The Microstructural Response of Mill-Annealed and

Solution-Annealed INCONEL 600 to Heat Treatment

ERNEST L. HALL and CLYDE L. BRIANT

Samples of INCONEL* 600 were examined in the mill-annealed and solution-annealed states, and
after isothermal annealing at 400 ~ and 650 ~ The corrosion behavior of the samples was ex-
amined, analytical electron microscopy was used to determine the microstructures present and the
chemistry of grain boundaries, and Auger electron spectroscopy was used to measure grain boundary
segregation. Samples of different alloys in the mill-annealed state were found to have quite different
microstructures, with Cr-rich M7C3 carbides occurring either along grain boundaries or in intragranular
sheets. The corrosion behavior of the samples correlated well with the occurrence of grain boundary
chromium depletion. Solution annealing at 1190 ~ caused dissolution of all carbides, whereas at
1100 ~ the carbides either dissolved or the grain boundaries moved away from the carbides, de-
pending upon alloy carbon content. Low-temperature annealing at 400 ~ had little effect on mill-
annealed or fully solutionized samples, but in samples with intragranular carbides present, the grain
boundaries moved until intersecting or adjacent to the carbides. Isothermal annealing at 650 ~ caused
carbide nucleation and growth at grain boundaries in fully solutionized samples. Chromium depletion
at grain boundaries accompanied carbide precipitation, with a minimum chromium level of 6 wt pct
achieved after 5 hours. Healing was found to occur after 100 hours. Solution-annealed samples with
intragranular carbides present had more rapid corrosion kinetics since the grain boundaries moved back
to the existing carbides. Thermodynamic analysis of the chromium-depletion process showed good
agreement with experimental measurements. The Auger results found only boron present at grain
boundaries in the mill-annealed state. Aged samples had boron, nitrogen, and phosphorus present,
with phosphorus and nitrogen segregating to the greatest extent. The kinetics of phosphorus segre-
gation are much slower at 400 ~ compared with 650 ~

I. INTRODUCTION INCONEL 600 is isothermally heated in the temperature

range of 600 to 800 ~ One of these is the precipitation of
INCONEL600 is an austenitic Ni-Cr-Fe-C alloy which is Cr-rich carbides at grain boundaries in the material, 9'11'13'1a
used extensively for tubing and other components in nuclear
which causes chromium depletion (sensitization) at the grain
power plants. Consequently, there has been a great interest
boundaries and vulnerability to intergranular corrosion. If
in the stress corrosion cracking (SCC) properties of this
the alloy is heated for a sufficiently long time at the tem-
alloy. Studies have been performed evaluating the effect of
perature which initially caused sensitization, the inter-
factors such as electrochemical potential, environment
granular corrosion resistance will return (healing). ~5 In
chemistry, temperature, and alloy heat treatment, grain size,
addition, heat treatment in the temperature range 600 to
composition, and processing history on the SCC resis-
800 ~ may cause segregation of impurities such as sulfur,
tance of INCONEL 600 (for a review, see Serral). These
phosphorus, and boron to grain boundaries. One major limi-
studies have shown that an important metallurgical vari-
tation in the attempt to describe microstructural changes
able in the SCC process is the thermal treatment which
accompanying the heat treatment of INCONEL 600 and
the alloy has received. Many studies 2-~~have shown that if
their affect on SCC behavior has been that until recently
INCONEL 600 in the as-received condition (often referred
changes in grain boundary chemistry could not be measured
to as "mill-annealed") is given a heat treatment in the tem-
directly. However, in the past few years Auger electron
perature range of 650 to 700 ~ the SCC resistance in
spectroscopy (AES) has been used to measure impurity
caustic solutions or pure high-temperature water is im-
segregation to grain boundaries in INCONEL 600,16'17'18
proved, but the material is more susceptible to attack in
and energy-dispersive X-ray spectroscopy in the analytical
oxidizing solutions and sulfur-containing environments. ~1.i2
electron microscope (AEM) has been used to measure chro-
However, there is considerable confusion about the gener-
mium depletion. 17,19 One major drawback of many of the
ality of these results since a number of counter-examples can
be found. 1 previous corrosion studies has been the use of samples in
either the mill-annealed or solution-annealed states without
The exact causes of the change in SCC response of
complete microstructural characterization of these condi-
INCONEL 600 as a result of heat treatment are not clear.
tions. In practice, tremendous variability is found in the
Several microstructural changes are known to occur when
corrosion response of different mill-annealed samples. In
the present study, three samples of INCONEL 600 were
*INCONEL is a trademark owned by the INCO family of companies.
chosen which displayed very different corrosion properties
in the mill-annealed state. Differences in the microstructures
ERNEST L. HALL and CLYDE L. BRIANT are Members of the Tech-
nical Staff at the General Electric Corporate Research and Development of mill-annealed samples were characterized and the effec-
Center, P.O. Box 8, Schenectady, NY 12301. tiveness of different solution anneals was examined. The
Manuscript submitted August 30, 1984. effect of isothermal heat treatment on mill-annealed and

