ELSEVIER

Microstructural
Evolution during Solidification
of Austenitic Stainless Steel Weld Metals:
A Color Metallographic and Electron Microprobe
Analysis Study
K. Rajasekhar, C. S. Harendranath,+ R. Raman, and S. D. Kulkarni
*Department of Metallurgical Engineering and Materials Science and tRegional Sophisticated
Instrumentation Center, Indian Institute of Technology, Powai, Bombay, 400 076, India
Structural evolution
role in solidification

during solidification of austenitic stainless steel welds plays a crucial

cracking and microsegregation.
Currently, there is no unambiguous

method available to study the solidification

mechanism

in detail. The present investigation

was undertaken to explore the potential of color metallography for revealing solidification
structures. Weld composition was altered by adding varying amounts of nitrogen such that
its location with respect to the phase diagram is moved in a specified direction. The controlled variations in the solidification mechanism thus brought about were studied metallographically, using Berahas etchant and electron microprobe analysis. Metallographic studies complemented by electron probe microanalysis demonstrated color metallography to be
a highly useful, simple, and reliable technique for revealing solidification structures. Color
etching enables the quantitative estimation of high-temperature phases in the ferritic-austenitic mode of solidification.
It also reveals the three-phase reaction mechanism in the
(L+S+ y) region in detail. In fully austenitic structures, color etching reveals the growth
patterns of cell structures and the effective interface area where impurities
segregate.
0 Elsevier Science Inc., 1997

are expected to

now recognized that the sequence of solidification, rather than the retained ferrite content, is more relevant to cracking behavior
[l, 21. More significantly, the phase balance
and evolution of the structure during solidification play a critical role [2]. It has also
been found that different magnitudes of
phase balances at high temperatures can
give rise to the same room-temperature ferrite values [3] but with differences in cracking
susceptibility. The central issue in the assessment and control of solidification cracking
during the welding of stainless steel, therefore, is to obtain knowledge of the structural
evolution during solidification.
The conventional
metallographic
approach, wherein the ferrite location is used

INTRODUCTION
A major problem in the welding of austenitic stainless steels is their tendency to crack
during solidification, popularly known as
solidification cracking. Conventionally, this
problem has been handled by maintaining
some amount of ferrite in the microstructure, which effectively improves the cracking resistance. But, at the same time, the
presence of ferrite in an austenitic structure
causes numerous other problems, such as
lower toughness (more pronounced at cryogenic temperatures), deterioration of corrosion properties, brittle intermetallic phase
formations at high service temperatures,
and so forth. Through extensive studies, it is
53
MATERIALS CHARACTERIZATION 38~53-65 (1997)
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655 Avenue of the Americas, New York, NY 10010

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54

K. Rajasekhar et al.

as an indicator of the solidification mode, is

unable to provide information about the high
temperature structure features. Berahas [4,5]
tint etchant suitably modified by Lichtenegger and Bloch [6] is known to act as a
primary etchant for stainless steel weldments responding to segregation in the solidification structure. Lichteneggers modification consisted of completely eliminating
HCl from the etchant formulation, because
HCl attacks ferrite in y-6 welds, which lead
to poor etching results. More recently, Thier
et al. [7] have used a color etching process
to differentiate between primary and secondary ferrite, corresponding to ferritic and
austenitic modes of solidification. However,
the colors developed have been interpreted
vaguely or ignored completely. For this
reason, the problem of visualizing structural evolution remains unresolved.
The present investigation, therefore, was
undertaken to explore the potential of color
metallography
in revealing high-temperature structures, with particular emphasis
on the quantitative estimation of phases
present at high temperatures and the precise mechanism
that takes place in the
(L + 6 + y) three-phase region.

SOLIDIFICATION

MECHANISM

A summary of the current knowledge of solidification mechanisms is presented in this

section to facilitate the descriptions
and
discussions in subsequent sections.
Nonequilibrium
conditions
prevailing
during weld metal solidification
and the
presence of alloying elements other than Cr
and Ni limit the use of available phase diagrams (such as the ternary Fe-Cr-Ni diagram)
for assessing the solidification sequence.
However, experimental investigations using
directional solidification, weld pool quenching, and so forth, followed by microscopical examination
and electron probe microanalyses,
established
the following
mechanisms for stainless weld metal solidification [8-121. The various mechanisms
proposed were related to chemical composition, as shown below.

