain history at interface width
I
Thermodynamic parameters I
I
Degree of
Activity coefficients sensitisation
Fig. 28 - - Flow di-
agram for predic-
Composite Cr
C solubility [ dence of attack, and much more rapid
tion of sensitiza- Equilibrium constant I IGSCC
tion in austenitic Carbide concentration susceptibility
steels (Re£ 59)
146-s I M A Y 1996
~ - ( Cr~ - Cri I
m= 2~/Dtl ~ ) (4)
where m is the depleted zone width,
while Cr o, Cr i and Crp are the chromium
levels in the bulk material, at the carbide
interface, and necessary for passive film
stability, respectively. Since this study,
the development of depletion has been
well modeled, both under isothermal
conditions (Refs. 57, 58) and during a
weld thermal cycle (Fig. 28) (Refs. 59,
60). Using a short-term electrochemical
potentiokinetic reactivation (EPR) test,
Bruemmer was able to obtain good cor-
relation between the degree of sensitiza-
tion and material variables, composition,
heat treatment conditions, and thermo-
mechanical history (Fig. 29) (Ref. 57). It
has been assumed that Crp in Equation 4
is about 13% (Refs. 56, 57), i.e., the
chromium content necessary to render
iron alloys capable of forming a passive
film. In fact, any reduction in chromium
below the matrix content will expand the
potential range over which the material
is in the active state (Fig. 2) (Ref. 3), and
will thus lead to some susceptibility to
preferential intercrystalline corrosion
(Ref. 61 ). Whether or not an attack occurs
then depends on the service redox po-
tential relative to the grain boundary ac-
tive range, i.e., the risk of weld decay de-
pends on the specific environmental
conditions, as well as on the steel com-
position and welding procedure. A small
reduction in grain boundary chromium
content will be significant only in media
close to the active/passive transition,
whereas extensive carbide formation can
lead to intercrystalline attack over the en-
tire potential range giving a stable pas-
sive film on the grain centers (Fig. 30)
(Ref. 61 ). Further to this thermodynamic
effect on passive film stability, the car-
bide particles also act to accelerate pas-
sive film breakdown (Fig. 31 ), increasing
the chance of attack under transient plant
conditions associated, for example, with
changes in oxygen activity.
Given that carbide precipitation is
time dependent, as illustrated by Equa-
tion 4, reduction in arc energy, and the
time spent in the sensitizing temperature
range, is advisable (Ref. 55). This is com-
for austenitic steels which stipulate max-
imum levels of arc energy and interpass
temperature. The effect of varying cool-
ing time was modeled by Solomon (Ref.
60), who demonstrated the relationship
between increased cooling time or car-
bon level and enhanced susceptibility to
intercrystalline corrosion. The work fur-
ther showed the environmental depen-
cooling was necessary to avoid attack in
the electrolytic oxalic acid test (ASTM
 A262A) than in acid CuSO 4 (ASTM
! ! I
A262E). Two caveats to this approach
°
must be added. First, in an actual weld,
concern attaches to the maximum sensi- 100
tizing time experienced, and this will ' ,3
occur at some distance from the fusion
boundary where the peak temperature is /6) m •0
,4
high enough to enter the sensitizing
range, but not so high that the region is
in effect solution treated, i.e., sensitiza-
1.0
L~. "'1"
tion takes place on heating as well as on
cooling. Second, the conjoint strain from =m| ° •
local expansion and contraction during ° •

welding can act to accelerate the sensiti- 0.1 • 00 Fig. 29 - - Measured

sation process, as illustrated by Atteridge and predicted sensi-
and his coworkers (Fig. 32) (Ref. 59), tization times for
Although the general reduction in car- 304 and 316 steels.
bon content from AOD/VOD steelmak- 0.01 Isothermal heat
I I
ing has diminished the practical problem 001 01 1 10 treatment at
100 600°-700°C.
of weld decay, experience in pipework l'fe.asured hme, h
for light water reactor power generation
plants has indicated that the conse-
quences of precipitation and sensitiza-
tion can be greatly increased by residual
welding stresses, and intercrystalline
cracking has been experienced in a num- Fig. 30 - - Relation-
ber of units. A considerable amount of 0.50 ! ! ship between
work has been carried out, therefore, to potential necessary
address residual stress patterns at welds. ~ O25 Ior grain boundary

./ /
Techniques such as "heat sink" welding, 0.15%C / passivation and
minimum aging
with or without local induction heating,
time between 500 °
have been employed to induce compres- o
and 850°C, 18%Cr-
sive stresses on the inner wall of pipe,
10%Ni austenitic
thereby avoiding cracking (Ref. 62). At
"-0.25
i 0.osO/oi steel 20% H2SO4
the same time, the problem is especially with 0. l g/L
associated with the environmental con- NH4CNS at room
ditions encountered in some light water -0.50 l ) l i m ~ m ,, i l• im l i l ~,, qim ° i i m, , ~ m i N

/0 temperature, gen-
systems, and these measures would not ).Ol 0.1 1
eral passive/active
normally be employed for the typical Ageing hme,hrs transition for grain
welded chemical plant, for example. centers below-0.48
Again, in the context of light water re- VSHE (Re£ 61).
actor power plants, it is recognized that
initiation of grain boundary carbide pre-
cipitation in the HAZ can take place very
rapidly. Hence, although a controlled
i !