METALLURGICALTRANSACTIONS A VOLUME 16A, JULY 1985-- 1225

solution-annealed samples was studied. Analytical electron
microscopy was used to determine the microstructure and
grain boundary chromium content of the samples. Auger
electron spectroscopy was employed to measure segregation
to grain boundaries. These results were correlated to macro-
scopic corrosion tests.
II. EXPERIMENTAL PROCEDURE
The chemical compositions of the three mill-annealed
(MA) samples chosen for study in this investigation are
listed in Table I. These alloys were obtained from a single
commercial supplier and had received nominally the same
mill-anneal treatment although the exact mill-anneal treat-
ment is generally not available from the vendor. The alloys
have somewhat different carbon contents.
The effects of two different solution-anneal treatments on
the mill-annealed microstructures were examined. These
two treatments were 1100 ~ for 0.5 hour and 1190 ~ for
1 hour and will be subsequently referred to as SA1 and SA2,
respectively. The first of these is common industrial prac-
tice, and the second an experimental high-temperature solu-
tion anneal. The solution anneals were conducted in argon
and followed by water quenching.
Isothermal aging experiments were also conducted at two
temperatures which simulate various service conditions.
The first of these was 620 to 650 ~ which is the tem-
perature range used for the stress relief heat treatment
given to the reactor pressure vessel after attachment of
INCONEL 600 parts. Samples were aged in this tem-
perature range for 0.5 to 100 hours. The second temperature
is 400 ~ which should simulate at somewhat shorter times
microstructural changes that would occur at the normal reac-
tor service temperature of 288 ~ Samples were aged at this
temperature for 200 to 2000 hours. These isothermal aging
treatments were applied in various combinations to mill-
annealed and/or solution-annealed specimens.
The Auger experiments were performed using a Physical
Electronics Model 590 Scanning Auger Spectrometer. Sam-
ples were cut from a heat-treated bar and notched. They
were then cathodically charged with hydrogen for approxi-
mately 24 hours. This step was included to produce inter-
granular fracture. After charging, the samples were plated
with cadmium to retain the hydrogen. They were then im-
mediately loaded into the spectrometer, and it was evacuated
to a pressure of 5 • 10 -9 torr. The samples were fractured
in the spectrometer, and Auger spectra were taken from a
number of individual grain boundary facets. The use of
hydrogen charging has a drawback in that the spectrometer
cannot be baked. Consequently, carbon and oxygen will be
adsorbed into the fracture surface and the peak heights of
other elements may be slightly altered. However, without
hydrogen charging no intergranular fracture is obtained in
these INCONEL samples.
Table I. Composition of Alloys Used in This Investigation, Weight Percent
Alloy C Ni Cr Fe Mn
A 0.05 74.12 16.32 8.68 0.24
B 0.07 73.74 16.05 9.35 0.22
C 0.04 74.68 15.11 9.47 0.22
1226--VOLUME16A,JULY1985
Samples suitable for observation in the analytical electron
microscope were prepared by jet electropolishing. In some
cases, second phase particles were extracted for analysis
using the carbon extraction technique. A Hitachi H-600-1
analytical electron microscope, which operates at 100 kV,
was employed for the microscopy. This instrument
has the usual transmission capabilities, and in addition is
equipped with an energy-dispersive X-ray (EDX) detector
and scanning transmission capabilities. Microchemical
analyses of matrix and grain boundary regions and of
second-phase particles were performed using methods de-
scribed previously. 2~
Two types of corrosion tests were used in this investi-
gation: Some samples were examined using stress corrosion
tests in high purity, high temperature water containing
8 ppm oxygen. 22 In addition, a nitric acid test was used,
which consists of immersing the sample in a 25 pct aqueous
solution of boiling nitric acid for two days. Weight loss,
normalized by the initial surface area, is used as a measure
of corrosion. This test is similar to the Huey test used for
stainless steels. ~2 A complete description of the corrosion
testing will be given in a companion paper. 23
III. RESULTS
A. Corrosion Tests
The results of the corrosion tests on the mill-annealed
alloys in Table I are given in Table II. Despite nominally
identical mill anneals, alloys A and B showed significant
susceptibility to intergranular corrosion in both the nitric
acid and stress corrosion tests, while alloy C was resistant
to corrosion in both. There is thus good correlation between
the results of the simple nitric acid test and the stress corro-
sion test. In all cases the corrosion was intergranular. After
the samples in Table I had been solution annealed using
either treatment SA1 or SA2, the corrosion rate in nitric acid
for all samples dropped to near zero.
The corrosion response of the solution-annealed alloys
upon aging at 650 ~ will be illustrated using results from
alloy A (Figure 1). Some differences were seen when com-
paring the two different solution anneals. The samples
which had been solution annealed for 1 hour at 1190 ~
(SA2) showed no measurable effect of the 650 ~ anneal for
annealing times of 0.5 to 1.0 hours (Figure l(a)), although
scanning electron microscopy showed evidence of grain
boundary corrosion. In samples annealed for 3 hours little
weight loss was observed, but sufficient attack had taken
place to cause the sample to break apart along the grain
boundaries upon bending after the test. The amount of
weight loss increased dramatically for an anneal of 15 to
23 hours. However, an anneal of 100 hours produced no
weight loss and the sample did not break upon bending.
The solution anneal of 0.5 hour at 1100 ~ produced the
results shown in Figure l(b). Attack occurred at earlier
S P B Ti N Mo
0.007 0.009 0.0022 0.26 0.015 0.10
0.002 0.01 0.0021 0.23 0.012 0.18
0.001 0.01 0.0018 0.22 0.007 0.18
METALLURGICALTRANSACTIONSA
 0.5 ' ' ' ' I ' ' ' ' I . . . . I 0.5 , ' ' ' I . . . . I . . . . I

