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Previously published in METALLOGRAPHY 18:215-225 (1985)

Characterization of the Weld Structure in a Duplex Stainless


Steel Using Color Metallography

D. E. NELSON

AND

W. A. BAESLACK 111

Depurtmerrt ,?f Wc/iing l?rrgirreerirrg,


The (lhio Stute University, Columbus, ohio 43210
ANO

J. C. LIPPOLLl

Sunuiu Nutionul Luboruroric.\, Li\wmwe, Cul(fiwri[i945S0

A three-step etching technique. utilizing a Glyceregia etch. a 10%oxalic acid electrolytic


etch, and a boiling P4urakamisreagent etch, was employed to reveal the weld structure in
a commercial duplex stainless steel alloy. Color metallography indicated that chromium
segregation, which i>residual from significant phase composition differences in the original
ferriteaustenite ba:,e metal structure, existed in all areas of [he weld heat-affected zone.
Evidence of fine ct romium-rich precipitates distributed homogeneouslywithin the ferrite
grains and heteroger ously at ferrite subgrain boundaries in the middle and near heat-affected

zone regions was ot)servecland correlated with local variations in chromium con(ent.

Introduction

Duplex stainless steels represent an important and expanding class of


stainless steels. The duplex ferriteaustenite microstructure exhibited
by these high-cllrom.iumalloys promote a desirable combination of properties, includin~:strength levels and stress-corrosion cracking resistance
superior to those of the 300-series austenitic stainless steels [1j. Such

property combinations have led to an increased application of these alloys


by the chemical andimarine industries.
Welding is an important method of fabrication for a variety of applications in which duplex stainless steels are used, and consequently it is
important to have an understanding of the weld structure. In the present

study, microstructural characteristics and phase transformations in the


467
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10N39:467--477
(1997)
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Nelson, Baeslack, and Lippold

468

weld zone of the commercial duplex stainless steel Ferralium 2551were


studied using a three-step etching technique and color metallography.
Experimental

MATERIALS
The plate material investigated was Ferralium Alloy 255 (UNS Number
S32550), a commercial, nitrogen-containing duplex stainless steel. The
alloy nominally contained 25 wt.% Cr, 5 wt.% Ni, 3 wt.% Mo, 2 wt.%
Cu, 0.20 wt.% N, and exhibited a solution-annealed (1038Cfollowed by
a rapid cool) microstructure containing approximately equal amounts of
the ferrite and austenite phases. Table 1 provides the actual base metal
chemistry for the alloy investigated.
Full-penetration, autogenous (no filler metal added) welds were produced on the 6.35-mm-thick plate material using the gas tungstenarc
welding process (Table 2). Subsequent to welding, specimens were sectioned transverse to the weld direction and mounted for metallographic
examination.

TABLE 1
Chemical Analysis of Ferralium Alloy 225 (Wt.%)
Manganese
Silicon
Chromium
Nickel
Molybdenum
Titanium
Magnesium
Calcium
Copper
Aluminum
Cobalt
Carbon
Sulfur
Phosphorus
Nitrogen

1.05
0.51
24.90
5.39
3.13
o. I 1
0.13
0.0027
1.72
0.99
0.22
0.27
below 0.001
0.023
0.17

Registered trademark of the Cabot Corporation.

Color Met. Chatucterization of Stainless Weld

469

TABLE 2
C;asTungstenArc Welding Parameters
Current
Voltage
Travel spexi

180amperes
17 volts
2,5 mmls

Electrode-t mwo]rkdistance
Electrode
Electrode diameter
Shielding gas

2.5 mm
Thoriated tungsten, 60 included angle
2.38 mm

Flow rate (torch)


Flow rate (trailing)

Argon
0.29 liter/see
0.53 liter/see

METALLOGRAPHIC TECHNIQUES

A three-step etching technique was used to reveal the microstructure


and to deposit al interference film on various phases for color metallography. The specimen was initially etched using a Glyceregia solution consisting of 30 parts hydrochloric acid, 20 parts glycerin, and 10parts nitric
acid. This initia etch preferentially attacked the ferrite phase, thereby
allowing clear delineation of the austenite phase morphology. Secondly,
an electrolytic etch of 10f%oxalic acid was given to better reveal grain
boundaries and lineprecipitates. Finally, the specimen was immersed in
boiling Murakamis reagent (10 g permanganate and 10 g potassium hydroxide in 100 ml water) for 10 min in order to produce an interference
film. Color photographs were obtained using an optical metallograph. In
order to relate the observed colors to the actual local compositions, electron-microprobe point analyses were conducted at selected regions on the
specimens.