weld thermal cycle may not induce suf- HAZ of electron beam weld (0.16kJ/mm
ficient precipitation to cause sensitiza- "me= H A Z of friction weld
tion directly, the nucleated carbides .... H A Z of S M A weld (1 k J / m m )
might grow in subsequent long-term ser- 0.6 ------ H A Z of G M A weld (0.6 k J / m m )
vice at lower temperatures, in this case ~--- Solution treated material
roughly 300°C (572°F). Indeed, from
0.4,
evaluation of the activation energy as de-
termined by slow strain rate tests, Povich
02 , ,4##amntFl~e
and Rao demonstrated that some mea- peter,~l
sure of "low-temperature sensitization"
of welded Type 304 pipe could be antic- 0
ipated after, say, 10 years exposure to I
300°C (Ref. 63). -02 - ~I " ~ . ApparenfFlade "
Fi~¢. 31 - - Decay of
Most environmental conditions in HAZ passive film
which stainless steels are used corre- "" - 0 4
tbllowing anodic
spond to a moderately low redox poten-
tial. Under highly oxidizing conditions, -0.6 "" ,I
polarization at
0.4VsH E tbr 10 rain,
exemplified by a nitric acid plant, the ef- 20% HjSO 4 with
fect of chromium depletion can be very -0.8 ! • #
0.1 g/L NH4CNS,
marked, while it is possible also for the 0 0.1 1 10 100 18%Cr- 10%Ni-
carbides to be dissolved. As a result, Time,rain 0.15%C austenitic
these media are very searching and either steel.

W E L D I N G RESEARCH SUPPLEMENT[ 147-s

 an extremely low on the supply of carbon from the austen-
carbon content or ite and of chromium from the ferrite, but
40 ! I I I
overall the effects of precipitation are re-
effective stabiliza-
Thermal only

,/"
tion is essential for duced, both by the high phase boundary
Pass by pass strain
• Cumulative strain • satisfactory service area available and also by the higher
30 chromium content in the ferrite phase.
to be obtained. Fur-
ther, boron added to Thus, materials containing appreciable
the steel for im- amounts of ferrite are resistant to sensiti-
proved hot worka- zation (Ref. 66), although they are by no
kj bility can stabilize means immune to the problem given pro-
the carbides to longed exposure to elevated tempera-
10 higher tempera- tures for postweld heat treatment or in
tures, and this has service (Ref. 67). As a consequence, weld
led to the develop- metals can contain higher carbon con-
i 1 ~..~pv
. , , , , . ~ 1 0 .... I I ment of low-boron tents than base metal (Ref. 55), and this
0
"nitric acid grade" permits the use of shielding gases con-
0 0.02 0.03 0.04 0.05 0.06
Carbon contenf, vf % (NAG) alloys, in taining some CO 2, provided that a suffi-
which silicon and cient ferrite level is maintained. For gas
phosphorus are also metal arc welding, an addition of CO 2
Fig. 32 - - Predicted sensitization in a 304 steel pipe weld, assessed by controlled to mini- may improve metal transfer characteris-
EPR test. Effect of local strain (Ref. 59). mize adverse effects tics across the arc, and reduce porosity
of grain boundary from shielding gas entrapment.
segregation (Ref.
64). Even with stabi- Martensitic and Ferritic Steels
I lized steels, there is
an advantage in re- Carbide formation and associated
ducing carbon for chromium depletion as a result of weld-
nitric acid duty. ing is by no means confined to austenitic
When making a grades but can develop also with marten-
weld, the material sitic and ferritic alloys (Ref. 54). With
immediately adja- martensitic steels, the problem is primar-
cent to the fusion ily associated with medium- to high-car-
boundary is effec- bon contents (e.g., 0.2-0.5%) as may be
tively solution employed for surfacing applications. The
treated at high tem- loss in corrosion resistance takes place
/
perature, and some not only at prior austenite grain bound-
carbon is thus re-
aries but also within the martensitic
leased into solid so-
i~ ,, lution to form structure of the matrix (Ref. 68). The ef-
0 fect is again controlled by chromium dif-
M23C 6 on cooling.
Intercrystalline cor- fusion, and, since this is more rapid in a
,0.2mm, AF1035 rosion in this region martensitic or ferritic matrix than in fcc
in a nitric acid plant austenite, depletion can occur in regions
Fig. 33 - - Intercrystalline attack at weld in $40900 ferritic steel, 50X. is known as "knife- heated to a peak temperature rather
line attack"(Refs. 54, lower than the austenitic case, typically
65), and experience 450°-500°C (842°-932°F). Low arc en-
has indicated that ergy is preferred, but the situation is com-
niobium is more ef- plicated by the need for fairly high pre-
fective at gettering heat levels to avoid hydrogen cracking
carbon in the high- on cooling to room temperature. In most
temperature HAZ applications, martensitic stainless steels
than titanium. will receive a postweld heat treatment to
The effect of temper the material. This will lead to
carbide formation healing of any chromium-depleted areas,
depends upon the and from the practical standpoint, the
density of precipita- problem is encountered only at weld-
tion at a single point, ments put into service in the as-welded
and thus on the grain
condition or tempered at very low tem-
size or total bound-
peratures to maintain high material hard-
ary area. With cast-
ings and weld metals ness.
that contain some Because of the high chromium diffu-
ferrite, precipitation sion rate and low carbon solubility, sen-
occurs initially on sitization develops rapidly in ferritic
the ferrite/austenite steels (Refs. 54, 68, 69). The critical tem-
boundaries (Refs. perature range is similar to that for
Fig. 34 - - Fracture face of intercrystalline attack in low-carbon 12% Cr 58, 66, 67). The ini- austenitic alloys, but sensitization in fer-
steel. Corrosion took place at ferrite/ferrite and ferrite/martensite tial development of ritic grades requires only a fairly short ex-
boundaries, leaving martensite units unattacked, 200X. depletion depends posure time even at temperatures below

148-s I M A Y 1996
say 500°C (Fig. 27). It can therefore be
difficult or impossible to avoid sensitiza-
tion conlpletely by use of low arc: energy,
especially if multipass welding is in-
volved. This is the case for virtually all
ferritic stainless steels, from lean alloy
11-12%Cr grades (Ref. 70) up to "super-
ferritic" materials containing 25 30%Cr
(Ref. 71). In ferritic materials, nitrogen
has an analogous effect to carbon, al-
though probably less severe on a wt-%
basis. Attempts have been made to avoid
the problem by steel processing proce-
dures giving exceptionally low total
(C+N) levels, but in general practice, it
has been found more satisfactory to em-
ploy stabilization by titanium or nio-
bium. It is remarked that nitrogen is not
recognized in standards such as UNS
$40900, yet preferential intercrystalline
attack has been observed in practice at
welded joints in such stainless steel com-
plying with specification limits on car-
bon and titanium but having relatively
high nitrogen levels - - Fig. 33.