1190*C/lOhr $ $ ~"0.4- 1 1 0 0 * C / 0 . 5 hrs $ $ $

0.4 + AGE AT 650~ -,= + AGE AT 6 5 0 * C
oE ,.,

"~0.3 ~0.3 -
(fJ
(,t3
._1
~=0.2 ~ 0z
hl

01 0.1
o

, - , ,~ , o ,o, ,I , , , ,r Oc , ,o, ,~ , I I II I , , ,6
- 10 10 100 1.0 t0 100
TIME (hrs) TIME (hrs)

(a) (b)
Fig. 1 --Corrosion behavior (weight loss during test) v s annealing time at 650 ~ for samples of alloy A (a) solution annealed for 1 h at 1t90 ~ (b) solution
annealed for 0,5 h at 1100 ~ Closed circle: no attack; open circle: broke upon bending after test; closed circle with arrow: disintegrated during test.

Table II. Corrosion Response of Mill-Annealed
Alloys Used in This Investigation
Corrosion Rate
in Nitric Acid Stress Corrosion
Alloy (mg/cm ~) Test Response
A 0.134 intergranular SCC observed
B 0.164 intergranular SCC observed
C 0.014 no SCC observed
times, with samples breaking upon bending after the test for
annealing times of 0.5 and 1 hour. Some weight loss was
seen after 3 hours, and the 5, 15, and 23 hour samples all
showed large amounts of weight loss. Once again, after
100 hours no attack or weight loss occurred.
B. Analytical Electron Microscopy Results
1. Mill-annealed samples
The microstructures present in the mill-annealed samples
are shown in Figure 2. Figure 2(a) shows a typical grain
boundary in sample B. Extensive precipitation is seen along
the boundary, and some precipitation has also occurred
along dislocation lines near the boundary. All precipitates
were identified by electron diffraction as M7C 3. EDX spec-
troscopy showed that the composition of the M portion of
this carbide was 94 wt pct Cr, 3 wt pct Ni, and 3 wt pct Fe.
The composition of grain boundary regions between car-
bides in this sample was also measured using EDX spec-
troscopy. Chromium contents in the range 9.2 to 10.3 wt pct
were measured, with a mean of 9.8 wt pct. Several com-
position profiles across grain boundaries in the vicinity of
carbides were also obtained, and one result is shown in
Figure 3. The width of the chromium-depleted region is
approximately 800 nm (0.8/xm).
A typical area in the mill-annealed sample of alloy C is
shown in Figure 2(b). Only occasional particles, again
M7C3, were found along grain boundaries. Strings of M7C3
carbides were found in the matrix apparently delineating the
prior positions of grain boundaries. When the grain bound-
ary chromium concentration very near to the carbides was
measured in this sample, values from 10.3 to 13.1 wt pct
were found, with a mean of 11.9 wt pct. However, the low
density of carbides at grain boundaries in this sample re-
suited in very little chromium depletion for most areas of the
grain boundaries.
The mill-annealed microstructure of sample A was found
to be very complex and heterogeneous. The majority of the
sample had moderate M7C3 precipitation along the grain
boundaries (Figure 2(c)) and grain boundary chromium lev-
els between carbides of - 1 2 wt pct. This is quite similar to
the previous sample. However, some regions of this sample,
occurring in bands, had a very different microstructure
which is difficult to display using transmission electron im-
ages. Figure 2(d) is a secondary electron image of one of
these regions, in which the M7C3 carbides appear bright.
These regions consist of large grains with rod-shaped intra-
granular carbides present, and smaller grains with massive
grain boundary precipitates. It was not possible to find suit-
able grain boundary regions between carbides in these re-
gions for the measurement of chromium concentration due
to the extensive precipitation. However, the carbide size and
density is larger than that seen in either of the other mill-
annealed samples.
2. Mill-annealed plus heat treated samples
The effects of three different heat treatments on the
previously-described mill-annealed microstructures were
examined. These heat treatments consisted of 400 ~ for
200 and 2000 hours and 650 ~ for 100 hours. The results
showed that neither of the 400 ~ heat treatments had a
significant effect on the microstructures. A slight increase in
carbide size and density may have occurred.
The effect of heat treating the mill-annealed samples for
100 hours at 650 ~ can be illustrated by the results for
alloy A, shown in Figure 4. Comparing this microstructure
to Figure 2(c), it can be seen that significant carbide nucle-
ation and growth has occurred. The M7C3 grain boundary
precipitates in Figure 2(c) have grown, often along planes
not corresponding to the grain boundary plane. Additional