L+-(L+y)+y
(Cr,,/N&)

< 1.25l

(A mode)

L+(L+y)-+(L+y+Z)+(y+@
1.25 < (Cr,,/Ni,,)

< 1.48

(AF mode)

< 1.95

(FA mode)

L+(L+6)+(L+Zi+y)--+(y+6)
1.48 < (Cr,,/Ni,,)
L+(L+6)+6+(y+6)
(Cr,.,/Ni,,)

> 1.95

(F mode)

Relative positions of the various modes

of solidification
on a pseudobinary
diagram, the resulting ferrite morphologies,
and the associated direction of microsegregations are illustrated
in Fig. 1. Even
though both AF and FA modes contain
some ferrite in the room-temperature
structure, the cracking susceptibility
is totally
different in both cases. The FA mode provides the best resistance to cracking, whereas
AF-mode alloys are highly susceptible to
cracking similar to that of A-mode solidified structures. Within the FA mode of solidification, structural evolution plays an
important role. The three-phase reaction
(L+6+ y) in the Fe-Cr-Ni ternary system is
peritectic at one end and eutectic at the
other. Even though it is stated that, at about
75% Fe, the peritectic reaction changes to
eutectic, the actual mechanism of three-phase
reactions is not clear to date, and most often it is referred to as peritectic/eutectic.

EXPERIMENTAL
METHODOLOGY

PROCEDURE
AND WELDING

Required compositions of welds were obtained by a planned set of experiments. Although the mode of solidification is mainly
a function of the Creq/Nieq ratio, the total

Thromium equivalent (Cr,,) = % Cr + % MO + 1.5%

Si + 0.5% Nb. Nickel equivalent (N&) = % Ni + 30 %
C + 0.5% Mn. The estimated value 1.25 is based on the
0 FN line of WRC-1992 constitution diagram [13] at a
chromium equivalent of 20, and the other two ratios
(1.48 and 1.95) are according to Suutala et al. [14].
A, austenitic; F, ferritic.

55

Austenitic Stainless Steel Welds

Ni*

\
\
SOLIDIFICATION

Eutectic

* Cr

\PRIMARV F\ERRITE
SOLIDIFICATION
\
\

Skeletal

Widmanstatten

FIG. 1. The respective locations of various modes of solidification on a constant iron vertical section of Fe-CrNi ternary diagram, resulting room-temperature
structures, and the direction of microsegregations
during solidification [l, 101.

alloy content of a particular weld has an

important role in the overall mechanism of
solidification. Hence, the total alloy content
(Cre4+Ni,,) was varied by using suitable
combinations
of AISI 304 base plate and
various filler materials
such as E308L
(20Cr/lONi), ER312 (30Cr/lONi) and doping of pure Ni powder in some cases. In addition, the Cr,/N&
ratio of the weld pads
was varied by adding controlled amounts
of nitrogen, a powerful austenite stabilizer.
Resulting
compositions
of the different
welds prepared are given in Table 1.

Intended levels of nitrogen were achieved

by using Ar+Nz shielding during mechanized gas tungsten arc welding. In the FA
mode of solidification, the composition was
altered to move Cr,,/N&, ratios from 1.95 to
1.48 so as to vary the proportion of hightemperature
phases. Obtaining a precise
variation by adjusting the main alloying elements, Cr and Ni, is difficult owing to the
narrow range. More importantly, nitrogen
being an interstitial solute with a high diffusion rate helps in attaining the equilibrium phase balance, which is not possible

56
Table 1

K. Rajasekhar et al.
Chemical Composition (wt%) of Various Alloys Studied
&Ferrite
C

Cr

Fig. Z(a)

0.09

24.6

8.8

1.7

0.43

Fig. 2(b)

0.04

18.8

8.6

1.6

0.38

Sample

Ni

Mn

Si

0.07

Creq/Nieq

(%J

2.05

30

1.69

7.8

Fig. 2(c)

0.03

18.4

13.0

0.73

0.74

1.37

1.6

Fig. 2(d)

0.09

24.6

8.8

1.7

0.43

0.60

1.29

Nil

Fig. 3(a)

0.04

18.8

8.6

1.6

0.38

0.11

1.62

5.7

Fig. 3(b)