Time risk of sensitization of low-carbon
12% Cr alloys depends also on the weld
a r e a phase balance. Fully ferritic materi-
als are appreciably more prone to the
problem than ferritic/martensitic alloys,
the adverse effect of precipitation being
increased by the local grain growth in-
herent in welding these steels. It has been
suggested that the formation of grain
boundary austenite, and hence marten-
site (Refs. 54, 69), during a weld thermal
cycle has a deleterious effect either by
leading to increased strain in the sur-
rounding lattice, or because the austen-
ite has a lower chromium content than
the matrix. The latter mechanism is not
valid, since, with normal welding condi-
tions and cooling rates, EDX analysis at
TWl has shown the final martensite and
ferrite to have virtually the same
chromium level. Moreover, welds which
have suffered intergranular attack display
no evidence of preferential corrosion of
time martensite - - Fig. 34. Overall, there
is no doubt that high niartensite contents
are beneficial from the corrosion view-
point, and apart from the high interphase
boundary area, this is probably associ-
ated with the higher solubility of carbon
and nitrogen in austenite than in ferrite,
together with the fact that, when nlarten-
site formation occurs, it takes place at a
temperature below the sensitizing range.
Further, if precipitation then occurs on
reheating in multipass welds, the "den-
sity" will be reduced by the high number
of nucleation sites within the martensite
and at the martensite/ferrite boundaries.
The extent of transformation to marten-
site at welds is therefore important, and it
must be recognized that, even though a
/00
80
50
4,0
20
0 TWI. Ferrite l~ctor =
5 10 15 20
Keltmt~user ferrite ~ d o r
12%Cr steel may be two phase (ferrite
and tempered nlartensite) in the an-
nealed condition (Ref. 72), rapid cooling
during welding can lead to retention of
the ferrite formed at high temperature
(Fig. 35) (Ref. 73). Direct analogy can be
drawn with duplex ferrite/austenitic ma-
terial (Ref. 40), and, in both cases, devel-
opment of a predominantly ferritic struc-
ture at welds increases the risk of
intergranular corrosion in service.
The coarse grain structure normally
produced in ferritic stainless steel weld
metals can lead to unacceptable loss of
toughness, as well as sensitization, and
the materials are therefore sometimes
welded with austenitic consumables.
The activity of carbon and nitrogen will
depend upon the levels of chromiun] and
other elements, but if carbon and nitro-
gen contents in an austenitic weld metal
are appreciably higher than in the base
metal, these elements will diffuse into the
high-temperature HAZ (Ref. 74). This can
promote precipitation of chromium car-
bides or nitrides on cooling and thus loss
of corrosion resistance in this area, and
must be recognized by minimizing heat
input or ensuring that the base metal is
"overstabilized."
Intermetallic Phases
In the past, intermetallic formation in
conventional austenitic stainless steels
has been associated primarily with ex-
tended cycles at between perhaps
500 ° 900°C, during PWHT or service
(Ref. 54). More recently, it has become
evident that significant precipitation of
W E L D I N G RESEARCH SUPPLEMENT I 149-s
Fig. 3 5 - - Eftect o f
composition on
.structure o f 1 2 % C r
territic/martensitic
steels, x = base
m e t a l (Ret: 27);
h a t c h e d area = H A Z
data o b t a i n e d at
Cr + 6%Si+ *%Ti +
"2F 30 4%Mo + 2%AI +
4%Nb - 2%Mn
4 % N i - 4 0 ( C + N).
intermetallics can occur in the course of
welding, especially ill high-alloy
austenitic and duplex steels, leading to
loss of corrosion resistance. A number of
intermetallic types has been identified,
and, since they are highly alloyed and
presumably resistant to direct corrosion
in a wide range of media, it would seem
that the precipitation has an adverse ef-
fect by a depletion mechanism, analo-
gous to that with carbide formation.
Intermetallic precipitation in
austenitic grades can be enhanced in
weld metal by alloy element segregation,
possibly contributing to the decreased
corrosion resistance of autogenous weld
metals (Ref. 32). Intermetallics can form
also when high-molybdenum nickel-
based filler metals are used, but joint be-
havior remains controlled by the UMZ.
Grain boundary intermetallic precipita-
tion has been further observed in the
HAZ of superaustenitic weldments (Ref.
75), although reduced corrosion resis-
tance in this region is apparent only
when solidification conditions have
been such that the UMZ is m i n i m i z e d - -
Fig. 36. Nonetheless, the effect renders it
difficult to achieve weldment corrosion
properties matching those of the base
steel unless some form of PWHT is car-
ried out for homogenization. Nitrogen
retards intermetallic formation (Refs. 21,
76), and the problem may be ameliorated
in new superaustenitic steels containing
very high levels of nitrogen (circa
0.4-0.5%) for improved resistance to pit-
ting and crevice corrosion in chloride
media (Ref. 77).
The consequences of intermetallic
1 Fig. 40. Indeed there
Fig. 36 - - FIAZ attack at weld in $31254 steel, 5X.
formation are very much more severe in
duplex and especially superduplex
grades (Ref. 78). The rapid diffusion in
ferrite means that precipitate nucleation
and growth can be extremely rapid (Figs.
37 and 38), and the concomitant deple-
tion in chromium and molybdenum is
sufficient to cause drastic loss in pitting
resistance (Fig. 39), although with some-
what less severe effect on general acid
corrosion resistance (Ref. 79).