METALLURGICAL TRANSACTIONS A VOLUME 16A, JULY 1985-- 1227


(a)
(c)
Fig. 2--Microstructures in mill-annealed samples: (a) transmission electron image (TEl) of alloy B, (b) TEl of alloy C, (c) TEl of alloy A, and
(d) secondary electron image of alloy A.
smaller carbides have nucleated and grown both along grain
boundary regions between large carbides and also along the
interfaces between large carbides and the matrix. Exten-
sive new precipitation along dislocations in the vicinity of
the grain boundary is seen. Unlike the grain boundary pre-
cipitates, the dislocation precipitates are Cr-rich M23C 6
which have a cube-cube orientation relationship with the
Ni matrix.
3. Solution-annealed samples
The mill-annealed samples described previously were
solution annealed using one of two different treatments:
1100 ~ for 0.5 hour (SA1) or 1190 ~ for 1 hour (SA2).
1228--VOLUME 16A, JULY 1985
(~)
(d)
The results showed that the higher solution-anneal tem-
perature (SA2) caused all precipitates to dissolve, so that the
microstructures of all samples were free of precipitates after
that treatment. The SA1 treatment produced different re-
suits. For sample C, which had the lowest carbon content
and had moderate precipitation at the grain boundaries in the
mill-annealed state, SA1 caused all precipitates to dissolve.
After the solution-anneal, the only precipitates present were
some very small (0.1 /xm) Cr-rich carbides at some grain
boundaries. However, in sample A, which had large, nu-
merous precipitates at the grain boundaries in the mill-
annealed condition and an intermediate carbon content, SA 1
METALLURGICALTRANSACTIONSA
Fig. 3--Composition profile across grain boundary in mill-annealed
alloy B. Error bars shown are typical for each point. Lines at right indicate
nominal alloy composition.
Fig. 4--Transmission electron image of mill-annealed alloy A after aging
at 650 ~ for 100 h.
was insufficient to dissolve all of the particles, and the
microstructure shown in Figure 5 results. Rows of M7C3
carbides were found outlining the positions of prior grain
boundaries. These carbides have an arrangement which ap-
proximates the large grain boundary carbides in Figure 2(d).
All other particles found in this sample in the mill-annealed
state--the grain boundary precipitates in Figure 2(c) and
the intragranular precipitates in Figure 2 ( d ) - - a r e not pres-
ent after SA1. For sample B, with the highest carbon con-
tent, some carbide dissolution occurred during SA1, but the
boundaries remained pinned by carbides ranging in size
from 0.2 to 1.0/xm.
4. Solution annealed plus heat treated samples
The effects of isothermal annealing at 400 ~ and 650 ~
on the solution-annealed microstructures were examined,
Once again, the two solution anneals produced somewhat
different results. For samples solutioned at 1190 ~ (SA2),
heat treatment at 400 ~ for 200 to 2000 hours had no effect
on the microstructure. No carbide nucleation or growth
was observed. In samples given the SA1 solution anneal,
METALLURGICAL TRANSACTIONS A
Fig. 5 --Transmission electron image of alloy A after a solution anneal of
0.5 h at 1100 ~
some changes were caused by the low-temperature heat
treatments. Sample A contained rows of intragranular car-
bides after SA1. Subsequent heat treatment at 400 ~ for
200 hours apparently caused the grain boundaries to migrate
until these carbide rows were encountered. In some cases,
the boundaries appear to intersect the carbides (Figure 6(a));
in others, the boundaries move until they are adjacent to the
carbides (Figure 6(b)). However, it is important to stress
that no chromium depletion was detected at boundaries such
as that in Figure 6(a), most likely because very little chro-
mium diffusion and carbide growth occurs at 400 ~ In
sample C, the very small carbides that were present in the
solution-annealed samples had not visibly grown during the
LTA heat treatments.
The isothermal annealing experiments at 650 ~ were
conducted using samples of alloy A which had been solu-
tioned at 1190 ~ for one hour (SA2). This alloy was chosen
since it has an intermediate carbon content, and the SA2
treatment provides a microstructure initially free of precipi-
tation. The corrosion response of these samples was shown
in Figure l(a). Typical grain boundaries in samples an-
nealed for 0.5, 5, 23, and 100 hours at 650 ~ are shown in
Figure 7. After 0.5 hour (Figure 7(a)), small (0.1 /~m) pre-
cipitates are seen along some grain boundaries. With in-
creasing time in the range 0.5 to 5.0 hours, there is an
increase in the size and density of the grain boundary pre-
cipitates and in the number of boundaries with precipitates
present. Precipitation along dislocation lines near bound-
aries is first seen after 3 hours. After 5 hours (Figure 7(b)),
a nearly continuous string of particles, - - 0 . 2 / z m in width,
is observed along grain boundaries, and precipitation along
dislocations is evident. With increasing time to 100 hours,
little further change is seen in the grain boundary precipi-
tates, but increases in the size and density of precipitates
along dislocation lines are seen (Figures 7(c) and 7(d)). In
these samples, the grain boundary and dislocation line pre-
cipitates were found to be a mixture of M7C3 and M23C6,
with neither of these two carbides clearly dominant.
VOLUME 16A, JULY 1985-- 1229
 (a) (b)
Fig. 6 - - ( a , b) Transmission electron images of alloy A after solution annealing for 0.5 h at ll00 ~ and then aging at 400 ~ for 200 h.

(a) (b)

(c) (d)
Fig. 7--Transmission electron images of grain boundaries in alloy A after solution annealing at 1190 ~ for 1 h and then aging at 650 ~ for: (a) 0.5 h,
(b) 5 h, (c) 23 h, and (d) 100 h.