Results and Discussion

The evolution of weld fusion and heat-affected zone (HAZ) microstructure is often difficult to understand due to the rapid heating and cooling
rates associated with the fusion welding process. In the case of the duplex
stainless steels, 1he process is further complicated by the transient phase
stability of the ~erriteand austenite in the temperature range between
room temperature and the melting point of the alloy. An equilibrium phase
diagram, although not rigorously applicable, is often useful as a means
for revealing the orig;inof the weld microstructure.

Nelson, Baeslack, and Lippold

470

1 200 pm I
FIG.1. Opticrd micrograph of fusion boundary region. Arrows indicate approximate fusion boundary.

40pm

FIG.2. Optical micrograph of unaffected base metal. Note the directionally oriented
white austenite (y) and blue ferrite (8) phases.

...

471

I 40 pm

FIG.3. Optical micrographof far HAZ. B1ueand brown areas are ferrite(8), white areas
are austenite (y).

I 40 Mm J

FIG.4. Opticalmicrclgraph
ofmiddleHAZ.Austeniteplateausareindicatedbylarge
arrows.Notewhiteausteniteat ferritegrainboundaries
andsmallprecipitates
at ferrite
subgrainboundaries
(smallarrows).

Nelson, Baeslack, and Lippold

472

Ferralium 255 is a multicomponent alloy consisting of alloying elements


that can be separated into those that stabilize either the ferrite (Cr, Mo,
Si, Ti, Al) or the austenite (Ni, Mn, Cu, N, C) [2]. As a consequence,
the FeCrNi ternary system provides a simplifiedapproach for studying
phase stability in the duplex stainless steels. A vertical section of the
ternary system at 60 wt.$%Fe (a pseudo-binary section) is shown in
Fig. 5. A nominal composition, denoted as COin Fig. 5, has been chosen
as representative of the Ferralium 255 alloy. The diagram predicts that

1600

II

LIQUID

~/

1 2600

=y+~+L

1400

1---=2200

1200
-.
0
u
~ 100a
1<
a

L
o

u
a
z
2

\
000

# /

600

- -:

---q------\I
I

Y+u

, y+~+(J

- 1000
;

40C

a
w
a

1400 :

If
/

w
- 1800 ~
1<

:0

:
1

60 % I RON

15

20

25

30

35

40

25

20

15

10

WT ~

Cr

WT b Ni

FIG. 5. Verticalsection of an Fe-Cr-Ni phase diagram at Wo Fe. COcomposition line


represents Ferralium Alloy 255. (From ref. 3 with permission.)