Intermetallic formation has been ex-
tensively studied in the context of weld-
ing superduplex stainless steels since it is
seen as a major hindrance in obtaining
optimum joint properties. Its reliable
avoidance necessitates use of low arc en-
ergy and very low interpass tempera-
tures, which severely restricts overall
joint completion rate (Ref. 46). Only a
small amount of intermetallic phase can
diminish pitting resistance (Ref. 80) - -
• UNS $32304
[] UNS $31803
1000
UNS $32550
[] Modified UNS $32550: 3.8%Mo, 0.26%N
.,800
S 600
D lent to a drop in PRE
I
2O0
0
10 "100 1000
Time,see
Fig. 3 7 - - Time-temperature transformation curves for duplex stainless sigma particle in Cr
steels (Ref. 78). Intermetallic formation, 550 ° - 1000°C; (z', 300°-550°C.
150-s I MAY 1996
is debate as to Table 5 - - Reported Analyses (wt-%) for
Intermetallic Phases in Duplex Stainless
whether any inter- Steels (Refs. 80-82)
metallic formation at
welds in superduplex Phase Cr Mo Ni
steels is tolerable, yet
it is difficult to see Sigma 30 6 5
34 7 4
how it can be 30 10 4
avoided entirely. Chi 27 12 5
Certainly, the rapid- 28 18 3
ity of intermetallic R 20 39 3
formation (Fig. 37) 26 25 4
makes it problematic
to design welding quire diffusion from a radius roughly two
consumables for su- times that of the particle, to decrease the
perduplex steels that PRE by 7 units, i.e., a reduction of 2.3%
are overalloyed to a Cr and 1.4% Mo in the ferrite. This as-
significant degree to sumes that sigma formation is controlled
mitigate the effects of by diffusion in ferrite and the ferrite com-
partitioning during position. The fall in CPT in Fig. 40 is as-
the ferrite/austenite sociated with intermetallic particles
transformation (Ref. 53). Accordingly, some 0.5 to 1.0 IJm in diameter. The as-
nonmatching nickel-based fillers are sociated volume of alloy depleted mate-
being explored (Ref. 81), and, provided rial of 1-2 pm radius is certainly large
that adequate joint strength can be enough to constitute a stable pit nucleus
achieved, these may well prove of prac- (Ref. 9) and the observed effect on pitting
tical advantage for superduplex steels. resistance would be expected.
The effect of intermetallic formation This represents an extreme case, since
when welding duplex/superduplex steels such a particle size requires a fairly ex-
has received particular attention with re- tended time in the precipitating tempera-
spect to pitting attack in chloride media. ture range. Diffusion of Mo and Cr (Ref.
From data such as in Fig. 40, the need has 44) over 1pm would involve several min-
been expressed for definition of a maxi- utes exposure at, say, 800°C (1472°F),
mum tolerable intermetallic volume frac- equivalent to an arc energy of well over 2
tion. This, however, is not the critical pa- kJ/mm (51 kJ/in.) on 12-ram (0.47-in.)
rameter. The form of Equation 4 is of plate, given room temperature "preheat."
general application to describe the de- This arc energy would now be regarded
pleted zone round a precipitate particle. as excessive, following procedural devel-
Both the width of a depleted region and opment trials over the last few years. From
the local reduction in alloy content will TTT curves such as in Fig. 37, intermetal-
increase with increasing time in the pre- lic formation may be more rapid than in-
cipitation range, and pitting resistance dicated by bulk diffusion data, and it is
will thus depend on likely that growth is influenced by faster
the maximum size of phase boundary diffusion, which will
an intermetallic par- modify the elemental depletion pattern
1 ticle, and not the vol-
| and the ease of initiation of stable pitting.
ume fraction. Nevertheless, a particle size of 0.1-0.2
1 Intermetallic for-
mation in HAZs or
weld metals of su-
perduplex grades
may readily reduce
lam could be attained with welding con-
ditions deemed entirely acceptable for
22% Cr alloys, the concomitant alloy de-
pletion being sufficient to reduce the CPT
by perhaps 10°C (18°F). This particle
the CPT in a ferric width is at the limit of resolution by opti-
chloride test by some cal microscopy, while, assuming contin-
20°C (36°F), equiva- uous phase boundary precipitation and a
ferrite/austenite lamellar width in the sub-
of about 7 units in the critical HAZ of say 20-40 pm, the volume
adjacent material fraction would be less than 0.5%. Clearly,
(Fig. 6). Typical com- a weld procedure qualification specifica-
positions of inter- tion requiring intermetallic phases to be
metallic phases are below, say, 1% would not offer a safe-
10000
given in Table 5 guard against loss of pitting resistance due
(Refs. 82-85), and to intermetallic precipitation during
enrichment of a welding, and it is better to place reliance
on actual corrosion testing.
and Mo would re-
Discussion
The need to consider weldability is
well recognized by steelmakers and has
appreciably influenced alloy design in
recent years, for example in the develop-
ment of NAG austenitic steels and of cur-
rent production duplex alloys. The in-
dustrial importance of welding has
further led to significant study of the fun-
damental changes that take place during
a welding cycle, with regard to solidifi-
cation, partitioning and precipitation.
Equally, factors contributing to passive
film stability and breakdown have been
increasingly researched, and in combi-
nation the two lines of investigation have
greatly clarified the practical effects of fu-
sion welding on corrosion behavior of
stainless steels.
Perhaps inevitably, the greater part of
research directly aimed at corrosion
properties of weldments has been in re-
sponse to industrial problems. This has
normally entailed identification of con-
trolling metallurgical or process factors,
followed by trials to optimize the key
variables. This is well illustrated by the
extensive work in the last two decades on
the problem of sensitization of stainless
steels and nickel alloys for nuclear power
plants, which has led to a good under-
standing of the interplay between mater-
ial, welding and environmental factors
and to demonstration of the effects of ap-
plied stress upon passive film breakdown
at chromium depleted areas (Ref. 62).