1230--VOLUME 16A, JULY 1985 METALLURGICAL TRANSACTIONS A


Fig. 8--Chromium distribution across grain boundaries in alloy A after
solution annealing for 1 h at 1190 ~ and then aging at 650 ~ for: (a) 3 h,
(b) 5 h, (c) 23 h, and (d) 100 h.
The chromium distribution across grain boundaries was
studied as a function of annealing time, and some typical
results are shown in Figure 8. Significant chromium de-
pletion in the vicinity of carbides is first seen after 3 hours,
with a minimum Cr level of 9 wt pct and a width of
100 nm for the depleted zone observed (Figure 8(a)). Af-
ter 5 hours (Figure 8(b)), the Cr concentration at the grain
boundary has dropped to 6 wt pct, and the depleted region
has widened slightly. With increasing annealing time to
23 hours (Figure 8(c)), the principal change is an increase
in the depleted zone width. In Figures 8(c) and 8(d), the
dashed line denotes regions in the sample where carbides
growing on dislocations were present and hence no EDXS
measurements were made. After 100 hours (Figure 8(d)),
the depleted region has widened to nearly 800 nm, but
the minimum chromium concentration found has risen
to t2.5 wt pct.
One important point must be made concerning the com-
position profiles in Figure 8. In any given sample, some
differences are seen in the size and density of carbides at
different boundaries. The chromium distribution across a
boundary is affected by the size and density of the carbides
present and by the distance of the measurement from the
nearest carbide. This effect has been studied in detail by
Hall and Briant 2~ for the sensitization of stainless steel.
Therefore, the profiles in Figure 8 represent trends only;
some variation will be seen from boundary to boundary in
the width of the Cr-depleted zone and in particular in the
precise value of the chromium concentration at the bound-
ary. However, comparison of the present results with those
METALLURGICALTRANSACTIONS A
from austenitic stainless steels 2~ shows that significantly
more d e p l e t i o n o c c u r s at a g i v e n t e m p e r a t u r e in
INCONEL 600 for the particular alloys studied.
One additional precipitate type was found along the grain
boundaries in these samples, interspersed between Cr-rich
carbides. It was found to be structurally identical to M23C6
(fcc, a0 = 1.06 nm) and, when located at boundaries be-
tween M23C6 particles, had the same cube-cube orientation
relationship with one of the austenite grains as the adjacent
carbides. However, the composition of these precipitates
was 90 wt pct Ni, 2 wt pct Cr, 4 wt pct Fe, 2 wt pct Ti,
and 1 wt pct Mn. It is most likely that these precipitates are
of the type (Ti,Mn,Fe)2 Ni2j (B,C)6, which had been pre-
viously discovered. 24,25It is not clear if the presence of these
precipitates affects the intergranular corrosion behavior of
INCONEL 600; however, it should be noted that the chro-
mium content of these precipitates is very low.
For comparison, samples of alloy A which had been solu-
tioned at 1100 ~ (SA1) and then isothermally aged at
650 ~ were examined. The corrosion response of these
samples was given in Figure l(b). It was found that in this
case the boundaries moved back to the particles and particle
growth took place very rapidly at 650 ~ Figure 9 shows a
secondary electron image of the microstructure of a sample
which had been annealed for 1 hour at 650 ~ Some very
large carbides are seen, with smaller carbides present be-
tween the large carbides and attached to the large carbides.
The grain boundary precipitation was too extensive to mea-
sure the grain boundary chromium concentration. While the
large grain boundary carbides in this sample w e r e M7C3,
some of the smaller carbides w e r e M23C 6. Annealing for
times longer than 1 hour primarily caused an increase in the
amount of precipitation along dislocation lines.
C. Thermodynamic Analysis of Carbide Precipitation
In the previous section it has been clearly shown that both
M23C6 and M7C3 carbides precipitate in INCONEL 600 and
that both appear to cause significant chromium depletion.
Since it is not possible to measure precisely the chromium
concentration at the carbide-matrix interface, this section
will use a thermodynamic analysis to examine this point,
and the results will be compared with the experimentally
Fig. 9--Secondary electron image of alloy A after solution annealing for
0.5 h at 1100 ~ and then aging at 650 ~ for 1 h.
VOLUME I6A, JULY 1985--1231
measured grain boundary compositions. Details of these
calculations can be found in Reference 20; in this section