0.04

18.8

8.6

1.6

0.38

0.30

1.36

Nil

0.21

1.48

1.2

1.40

2.5
4.8

Fig. 7(a)

0.04

18.8

8.6

1.6

0.38

Fig. 7(b)

0.10

30.0

18.0

1.7

0.39

Fig. 7(c)

0.03

18.4

10.8

0.73

0.74

1.63

Fig. 7(d)

0.09

24.6

8.8

1.7

0.43

0.45

1.50

1.5

Fig. 9(a)

0.04

48.8

8.6

1.6

0.38

0.30

1.36

Nil

Fig. 9(b)

0.09

24.6

8.8

1.7

0.43

0.60

1.34

Nil

*Nickel equivalent coefficient of nitrogen is taken as 12 for solidification shuctures [15]. High amounts of nitrogen produced the A
mode directly from the FA mode, eliminating the intermediate AF mode [Figs. 2(d) and 9(b)].

with the substitutional type of alloying elements, Cr and Ni.

Shielded metal arc welding (SMAW), gas
tungsten arc welding (GTAW), and gas
metal arc welding (GMAW) processes were
used for obtaining various weld pads. In
the case of GTAW and GMAW, the welding torch was mounted on a variable-speed
trolley to have better control over welding
parameters. Required amounts of nitrogen
were obtained by varying the partial pressure of nitrogen in the Ar-N2 shielding gas
[15] during GTAW. All nitrogen-modified
welds were analyzed for nitrogen, using a
Leybold-Heraeus
NOA 2000 analyzer. The
room-temperature
S-ferrite values were estimated by using a Fischer ferritescope.
METALLOGRAPHY
The composition
of Berahas etchant, as
modified by Lichtenegger et al. [6], is 0.5g
K2S2O5 and 2O.Og N&FHF
in 1OOml distilled water. One of the difficulties often reported, and faced during the current study,
with the color etching process is the inconsistency in the development of coloration.
The severity of the problem called for some
experimentation
on the etching process itself. Study of various parameters such as
etching temperature, time, stirring, specimen surface condition, and the composi-

tion and pH of the etching solution revealed that the as-prepared

pH of the
etching solution varied between 2 and 3
with batch-to-batch variations of N&FHF
used to make the etchant. A pH value
maintained at about 2.5, by using either
N&OH or HNOs, helped to achieve consistent coloration.
Freshly prepared solutions were contained in plastic beakers. Because the etchant
contains ammonium bifluoride (which attacks glass), plastic beakers were used. Specimens, suspended from above, were immersed in the solution typically for 5 minutes
at room temperature. The solution was gently stirred, using a magnetic stirrer, throughout the etching period. The specimens were
observed with the light optical microscope,
using the bright-field mode at magnifications up to 1000 X .
ELECTRON

MICROPROBE

ANALYSIS

Microstructural examination and high-resolution microprobe

X-ray analysis were
carried out with the use of a Cameca SUSEM scanning electron microprobe. Specific regions of interest were marked with
micromdentations
to facilitate microprobe
analysis. A highly regulated electron beam
(stability better than 0.1%) having a probe
size c 0.2pm was used. Microprobe analysis

Austenitic Stainless Steel Welds

was carried out with the use of an inclined
wavelength-dispersive
spectrometer.

RESULTS

AND DISCUSSION

IDENTIFICATION
OF THE MODES
OF SOLIDIFICATION
Various modes of solidification
as developed by color etching are shown in Fig. 2.
The Cr,/N&
ratios of the weld samples
represented by Fig. 2(a-d) correspond to
the respective regions F, FA, AF, and A of
the phase diagram shown in Fig. 1. Both
the extreme structures, types A and F (i.e.,
either fully austenitic or fully ferritic solidifying structures) can be identified from
their
straightforward
final microstructures. The ferritic mode of solidification results in WidmansMten
austenite in a matrix; whereas, in the austenitic mode, the
absence of any further transformations
re-

(a)

57

tains growth morphologies of solidification

as they are, down to room temperature.
However, both AF and FA modes contain
some ferrite in the final microstructure and
require some care when identifying the
mode of solidification.
Ferrite present in
dendrite centers represents the FA mode,
whereas interdendritic
ferrite represents
the AF mode. Well-developed
solidification cell structure by color etching facilitated the identification of the FA and AF
modes.
The interpretations
based on metallography alone were further confirmed by
studying the concentration profiles developed by electron probe microanalysis. Figure 3(a,b) shows the concentration profiles
across solidification
cells of two samples
that were interpreted to have solidified in
ferritic and austenitic modes. The distributions of Cr and Ni were examined by using
the approach suggested by Brooks et al. [16]
to distinguish the modes of solidification.