The work has heightened awareness of
the importance of the metal/environment
potential in service relative to a pas-
sive/active transition, and this concept is
being increasingly employed in other in-
dustrial regimes (Ref. 86),
Much of the recent work on corrosion
of welds in stainless steels has entailed
newly developed alloys, both super-
austenitic and duplex grades. In the for-
mer context, the practical significance of
weld metal segregation and the fusion
boundary UMZ is now well recognized.
It remains to be seen if the latter can be
controlled by design of filler metal to ob-
tain a preferred freezing temperature
range or by welding techniques giving
more rapid pool stirring. It may be also
that new high-nitrogen steels (circa
0.5%N) (Refs. 76, 77) in which segrega-
tion of alloy elements may be rather dif-
ferent (Ref. 15) will be less sensitive to the
problem. If the unmixed zone can be
negated, then, in high-alloy austenitic
steels at least, weldment corrosion resis-
tance is likely to be limited by inter-
metallic formation. As a precipitation
process, this should be controllable by
use of suitable low arc energy and total
thermal cycle, albeit at some cost in pro-
ductivity. One area which does not seem
to have received attention is the conse-
quence of the base metal solution treat-
ment procedure. If the final anneal is set
at too low a temperature, residual inter-
metallic nuclei may remain, which could
act to form particles during a weld ther-
mal cycle, analogous to the problem of
low-temperature sensitization of 300 se-
ries alloys.
Turning to the duplex grades, the ad-
vances in modeling alloy element parti-
tioning (Refs. 42, 48) are extremely en-
couraging. With current welding
procedures, it would seem that the con-
sequences of partitioning are most
marked in consequence of secondary
austenite formation (Ref. 47), and in
many cases, the net corrosion resistance
is dictated by the formation of this con-
stituent. The general guidelines for weld-
ing are understood in that secondary
austenite is particularly likely to develop
when a low arc energy root pass is re-
heated by a high arc energy second run.
This situation can be avoided by appro-
priate design of the welding procedure.
However, the propensity for secondary
austenite formation depends also on the
bulk material composition, for example
WELDING RESEARCH SUPPLEMFNTI 151-~
Fig. 38 - - SEM backscat-
tered electron image
showing intermetallic for-
mation in a superduplex
steel (Ref. 80).
the presence or absence of tungsten (Ref.
47), and further effort is required to clar-
ify this effect. In superduplex steels espe-
cially, the susceptibility to intermetallic
formation is evident, and with present al-
loys, it must be accepted that low arc en-
ergy/interpass temperature conditions
are required, although again with loss of
productivity. A predictive model, as de-
rived for sensitization of 300 series steels
(Refs. 56-60), would be valuable, but
would necessitate careful consideration
of the range of intermetallic types and
compositions formed in superduplex al-
loys. More detailed quantification of the
effects of welding is needed, since the
recommendations for avoiding sec-
ondary austenite and intermetallic
phases are not entirely compatible. De-
velopment of the equilibrium austenite
content in a weld run so that there is lit-
tle tendency for secondary austenite re-
quires observance of a minimum arc en-
ergy, whereas suppression of
intermetallics will entail a restriction to
the usable heat input.
The increased use of duplex steels has
had a major effect on weldment testing
requirements. In the past, the principal
problem stemming from welding was
weld decay, and this was controlled by
Fig. 39 - - Chlo-
ride pitting due
to phase bound-
ary intermetallic
formation in su-
perduplex steel
(Re£ 80), 200X.

601 I I
Fig. 40 - - Effect
of intermetallic
precipitation in
superduplex
stainless steels
on reduction in
FeCI ~pitting 0 1
resistance
(Re£ 80).
specifying that the base steel should pass
on intercrystalline corrosion test as in
ASTM A262, following a simple isother-
mal sensitizing heat treatment to simu-
late a welding operation. This approach
is not viable for avoidance of weld area
attack in duplex steels, since both high
and low heat input may be damaging,
while it does not allow for loss of weld
metal properties. Hence, it has now be-
come the norm to include corrosion test-
ing in weld procedure qualification, usu-
ally involving ferric chloride solution at
one or more temperatures. The tendency
has been to specify conservative accep-
tance criteria, and the need to pass such
tests in practice had stimulated much of
the basic work carried out on the weld-
ing behavior of duplex steels.
The philosophy of incorporating a
corrosion test in stainless steel weld pro-
cedure qualification requirements is
gaining wider acceptance. However, it
means that study is needed of the practi-
cal consequences of a welding cycle on
corrosion behavior, in terms of the rela-
tionship between short tests and longer
term operation. To illustrate the point,
while intermetallic precipitation in su-
perduplex steels has an adverse effect in
chloride media at fairly high potential
(exemplified by the ferric chloride test
method), the critical size of the pit nu-
cleus to develop stable growth may well
be higher in service media of lower oxi-
dizing power, such as CO2-containing
brines. If this is the case, then intermetal-
lic formation will be of less practical im-
port than generally considered, provid-
ing of course that it does not
unacceptably reduce other service prop-
erties, notably toughness. Clearly, it must
be recognized that imposition of unreal-
istically demanding test procedures may
severely restrict the application of
welded stainless steels and incur appre-
ciable economic penalty.
Concluding Remarks
A review has been carried out of a re-
1 5 2 - s l M A Y 1996
I a
the passivity of a series of iron-choromium al-
loys in sulphuric acid. Corrosion Science 18:
15]-160.
photoelectron spectroscopic study on the role
of molybdenum in increasing the corrosion re-
sistance of ferritic stainless steels in HCI. Cor-
rosion Science 19:3-14.
m action of nitrogen with key alloying elements
4 5
ln~lic.%
cent study on the effects of fusion weld-
ing on the corrosion resistance of stain-
less steels. Reference has been made to
ferritic, martensitic and austenitic alloys
and to dual-phase grades. In all cases,
concern attaches primarily to the stabil-
ity of the passive film and the effects have
been addressed of 1) segregation during
solidification, 2) partitioning during
phase changes, and 3) precipitation of
second-phase particles. Advances have
stemmed from fundamental metallurgi-
cal and corrosion studies, and from prac-
tical procedural development trials, es-
pecially on recently developed alloys.