only the important results are described.
To calculate the chromium concentration in the matrix in
equilibrium with the carbides, the following two reactions
will be considered:
23Cr + 6C ~,~ Cr23C 6
and
7Cr + 3C .~--Cr7C3
For each of these reactions an equilibrium constant can be
defined as follows:
1 concentration at the grain boundaries, the experimental
KM23c6 = (ac)6 (5,r [Cr]23
and
1 mental profiles. 3~
KM7C3 = (ac) 3 (,YCr)7[Cr] 7
where KM23C6 and KM7c3 are the equilibrium constants for
reactions [1] and [2], respectively, ac is the activity of car-
bon in equilibrium with the carbide, and YCrand [Cr] are the
activity coefficient and the concentration of chromium in the
matrix, respectively, in equilibrium with the carbide. There-
fore, to determine the chromium concentration in equi-
librium with the carbide [Cr], one must have values for K,
ac, and YCr-
Values for both of the equilibrium constants were taken
from Reference 26. The value for the activity coefficient of
chromium was taken from Reference 27. This latter value
should correspond to a chromium concentration in the de-
pleted matrix that is in equilibrium with the carbide. In a
matrix with depletion below about 10 wt pct Cr, the activity
coefficient is very near 1.0, i.e., an ideal solution. There-
fore, a value of 1.0 was used for the calculations. To obtain
a reasonably accurate expression for the activity of carbon,
the effects of both Fe and Cr must be considered. Expres-
sions for the activity of carbon in Ni-Cr-C 28 and Ni-Fe-C 29
were obtained and were combined with the assumption that
Cr and Fe independently affect carbon activity. The results
of the calculations are given in Table III. Several impor-
tant points should be noted about these results. The first is
that with increasing temperature the amount of chromium
in equilibrium with the carbide increases. Secondly, the
amount of chromium in equilibrium with the MTC 3 carbides
is always significantly less than that in equilibrium with
M23C6.
As mentioned above, these calculations are valid only at
the start of precipitation when carbon has not been depleted
from the matrix. These calculated values should then be the
lowest chromium concentrations ever attained and should
always be equal to or less than our measured values. If the
calculated values are compared to the measured values re-
ported above (Figure 8), it would indeed appear that al-
[l]
though there is general agreement the calculated values are
lower than the measured values. Because of the mixture of
particle types at grain boundaries in the samples annealed at
[2] 650 ~ the exact equilibrium condition at the boundaries is
extremely difficult to predict, and so only qualitative agree-
ment is expected.
In addition to calculation of the equilibrium chromium
[31 profiles in Figure 8 Were compared with calculated pro-
files based on diffusion controlled growth of the carbides. 2~
Good agreement was found between calculated and experi-
[41
D. Auger Electron Spectroscopy Results
As described previously, Auger electron spectroscopy
was used to examine grain boundary segregation of im-
purities. In the mill-annealed state, boron was the only im-
purity observed on the grain boundaries. After aging the
mill-annealed samples at 400 ~ or 620 ~ phosphorus,
nitrogen, and boron were found on the grain boundaries.
Alloy C always had the greatest amount of phosphorus seg-
regation after any of the aging heat treatments. Alloy A had
the second greatest amount of phosphorus segregation after
any aging treatment and alloy B had the least (Table IV).
The kinetics of segregation as a function of aging time
were examined for heat A. The samples used for this study
were initially in the mill-annealed condition and had been
aged at either 400 ~ 650 ~ or 700 ~ One element
which segregated extensively was phosphorus, and Fig-
ure 10 shows the change in the amount of segregation with
time. At 650 ~ and 700 ~ (Figure 10(a)) segregation is
very rapid and equilibrium is achieved in less than 24 hours.
At 400 ~ (Figure 10(b)) the kinetics are considerably
slower, but after 1000 hours of aging there is a substantial
amount of phosphorus on the grain boundaries. However,
this value is still lower than that obtained in 24 hours at
650 ~ Nitrogen also segregates at 400 ~ 650 ~ and
700 ~ (Figures 10(b), 10(c)), and its kinetics of segre-
gation are faster than those of phosphorus at 400 ~ Boron
segregation at the high temperatures was quite variable, but
at 400 ~ the amount on the grain boundaries consistently
decreased with increasing aging times.