Color Met. Characterization of Stainless Weld

473

the alloy of composition C~jsolidifies as delta ferrite, and then cools


through a single-phase ferrite region before entering the two-phase austenite plus ferrit: phase field. The resultant fusion zone microstructure
would consist of a mixture of ferrite and austenite.
Evolution of the H.AZmicrostructure is more complicated and depends
upon several faclors, including the original base metal microstructure, the
peak temperature experienced by the particular HAZ region, the time
duration at peak temperature, and the rates of heating and cooling. The
solution annealir.g heat treatment at 1038Cresults in approximately equal
proportions of austenite and ferrite whose compositions are roughly predicted from the ~hase diagram by the SOIVUS
lines at the solution annealing
temperature. Sirce the width of the two-phase region is relatively large,
the different in composition between the ferrite and austenite should be
signiilcant (assuming that the composition tie lines lie in the plane of Fig.
1 and there is sufficient time to reach the equilibrium compositions).
The phase diagram in Fig. 5 predicts that at least two distinct microstructural regions should be generated in the HAZ of a duplex stainless
steel weld. One regicm, situated adjacent to the fusion line, would result
from heating into the single-phase ferrite region between approximately
700Cand the .sCdidu:s
temperature. The diagram predicts that this region
of the HAZ would transform entirely to ferrite upon heating and then reform austenite upon cooling to room temperature. A second HAZ region,
further from the fusion line, represents that portion of the HAZ heated
into the two-phase field above the solution annealing temperature. Again,
the phase diagram in Fig. 5 would predict that the proportion of ferrite
to austenite should increase as a function of increasing temperature in
this range. Much of this ferrite should revert to austenite upon cooling.
Since the heating and cooling rates in the fusion zone and HAZ of
conventional welds a:rerelatively high, the microstructure in these regions
is nonequilibrium in nature. Diffusion in the austenite is relatively sluggish
[4, 5] even at temperatures above the solution annealing temperature. As
a result, transformation of the austenite and/or homogenization of the
ferrite may be incomplete relative to the behavior predicted by the phase
diagram.
The low-magnification micrograph in Fig. 1 illustrates the weld fusion
boundary region between the base metal and the fusion zone. Differences
in the colors observed in various regions of the microstructure are attributed to differences in the thickness of the interference film that exists
on the specimen surface. As the film becomes progressively thicker, the
color changes from yellow to brown and finally to blue [6]. The following
paragraphs will describe each of the regions in this structure.

Nelson, Baeslack, and Lippold

474

40pm

FIG.6. Optical micrograph of near HAZ. Note appreciable ferrite grain growth. Arrows
indicate the weld fusion line.

I 40pm

I
FIG. 7. Optical micrograph of fusion zone. Arrow indicates fusion zone grain solidification direction.

Color Met. Characterization of Stainless Weld

475

BASE METAL
The rnicrograph in Fig. 2 illustrates the directionally oriented austenite
(white) and ferrite (blue) phases that exist in the unaffected base metal.
Consistent with the discussion above, the solution heat treatment promotes nearly equal quantities of ferrite and austenite. Electron microprobe analysis cf this structure shows that considerable alloying element
partitioning exists between the phases (Table 3), with the ferrite being
substantially enriched in chromium and depleted in nickel as compared
with the austenite.
HEAT-AFFECTED ZONE
In the far HAZ (Fig. 3), peak temperatures are sufficiently high to
promote a partial transformation of austenite to ferrite. The yellow and
brown ferrite regions surrounding the white austenite represent areas that
were originally austenite in the base metal microstructure, or possibly
ferrite adjacent to the original ferriteaustenite interface. Although these
austenite regioris are transformed to ferrite, and retained as ferrite on
cooling, there is insufficient time during the weld thermal cycle to diffuse
the chromium throughout the entire ferrite phase. Consequently, the
colors exhibited by these regions represent a transition between the blue,
chromium-rich original ferrite region cores and the white, chromium-poor
austenite. Microprobe analysis data for the ferrite and austenite in this
region differ little from those for the unaffected base metal (Table 3).
In the middle HAZ, nearly all of the austenite that exists in the roomtemperature microstructure transforms to ferrite on heating, the only exTABLE 3
Electron-hlicroprobe Analysis of Base Metal and HAZ Regions (Wt.%)
Near HAZ

F:rrite
Ferrite
(hlue)
(yellow)

Chromium
Nickel
Molybdenum
Silicon
Manganese
Copper

Far HAZ

Base metal

Ferrite
(blue)

Austenite
(white)

Ferrite

Austenite

(blue)

(white)

24.8
6,2
2.6
0.4

27.35
4,4s
3.49
0,44

23.05
7.37
2.19
0.36

I.10
1.35

I,15
2.05

26.4
~,~
3.2:
0,44

24.9
6.2
2.8
0.42

27,3
4.7
3.6
0.44

1.16
1.48

1.25
1.65

1.09
1,19

Ferrite that wa: originally austenite (see Fig. 6)