Service behavior will be determined
also by factors such as the degree of
residual oxide present on the joint on en-
tering service (Ref. 46), and study re-
mains necessary so that base metal cor-
rosion resistance can be reliably
obtained at welded joints and unforeseen
service failures are avoided. Nonethe-
less, a good level of understanding has
been established, and in most cases
quantitative recommendations on weld-
ing procedures can be made to obtain
optimum corrosion resistance at fusion
weld joints.
Acknowledgments
The author thanks colleagues at TWl
and associates throughout the world for
their detailed study of stainless steels, for
their published papers and for many in-
formative discussions. Their work is
gratefully acknowledged as the primary
input of this paper.
Reteren( es
1. Uhlig, H. H., and Revie, R.W. 1985.
Corrosion and Corrosion Control. New York,
N.Y., Wiley.
2. Jackson, R. if, and van Rooyen, D. 1971.
Electrochemical evaluation of resistance of
stainless steels to chloride media. Corrosion
27(5): 203-210.
3. Shaw, D., and Edwards, A. M. 1965. A
transistorised potentiostat system for corrosion
studies. Corr Sci 5:413-424.
4. Asami, K., et al. 1978. An XPS study of
5. Hashimoto, K., et al. 1979. An x-ray
6. Halada, G. if, et al. 1995. Electrochem-
ical and surface analytical studies of the inter-
in stainless steels. Corrosion '95, Orlanclo,
Fla., NACE, Paper 95531.
7. Palit, G. C., et al. 1993. Electrochemical
investigations of pitting corrosion in nitrogen-
bearing Type 316LN stainless steel. O)rrosion
49 (12):977 991.
8. Pawe[, S. J., etal. 1989. Role of nitrogen
in the pitting resistanceof cast duplex CF-l~/pe
stainless steels. Corrosion 45(2): 125 133.
9. Mattin, S. ff 1994. Nucleation of corro-
sion pits on stainless steel. Ph.D. dissertation,
Cambridge University, Cambridge U.K.
10. Galvele, ]. R. I981. Transport
processes in passivity breakdown II - - full hy-
drolysis of the metal ions. Corrosion Sci. 21 (8):
551-579.
11. Pistorius, P., and Burstein, T. 1992.
Metastable pitting corrosion of stainless steel
and the transition to stability. Phil. Trans. Roy.
So(. A341 : 531-559.
12. Easterling, K. 1983. Introduction to the
Physical Metallurgy of Welding. London. But-
ter~:orths.
13. David, S. A., and Vitek, J. M. t989.
Correlation between solidification parameters
and weld microstructures. International Mate-
rials Reviews 34(5): 213-245.
14. Hammar, O., and Svensson, U. 1979.
Influence of steel composition on segregation
and microstructure during solidification of
stainless steels. Solidification and Casting of
Metals. London, The Metals Society, Book
192: 401-410.
15. Marshall, P. I., and Gooch, T. G. 1993.
Effect of composition on corrosion resistance
of high-alloy austenitic stainless steel weld
metals. Corrosion 49(6): 514-526.
16. Garner, A. 1979. The effect of autoge-
nous welding on chloride pitting corrosion in
austenitic stainless steels. Corrosion 35(3):
108-113.
17. Suutala, N., and Kurkela, M. 1984. Lo-
calized corrosion resistance of high-alloy
austenitic stainless steels and welds. Stainless
Steels '84. Gothenburg, London, The Metals
Society, pp. 240-247.
18. Bernhardsson, S.-O. 1991. The corro-
sion resistance of duplex stainless steels. Du-
plex Stainless Steels '91. Beaune, France, Les
Editions de Physique, pp. 185-210.
19. Rabensteiner,G. 1989. The welding of
fully austenitic stainless steels with high
molybdenum contents. Welding in the World
27(1/2): 2-13.
20. Walker, R. A., and Gooch, T. G. 1991.
Pitting resistance of weld metal for 22Cr5Ni
ferritic-austenitic stainless steels. Brit. Corr. J.
26(1 ): 51-59.
21. Koseki, T., and Ogawa, T. 1991. An in-
vestigation on the weld solidification of Cr-Ni-
Fe-Mo alloys. Quarterly l. Jap. Weld. Soc. 9(1 ):
143-149.
22. Van der Horst, J. M. A., and Clark, G.
A. 1974. Weld corrosion in urea synthesis.
Corrosion Science 14 (11/12): 631-634.
23. Gooch, T. G. 1975. Welding and the
corrosion resistance of austenitic stainless
steels. The influence of welding and welds on
the corrosion behavior of constructions. Tel
Aviv, IIW: 1.53 1.75.
24. Ginn, B. J., and Gooch, T. G. 1993. Pit-
ting resistance of autogenous welds in UNS
$31254 high alloy austenitic stainless steel.
12th International Corrosion Congress, Hous-
ton, Tex., NACE, 4: 2895-2906.
25. Gunn, R. N., and Anderson, P. C. J.
1994. Development of special Ar-He-N 2 gases
for TIG welding of duplex and superduplex
stainless steels. Duplex Stainless Steels '94.
Glasgow, TWI, Paper 30.
26. Rogne, T., Fostervall, H., and R()rvik,
G. 1991. Plasma arc welding of duplex stain-
less steels, vide ref 18: 421-429.
27. Brooks, I. A., and Thompson, A. W.
1991. Microstructural development and solid-
ification cracking susceptibility of austenitic
stainless steel welds. Int. Mat. Rev. 36 (1):
16-44.