(b)

(d)
FIG. 2. Various modes of solidification observed in austenitic stainless steel welds as revealed by color etching: (a)
F mode; (b) FA mode; (c) AF mode; (d) A mode.

K. Rajasekhar et al.

58

Accordingly, the Ni-depleted cell cores in

Fig. 3(a) and the alloy-enriched intercellular regions in Fig. 3(b) show them as ferritic
and austenitic modes, respectively,
and
confirm the color metallographic interpretations. The next two sections contain a
brief description of the etchant behavior for
individual samples.

In general, the process of chemical etching

can be described as accelerated corrosion
with different rates of attack on different
phases. The difference in electrochemical
potentials of the microstructural
constituents causes a subdivision of the exposed

(a)

(b)

MECHANISM

OF ETCHING

FIG. 3. Concentration profiles of Cr and Ni across (a) a primary ferrite dendrite and (b) a primary austenite cell.
Nickel-depleted dendrite cores of primary ferrite and enrichment of Cr and Ni in intercellular regions of primary
austenite confirm the modes of solidification. Sample (a) is AISI 304 weld with 0.11% [N], and sample (b) is AISI
304 weld with 0.30% [N].

59

Austenitic Stainless Steel Welds

specimen surface into a network of very
small anodic and cathodic regions. Specifically, microsegregations
that occur during
solidification
produce variations
in the
electrochemical
potential of the structural
features. During the process of etching
with Berahas reagent, sulfide films in the
thickness range of 40-500nm are precipitated on the anodic areas. Films thus
formed produce interference
color when
viewed with the light microscope.
The
color developed is a function of the film
thickness at that location, and the color
changes in the following order as the thickness of the film increases:
Yellow + Red + Violet + Blue + Green
This sequence of coloration is a function
both of time of immersion and of the degree of proneness of the substrate surface
to attack. More-anodic areas go through the
sequence faster. However,
as the film,
which grows epitaxially, forms, the rate of
attack drops. Hence to get differentiation of
phases, the choice of immersion time is critical. A properly tint-etched specimen will
indicate, through the colors developed, the
regions of greater or lesser anodic activity.
DESCRIPTION OF
OBSERVED STRUCTURES
In the F-mode structures [Fig. 2(a)], austenite developed coloration, whereas ferrite remained unaffected. Because austenite in duplex structures is leaner in
chromium owing to partitioning, it becomes anodic, with respect to ferrite,
which is richer in chromium and remains passivated in the etching process.
A-mode [Fig. 2(d); a different sequence is
followed owing to the complexity
of
etchant behavior] structures, which are
fully austenitic, are depleted in Cr and Ni
in the cell cores, whereas the interdendritic regions are enriched by both alloying elements, making them cathodic. The
photomicrograph shows a part of a dendrite and some cut sections of secondary
arms. Dendritic regions have developed
green coloration, whereas interdendritic
regions are totally unaffected.

In a similar manner, the cellularldendritic structure of austenite is seen with

greenish centers in the AF-mode micrograph [Fig. 2(c)]. The intensity of the color
gradually decreases at cell borders, indicating the rising concentration of alloying
elements. The ferrite formed in the interdendritic areas remained unaffected and
is seen as distinct white zones. It is believed that the sharp rise in chromium
content makes ferrite more passive and
supports cathodic reaction.
The remaining FA-mode structures [Fig.
2(b)] are more complex, with a range of
colors seen in the structure. The area represented by the micrograph has undergone columnar dendritic growth. The
complexity of the structure arises from
the fact that, after a certain amount of the
liquid precipitates
as ferrite, austenite
precipitation
occurs through a peritectic/eutectic reaction (L+&+L+6+y).
This
changes the direction of microsegregations, as shown in Fig. 1. Moreover, the
subsequent solid-state transformation of
6+y causes additional partitioning, altering the existing concentration profiles.
The unaffected skeletal structure located
in dendrite cores is ferrite. Owing to austenite precipitation in the (L+S+y) stage,
the interdendritic
regions are enriched
with both Cr and Ni, compared with the
immediately adjacent regions. This is revealed by the yellow/red colorations of
the interdendritic regions compared with
the adjacent green regions.