Table llI. Chromium Concentration in Equilibrium

with M23C6 and M7C3 at the Start of Precipitation
IV. DISCUSSION
Temperature, ~ Carbide Type Cr, Wt Pct The results of this investigation can be used to clarify our
600 M23C6 5.3 understanding of the microstructural response of INCONEL
650 M23C6 6.8 600 to heat treatment, and the relationship of corrosion
700 M23C6 8.8 properties to microstructure in this alloy. In this section,
750 M23C6 l 1.0 these results will be considered in the order that they were
600 M7C3 1.1 presented in the Experimental section, and the important
650 M7C3 2.0 points that these results illustrate will be described.
700 M7C3 3.0 If we consider the microstructure and corrosion behavior
750 M7C3 4.2
for the mill-annealed samples (Figure 2 and Table II), it is

1232-- VOLUME 16A, JULY 1985 METALLURGICAL TRANSACTIONS A

 Table IV. P/Ni Auger Peak Height Ratio 0.1(; I I I I I I I
for Samples Aged at 620 ~ for 24 Hours
0.0s
Mill Anneal
Alloy +620 ~ Hours 0.0~
A 0.088

/I
B 0.054 o 0.07
I.--
C 0.160 r
~O.OE

",- 0.05 AGING TEMPERATURE

clear that very different microstructures can be produced in 9 650"C
different samples by nominally the same mill anneal treat- ~_0.04 x 700oc
ment. Further, in some samples the mill-annealed micro-
structure can vary significantly within a single sample ~. 0.03
(Figures 2(c) and 2(d)). At least two factors are important in
the understanding of this variability: alloy carbon content 0.02
and mill-anneal temperature. Scarberry e t a l . u have shown
that the temperature necessary to dissolve carbides com- 0.01
pletely is a function of carbon content, with approximate I I I I I I I
temperatures of 1050 ~ 1075 ~ and 1115 ~ necessary 0o 2O 40 60 80 100 t20 140 160 180
for carbon contents of 0.04, 0.05, and 0.07 wt pct, re- AGING TIME (hrs)
spectively. Therefore, for an identical mill anneal, much (a)
more carbide dissolution would have taken place for al-
loy C, compared with A or B. This may allow the grain 0.1
boundaries to break free of the carbides in alloy C, but not
in A or B, and result in the microstructures seen in Figure 2.
Banding of carbon may cause the microstructural variability 9 N/Ni
within a single sample which was seen for alloy A. 0 o p/Ni
Changes in the temperature of the mill anneal will also be
important. At 1100 ~ all carbides dissolved in alloy C
which had low carbon content. As the carbon content is (.~

raised (alloys A and B), only partial carbide dissolution 0.05

occurred, accompanied by the movement of grain bounda-
ries away from the carbides. A temperature of 1190 ~ was
sufficient to dissolve all carbides in all the alloys studied
(0.07 wt pct carbon or less), in agreement with the predic-
tion of Scarberry et al. H
In the mill-annealed state, there is good correlation be-
tween the occurrence of numerous large carbides at grain I
00 1000 2000
boundaries and poor corrosion behavior in the nitric acid test AGING TIME AT 400% (hrs)
for the samples in this study. The presence of these carbides
(b)
produced low values of chromium concentration at grain
boundaries in sample B, which was susceptible to corrosive 0.10
