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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
mechanism
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)
0 Elsevier Science Inc., 1997
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PI1 SlO44-5803(96)00132-5
54
K. Rajasekhar et al.
SOLIDIFICATION
MECHANISM
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)
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
55
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.
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)].
MICROPROBE
ANALYSIS
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
(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
(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
IDENTIFICATION
HIGH-TEMPERATURE
BOUNDARIES
OF
PHASE
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
Dendrite
4
b
Core
Boundary
Retained
i\
\\
\.
Chromium
s
.z
P
9
;
Nickel
/,
A/,
!.i
.
./ ,.*
6
_.H
: *.
GA.1
i
L_-
_,_ d
I-
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.
(a)
(b)
of dendritic to interdendritic
regions, depending
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
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
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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