IDENTIFICATION
HIGH-TEMPERATURE
BOUNDARIES

OF
PHASE

Of the four modes of solidification, the FA

mode is the most important. This is because
most of the austenitic stainless steel welds
are devised such that they undergo the FA
mode of solidification to overcome the hot
cracking problem. At the same time, the FA
mode happens to follow the most-complex
sequence of solidification, as explained earlier. In this mode of solidification, identification of the exact location of the onset of

K. Rajasekhar et al.
261

18

Nickel
t

16
14
12 I,II.II
0

4
Distance

in

microns

10

12

FIG. 4. Distribution of Cr and Ni across a primary ferrite dendrite determined by high-resolution analytical
microscopy. Analysis was from the core of the dendrite to the interdendritic region [typical direction is
marked on Fig. 3(a) Ni trace]. Arrows indicate the location of the interface betweentwo colors.

the peritectic/eutectic
reaction is essential
for estimating the high-temperature
phases
that affect weldability. For this reason, AISI
304 weld metal was alloyed with nitrogen
so as to shift the position of the alloy within
the FA region of Fig. 1, which will eventually vary the equilibrium S-y phase balance.
Deliberate variations thus obtained were
used to study the behavior of the color
etchant.
The portion of green dendritic regions
shown in Fig. 3(a) varied systematically
with variations in the nitrogen content of
AISI 304 weld metal. The rather systematic

variation in the proportion of different colorations with varying C%,/NL,, ratios indicated that the colors developed could
correspond to the delta and gamma phases
at the solidification temperature. To clarify
this, the specimen shown in Fig. 3(a) and
other nitrogen-added samples were further
analyzed by using high-resolution microanalysis. Analysis was typically carried out
across a single dendrite, starting from the
skeletal ferrite located at the dendrite center and progressing to the interdendritic region.
Typical profiles of Cr and Ni concentrations across a dendrite of a specimen with
0.21% nitrogen are shown in Fig. 4. The
most important observation of these profiles is the occurrence of a clear maximum
in nickel content and a minimum in chromium content at the green/yellow interface
marked with arrows in Fig. 4. Similar observations were made in other samples as
well and are shown in Fig. 5.
The consistent occurrence of this phenomenon can be explained as follows. Ferritically solidified alloys exhibit nearly uniform compositions
immediately
after the
completion of solidification owing to the
high diffusivities of alloying elements in
ferrite [8]. However, the subsequent solidstate transformation of ferrite into austenite
leads to a cored structure because of the
partitioning of alloying elements across the
6-y interface. The magnitude of this coring
can be estimated on the basis of the solvus

Chromium

1.0

2.0

Distance

3.0
in

4.0

5.0

microns

m
Distance

in microns

Distance

.
in

microns

FIG. 5. Variation of Cr and Ni across the color interface in AISI 304 weld metals containing varying amounts of nitrogen (arrows indicate the location of the interface between two colors): (a) 0.09% [N]; (b) 0.11% [N]; (c) 0.22% [N].

61

Austenitic Stainless Steel Welds

lines of austenite and ferrite in the Fe-Cr-Ni

pseudobinary diagram [lo]. Figure 6 shows
a modified
schematic
representation
of
both solidification segregation and the partitioning during the 6-+y transformation. It
is assumed that coring is similar to nonequilibrium solidification of the type wherein
diffusion is negligible in the solid and only
diffusional mixing takes place in the liquid
[S] as solidification
progresses. This assumption is based on the fact that the diffusion rate of solute elements in a-ferrite is
very high compared with that in austenite.
Because of this fact, the ferrite side of the
transformation
allows an extensive distribution of alloying elements, whereas a negligible amount of diffusion occurs in the
austenite side. For the same reason, the
fraction solidified as austenite through the
peritectic/eutectic
reaction retains the segregations down to room temperature.
As seen from Fig. 6, the high-temperature
interface between delta and gamma is represented by a dip in chromium concentration and a peak in nickel concentration.
This is similar to the behavior exhibited by
the experimental results of microanalysis
across the two color interfaces. So it can be
concluded that the green/yellow interface

Dendrite
4

b
Core

Boundary
Retained

i\

\\
\.