28. Brooks, J. A. 1990. Weld microsegre-
gation: modelling and segregation effects on
weld performance. Weldability of Materials.
Detroit, ASM International, pp. 41-47.
29. Aziz, M. K. 1982. Model for solute re-
distribution during rapid solidification. J.
Appl. Phys. 53:1158.
30. Nakao, Y. and Nishimoto, K. 1992. Ef-
fects of laser surface melting on corrosion re-
sistance in stainless steel and nickel-base alloy
clad layers of cast bi-metallic pipes. IIW Doc.
IX-1666-92.
]1. Woollin, P. 1995. laser beam surface
melting of high alloy austenitic stainless steel.
4th International Conference on Trends in
Welding Research. Gatlinbu rg, Ten n., ASM In-
ternational, Session V.
32. Gooch, T. G., and Elbro, A. C. 1995.
Welding corrosion-resistant high-alloy
austenitic stainless steel. Corrosion in natural
and industrial environments: problems and
solutions. Grado, NACE Italia, Paper 13.
33. Savage, W. F., Nippes, E. F., and Szek-
eres, E. S. 1976. A study of weld interface phe-
nomena in a low-alloy steel. Welding Journal
55(9): 260-s to 268-s.
34. Baeslack, W. A., Lippold, J. C., and
Savage, W. F. 1979. Unmixed zone formation
in austenitic stainless steel weldments. Weld-
ing Journal 58(6): 168-s to 176-s.
35. Flasche, L. H., and Ahluwalia, H. S.
1993. Localized corrosion of the unmixed
zone in nickel-base alloy weldments, vide ref
24: 2907-2925.
36. Gooch, T. G., Honeycombe, J., and
Walker, P. 1970. Potentiostatic study of the
corrosion behavior of austenitic stainless steel
weld metal. Brit. Corr. J. 6:148-154.
37. Oreper, G. M., and Szekely, I. 1984.
Heat and fluid-flow phenomena in weld
pools. J. Fluid Mech. 147: 53-79.
38. Choo, R. T. C., and Szekely, J. 1994. The
possible role of turbulence in GTA weld pool
behavior. Welding Journal 73(2): 25-s to 31-s.
39. Hibner, E. L., Hinshaw, E. B., and
Lamb, S. 1992. Weld fabrication of a 6%
molybdenum alloy to avoid corrosion in
bleach plant service. Proc. TAPPI Engineering
Conference. Nashville, Tenn., TAPPI,
reprinted by Nickel Development Institute,
No. 14 020.
40. Gooch, T. G. 1982. Weldability of du-
plex ferritic-austenitic stainless steels. Duplex
Stainless Steels "82. St. Louis, Mo. ASM, pp.
573-602.
41. Combrade, P., and Audouard, I.-P.
1991. Duplex stainless steels and localized
corrosion resistance, vide ref 18: 257-281.
42. Hertznlan, S., Roberts, W., and Lin-
denmo, M. 1986. Microstructure and proper-
ties of nitrogen alloyed duplex stainless steel
after welding treatments. Duplex Stainless
Steels '86. The Hague, Nederlands Instituut
voor Lastechniek, pp. 257-267.
43. Leone, G. L., and Kerr, H. 1982. The
ferrite to austenite transformation in stainless
steels. Welding Iourna161 (1): 13-s to 21 -s.
44. Brandes, E. A., and Brook, G. B., ed.
1992. Smithells Reference Book. Oxford,U. K.
Butterworth-Heinemann, Chapter 13.
45. Baeslack, W. A., and Lippold, I. C.
1988. Phase transformation behavior in du-
plex stainless steel weldments. Met. Con. 20
(1): 26R-31R.
46. Gooch, T. G. 1991. Corrosion resis-
tance of welds in duplex stainless steels, vide
ref 18: 325-346.
47. Nilsson, J.-O., Jonsson, P., and Wilson,
A. 1994. Formation of secondary austenite in
superduplex stainless steel weld metal and its
dependence on chemical composition, vide
ref 25, Paper 39.
48. Hertzman, S., and Jargelius-Petterson,
R. 1994. vide ref 25, Paper 1.
49. Ogawa, T., and Koseki, T. 1989. Effect
of composition profiles on metallurgy and (or-
rosion behavior of duplex stainless steel weld
metals. Welding Journal 68(5): 181 -s to 191 -s.
50. Gooch, T. G. 1986. A review of stress
corrosion cracking of welded duplex fer-
ritic/austenitic stainless steels. Welding in the
World 24 (7/8): 148 167.
51. Kudo, T., Tsuge, H. and Moroishi, T.
1989. Stress corrosion cracking resistance of
22%Cr duplex stainless steel in sinlulated sour
environments. Corrosion 45(10): 831-838.
52. Hoffmeister, H., and Lothongkum, G.
1994. Quantitative effects of nitrogen contents
and cooling cycles on 6-y transformation,
chromium nitride precipitation and pitting
corrosion after weld simulation of duplex
stainless steels, vide ref 25, Paper 55.
53. Fager, S-A. 1991. Design of consum-
ables for the welding of superduplex stainless
steel, vide ref 18, pp. 403-411.
54. Folkhard, E. 1988. Welding Metallurgy
of Stainless Steels. Vienna, Austria, Springer-
Verlag.
55. Gooch, T. G., and Willingham, D. C.
1975. Weld Decay in Austenitic Stainless
Steels. Abington, Cambridge, TWl.
56. Stawstr6m, C., and Hillert, M. 1969.
An improved depleted-zone theory of inter-
granular corrosion of 18-8 stainless steel. JISI,
207: 77-85.
57. Bruemmer, S. M. 1990. Quantitative
modelling of sensitization development in
austenitic stainless steel. Corrosion 46(9):
698-709.
58. Nakao, Y., et al. 1992. Effect of delta
ferrite on sensitization of austenitic stainless
steel. Welding International 6 (7): 523-530.