I,21
1.67

Nelson, Baeslack, and Lippold

476

ception being the small plateaus of austenite shown by the large arrows
in Fig. 4. This austenite dissolution allows the formation of large, nearly
equiaxed ferrite grains. Note, however, that although high temperatures
have been reached, distinct similarities still exist between the blue areas
in the middle heat-affected zone microstructure and the ferrite morphology in the original base metal, suggesting that chromium diffusion is limited. On cooling, austenite nucleates in the form of nearly continuous
grain-boundary allotriomorphs and to a lesser extent intragranularly in
regions of low chromium where austenite originally existed. In addition,
austenite grows epitaxially from the few plateaus of austenite that did
not completely dissolve at peak temperatures.
Evidence of fine precipitation is also observable in Fig. 4, both homogeneouslywithin the ferrite grains and heterogeneouslyat ferrite grain
and subgrain boundaries. Previous work [7] suggests that the precipitates
are CrzN. Since the proportion of austenite decreases with increasing
temperature, the amount of nitrogen dissolved in the ferrite must increase.
On cooling, supersaturation occurs and the nitrogen would be precipitated
primarily in the chromium-rich blue regions of the ferrite grains as CrZN.
In the near HAZ (Fig. 6), the alloy is transformed entirely to ferrite at
peak temperatures and significant grain growth occurs. As in the middle
HAZ, austenite forms on cooling at ferrite grain boundaries and occasionally within the grains. It is of interest to note that the fine precipitation
is less in regions near austenite, even if the region is chromium enriched,
suggesting that the austenite may provide a sink for nitrogen in the matrix.
It is also important to observe that the color pattern in the base metal
still remains to a degree in the region, although it appears more diffuse.
In the preceding discussion, a correspondence of different colors in
the HAZ regions with chromium segregation has been indicated. As in
the unaffected base metal and far heat-affected zone, blue areas correspond with chromium enrichment that is residual from the original base
metal ferrite (Table 3). Brown and yellow regions correspond to lower
chromium ferrite and white areas correspond to austenite with a low chromium content.

FUSION ZONE
The fusion zone region is illustrated in Fig. 7, and generally consists
of columnar ferrite grains with substantial amounts of austenite both at
grain boundaries and within the grains. Differences in the respective quantities of austenite and ferrite between the fusion and near heat-affected
zones appear to be greater than would be expected, since these regions
experienced comparable cooling rates. The reason for this difference is

..-

Color Met. Characterization of Stainless Weld

477

not clear. From the photomicrograph in Fig. 7, chromium segregation


resulting from nonequilibrium solidification of the fusion zone is barely
evident within the ferrite grains as faint blue lines oriented parallel to the
grain growth direction.
Summary

Color metallography has been used to characterize the microstructure


exhibited by thf composite weld structure in a duplex stainless steel. A
three-stage etch,ng treatment allows the clear delineation of both specific
phase morphologies and the chromium microsegregation. Microstructural
variations in the duplex structure between the unaffected base metal and
the fusion zone are fsignificant,and can be related primarily to the wide
range of peak temperatures and the rapid heating and cooling rates experienced during the weld thermal cycle.
References
1. T. G. Gooch, Wwiabihty of duplex ferriticaustenitic stainless steels, in Dup/ex Stainless.!
.$rds (R. A. Lola, cd.). American Society for Metals, Metals Park, Ohio (1983). pp.

573602.
2. F. C. Hull, Effects of composition on embrittlement of austenitic stainless steels, Welding
.JOWWUI
52:104s- 113(1973).
3. J, C, Lippold an.i W. F. Savage, Solidification of austenitic stainless steel weldments:
Part IA propo:ed mechanism, We/din#.J,~urna/58:361s-374s (1979).
4. R. A, Perkins, R. A. IPadgett,and N, K, runala. Tracer diffusion of 9Fe and 51Crin
Fe-17 wt pet. CI-12 wt pet. nickel austenitic alloy. Me[u//ur#ica/ Tran.\utrion.\4:25352540(1973).
5, R. A. Perkins. f[acerdiffusion of b3Niin Fe17 wt. pet. Cr12 wt pet. Ni, Meta/lur~ica/
Tran.suctiotrs4:1065-1669(1973).
6. E. Beraha and B. Shpigler. Co/or Me/a//ograph}. American Society for Metals, Metals
Park, Ohio (1977).pp. 321.
7. G. Herbsleb and P. Schwabb, Precipitation of intermetallic compounds, nitrides and
carbides in AF t 2 duplex steel and their influence on corrosion behavior in acids, in
Dup[e.r Sfairr/e,\s,\Stee[s (R. A. Lula, cd.), American Society for Metals, Metals Park,
Ohio (1983),pp. 15401.