Chromium

s
.z
P
9
;

Nickel

/,
A/,
!.i
.

./ ,.*
6

_.H

: *.
GA.1
i
L_-

_,_ d
I-

FIG. 6. Diagram showing the direction of microsegregations in the room-temperature

structures of welds
solidifying in the FA mode. Dashed line represents the
solidification segregations and the dot-dash line represents the partitioning that occurs during the subsequent solid-state 6+y transformation.
The onset of
the peritectic/eutectic
reaction is marked by arrows.

of the micrograph represents the onset of

the peritectic/eutectic
reaction.
THREE-PHASE
REACTIONS
FE-CR-N1 ALLOYS

IN

Findings such as the one that alloy compositions that pass through the eutectic triangle are more resistant to cracking for FAmode alloys suggested that the mechanism
of the three-phase (L+S+ y) reaction has
high practical significance [2]. Some alloy
compositions close to the eutectic triangle
and with different amounts of total alloy
content were studied to identify various
mechanisms.
Figure 7(a) represents an AISI 304 weld
alloyed with nitrogen (0.21%) that lies very
close to the eutectic triangle. During solidification of this specimen, the primary precipitation of ferrite was enveloped by austenite
precipitation (at the gray/green interface),
and further transformations, L+y and S+y
proceeded at the respective interfaces. The
rest of the solidification competed with austenite growth. This type of growth mechanism can be schematically represented as
shown in Fig. 8(a), in which the liquidus
(TL), peritectic (TP), and the solidus (TJ temperatures are indicated. In alloys having
the Creg/Ni,, ratio delicately balanced at
the transition point between AF and FA
modes, both austenite and ferrite dendrites
are observed side by side in the microstructure. Figure 7(b) shows a typical structure
of this kind, often referred to as a eutectic
structure. But these structures are totally
different from the normally observed aligned
eutectic structures that grow together by
cooperative mechanisms or divorced eutectics. Essentially, this type of composition
precipitates in different modes at different
locations of the weldment on a macroscopic
scale and represents only the transition
structures.
Figure 7(c) shows the structure of type
308L weld metal in which b-ferrite is seen
in both the dendritic and the interdendritic
regions. Solidification
in this case starts
with the precipitation of ferrite; as the temperature is lowered, austenite becomes

(a)

(b)

(d)
FIG. 7. Microstructural
evolution in the (L+S+y) three-phase region: (a) solidification of type 304 weld metal in
the eutectic triangle; (b) simultaneous precipitation of 6 and y; (c) interdendritic ferrite in the FA mode of solidification; (d) FA mode of solidification in a high alloyed weld.

more stable and envelops the precipitated

ferrite. As the austenite grows, microsegregations cause the liquid to become enriched
with ferrite-stabilizing Cr to a slightly greater
extent than with nickel; as a result, the solidification changes back to the ferritic mode

during the last stages. Another feature of

this structure is that both interdendritic ferrite and dendritic ferrite are connected at
some places. This indicates that austenite
does not envelop ferrite completely during
the assumed peritectic reaction, and perhaps

(a)

(b)

FIG. 9. Variation in the proportion

of dendritic to interdendritic

regions, depending

on the total alloy content.

Austenitic Staidess

63

Steel Welds

---------_

WHITE

~________________

WHITE

FERRITE

AUSTENITE

DENDRITE

RETAINED

TIP

FORMATION
SECONDARY

OF INSTABILITIES
ARM COMPETITIVE

SECONDARY

ARM

NUCLEATION

IN

SOLIDIFICATION
OSTWALD
DENDRITIC

t
;
0
2

FERRITE

GROWTH

THICKENING
REST
OF

-RIPENING
STRUCTURE

DENDRITIC

INTERDENDRITIC

METAL
REST

METAL

OF

SOLIDIFIED

AUSTENITE
AUSTENITE

FIG. 8. D&puns
showing
the mechanism of growth in various modes of solidification: (a, b) peritectic reaction in
FA mode; (c) dendritic growth in austenitic mode, with a schematic representation of the distribution of Cr during

the austenkc

mode of &lidification.