59. Atteridge, D. G., et al. 1992. Model
predictions of HAZ (heat-affected zone) grain
boundary chromium depletion development
for austenitic stainless steel. 3rd International
Conference on Trends in Welding Research.
Gatlinburg, Tenn. ASM International, pp.
681-685.
60. Solomon, H. D. 1984. Influence of
W F I D I N I G R F ~ F A R C H ~1 ]PPl F M F N I T I 1 ~'~-~
composition on continuous cooling sensitiza-
tion of Type 304 stainless steel. Corrosion
40(2): 51-60.
61. Gooch, T. G. 1968. Corrosion of AISI
type 304 austeniti( stainless steel. Brit. Weld-
ingJ. 15(7): 345-357.
62. Danko, J. C. 1992. Stress corrosion
cracking of weldments in boiling water reac-
tor service. Stress Corrosion Cracking, R. H.
Jones, ed., ASM International, Materials Park,
Ohio, Chapter 15, pp. ~45-354.
63. Povi(h, M. J., and Rao, P. 1978. Low
temperature sensitization of welded ]~/pe 304
stain less steel. Corrosion 34(8): 269-275.
64. Beckitt, E. R., Bastow, B., and Glad-
man, 1. 1987. Effects of residual element con-
tents on corrosion resistance of Type 304L
stainless steels in boiling nitric acid. Stainless
Steels "87, York, U.K., Institute of Metals, pp.
234-246.
65. Ikawa, H., Nakao, Y, and Nishimoto,
K. 1977. Study on the knifeline attack phe-
nomenon in stabilized austenitic stainless
steels. Trans. Jap. Weld. Soc. 8(1 ): 918.
66. Lundin, C. D. 1991. Repair welding of
austenitic stainless steel castings preservation
of corrosion resistance. Proceedin~,s Mainte-
nance and Repair Welding in Power Plants,
Orlando, Fla, AWS, pp. 46-56.
67. Devine, T. M. 1980. Influence of car-
bon content on the ferrite morphology and the
sensitization of duplex stainless steel. EPRI
Workshop Report, WS 79-174, Vol. 1, Paper 5.
68. Truman, J. E. 1994. Stainless steels.
Corrosion: Metal/Environment Reactions, 3rd
edition, ed. by Shriver, L. L., Jarman, R. A. and
Burstein, G. T., Oxford, U.K., Butterworth-
Heinemann, 3:34 3:77.
69. Bond, A. ff 1969. Mechanisms of in-
tergranular corrosion in ferritie stainless steels.
Trans. Met. Soc. of AIME 245(8): 2127-2134.
70. Devine, T. M., and Ritter, A. M. 1983.
Sensitization of 12 wt-pct chromium, tita-
nium-stabilized ferritic stainless steel. Met.
Trans (4). 14(A) (8): 1721-1728.
71. Nichol, T. J., and Davis, I. A. 1978. In-
tergranular corrosion testing and sensitization
of two high chromium ferritic stainless steels.
ASTM STP 656: 179-196.
72. Hewitt, J. 1992. High chromium con-
trolled hardenability steels. Ist International
Chromium Steels and Alloys Congress, Cape
Town, South Africa, SAIMM, Vol. 2, pp.
71-88.
73. Gooch, T. G., and Ginn, B. J. 1990.
Heat-affected zone toughness of SMA welded
12%Cr martensitic-ferritic steels. Welding
Journal 69(11 ): 431 -s to 440-s.
74. Honeycombe, J., and Gooch, T. G.
1983. Corrosion and stress corrosion of arc
welds in 18% chromium-2% molybdenum-ti-
tanium stabilized stainless steel. Brit. Corr. J.
18(1): 25-34.
75. Liljas, M., Holmberg, B., and Ulander,
A. 1984. Welding of a high-molybdenum
austenitic stainless steel, vide ref 17: 323-329.
76. Charles, J., etal. 1994. A new high ni-
trogen austenitic stainless steel with improved
structure stability and corrosion resistance
properties. 10th Anniversary C~;nference: Cor-
rosion and Materials Offshore. Oslo,
NITO/NKF.
77. Liljas, M., and Stenwall, P. 199~. Weld-
ing of UNS $32654 - - corrosion properties
and metallurgical aspects, vide ref 24: 2882-
2894.
78. Charles, J. 1991. Superduplex stainless
steel - - structure and properties, vide ref 18:
3-48.
79. Potgieter, J. H. 1992. Influence of
sigma phase on general and pitting corrosion
resistance of SAF 2205 duplex stainless steel.
Brit. Corr. J. 27(3): 219-223.
80. Gunn, R. N. 1993. Unpublished work
at TWl, Abington, U.K.
81. Karlsson, L., Andersson, S. L., and
Huhtala, T. 1994. New Ni-base consumables
for welding of duplex and superduplex stain-
less steels, vide ref 25, Paper 42.
82. Chance, J., Coop, W., and Gradwell, K.
154-sl MAY 1996
J. 1982. Structure property relationships in a Stainless Steel. Florence, Italy, AIM,
25Cr-7Ni-2Mo duplex stainless steel casting 2.191-2.195.
alloy, vide ref 40, 371-398. 86. Johnsen, R., and Olsen, S. 1992. Expe-
83. Karlsson, L., Ryen, L., and Pak, S. 1995. rience with the use of UNS $31254 in seawa-
Precipitation of intermetallic phases in 22%Cr ter systems-- case histories from the field. Cor-
duplex stainless steel weld metals. Welding rosion "92, Nashville, Tenn., NACE, Paper 397.
Journal 74(1 ): 28-s to 40-s.
84. Huhtala, T., etal. 1994. Influence of W
and Cu on structural stability in superduplex
weld metals, vide ref 25, Paper 43.
85. Kondo, K., et al. 1993. Precipitation
behavior of sigma-related phases in 25%Cr
based superduplex stainless steels. Innovation