liquid, austenite, and ferrite were in equilibrium during the final stages of solidification. A separate study revealed that this
structure provides the best resistance to solidification cracking.
Figure 7(d) is the structure developed by
an alloy of approximately
25% Cr, 9% Ni
and 0.5% N, which was expected to have
undergone the eutectic reaction owing to
the high alloy content. However, in principle, the mechanism of solidification in this
case was similar to that of relatively low alloyed (18-8 type) weld metals. The structure indicates that solidification was initiated in the ferritic mode, and the growth of
the ferrite phase was interrupted by the

precipitation of austenite. But the growth

rate of the dendrites in this case was not
fast enough to complete solidification, and
some interdendritic austenite grew from a
different direction (see the next section for
a description). A schematic of this type of
growth is shown in Fig. 8(b).
METAMORPHOSIS
OF PURELY
AUSTENITIC
STRUCTURES

In the fully austenitic structures, the area of

interdendritic
regions was considerably
varied in different alloys, as shown in Fig.
9. Particularly
in alloys containing high
amounts of alloying elements, the fraction

K. Rajasekhar et al.

64

of interdendritic
areas was considerable,
and the color interfaces between the dendritic and interdendritic regions were delineated, indicating that either the growth
direction or the mechanism was different.
This can be explained on the basis of a diagram-Kurz
and Kattamis, as cited in
Sahm and Schubert [17]-of
the metamorphosis of dendritic growth, as shown in
Fig. 8(c). The diagram indicates that the interdendritic regions observed in the present
case are freshly nucleated and grown. However, because continuous cooling takes place
in welds, separate nucleation is highly improbable and, instead, already solidified regions grow into the interdendritic regions
from a different direction.
The presence of large amounts of alloying elements, as in the weld shown in Fig.
9(b), decreased the growth rate and consequently increased the interdendritic areas.
The addition of large amounts of alloying
elements to the melt decreased the overall
interface undercooling
and reduced the
growth rates [18]. Quantitative microanalysis of Cr and Ni between the center of a
dendrite and an interdendritic
region [as
marked in Fig. 9(b)] is shown in Fig. 10. Because the equilibrium partition coefficient,
K,,, is less than one, maximum chromium
near the interface indicates that growth was
in two different directions. The composition in the interdendritic regions was more
or less uniform, presumably because of
faster growth. The same mechanism is applicable to the interdendritic precipitation observed in the sample represented in Fig. 7(d).
An idea of the practical significance of
the solidification
mechanism can be obtained by looking at its role in impurity
segregations.
For instance, the change in
the growth direction in the pure gamma
type of structures increases the interface
area between the dendritic and the interdendritic areas. Because interfacial regions
act as preferential sites for impurities and
second-phase formation, any increase in interfacial area decreases the effective impurity concentration. In addition, any increase
in the fraction of interdendritic regions dissolves the impurities to a certain extent ow-

Chromium

S
L
?

22

2011
0

L
Distance

in

microns

10

FIG. 10.Chromium and nickel distribution across the

dendritic/interdendritic
regions of a solidification cell
in the austenitic mode of solidification [typical direction of analysis is marked in Fig. 9(b)].

ing to faster growth rate. Because of the

higher solubility of impurities in ferrite
compared with austenite, the high-temperature phase balance plays a dominating
role in the magnitude of impurity segregations in the FA mode of solidification.

CONCLUSIONS
With the use of a combination of color metallographic and electron microprobe analysis studies, it was established that color
etching clearly reveals the various modes
of solidification in austenitic stainless steel
weldments. Well-developed
cell structures
distinguish AF and FA modes of solidification without any ambiguity. The colors developed in the FA mode of solidification reveal the high-temperature phase boundaries,
such as the onset of the peritectic/eutectic
reaction. Thus, a quantitative estimate can
be made of the high-temperature ferrite content, which has a critical effect on cracking
behavior. Color etching also helps in assessing the mechanism of solidification in the
(L+S+y) region. Purely peritectic or peritectic/eutectic
transformations
were observed in various weld metals. For complete austenitic solidification, color etching
vividly revealed the cell structure and so-

Austenitic

Stainless

Steel Welds

lidification boundaries. It permits a quantitative estimation of dendritic and interdendritic areas that have a determining effect
on the distribution of impurity elements
and the segregation of alloying elements.
Consistent colorations can be obtained by
maintaining the pH of the etchant at 2.5 by
using either N&OH or HN03. This makes
color metallography
a highly useful, simple, and reliable technique for the evaluation of solidification structures in austenitic
stainless steel weldments.

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65
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Received December 2995; accepted September 1996.