attack. On the other hand, sample C, which had little chro- I I I I I
mium depletion at grain boundaries, showed good corrosion
resistance. It is, therefore, likely that poor behavior in the 008
nitric acid corrosion test correlates with grain boundary
chromium level. This correlation was further substantiated -r
by tests on model alloys, where a number of solutionized ~- 0.06
U,.l
o 650"C ~
tNCONEL 600 samples with chromium contents from 6 to .-r- x 700* C
16 wt pct were subjected to the nitric acid test. It was found
that samples with < 10 wt pct Cr began to show weight loss ~- 0.04
in the test. Less Cr than 8 wt pct caused significant weight
Z
loss. These values agree well with a previous investigation ~2
in which attack in a variety of sensitization tests for 0.02
INCONEL 600 was noted for Cr contents below 10 wt pct.
The Auger experiments showed that, for the mill- 0 I I 1 I I
annealed samples, there was no correlation between cor- 0 20 40 60 80 I00
rosion behavior and the presence of impurities at grain AGING TIME (hrs)
boundaries. This further strengthens the argument that (c)
grain boundary chromium depletion alone accounts for dif- Fig. 10--(a) Phosphorus segregation v s aging time at 650 ~ and 700 ~
ferences in the corrosion response of the mill-annealed (b) Nitrogen and phosphorus segregation v s aging time at 400 ~
INCONEL 600 samples in the nitric acid test. (c) Nitrogen segregation v s aging time at 650 ~ 700 ~

METALLURGICALTRANSACTIONS A VOLUME 16A, JULY 1985-- 1233

 The microstructural changes accompanying heat treat-
ment at 400 ~ were shown to be very dependent upon the
microstructure of the sample prior to aging. In cases where
carbides were initially present at the grain boundaries, as in
the mill-annealed condition for all three samples in this
study, the 400 ~ age had no effect, other than to allow
some impurity segregation to grain boundaries. A similar
result was seen for samples which had been solutionized at
1190 ~ so that the starting microstructure was free of all
precipitates. However, if the initial microstructure consisted
of discrete sheets of particles in an otherwise relatively clean
matrix, with the grain boundaries free of precipitates, then
aging at 400 ~ caused the grain boundaries to move until
the particles were intersected. This was observed for alloy A
which had been solutionized at 1100 ~ (Figures 5, 6).
The effect of isothermal annealing at 650 ~ is also de-
pendent upon the starting microstructure of the material. If
extensive grain boundary coverage by carbides exists prior
to the 650 ~ age, then the aging treatment will cause addi-
tional precipitation at available nucleation sites, which are
primarily dislocation lines and existing carbide-matrix inter-
faces (Figure 4). If grain boundary chromium depletion
were present between the carbides prior to aging, then the
kinetic study (Figure 8) indicates that healing should occur
on subsequent aging.
When the initial microstructure consists of clean grain
boundaries and sheets of intragranular carbides (alloy A
after 1100 ~ solution anneal, Figure 5), then aging at
650 ~ causes the grain boundaries to move until the carbide
sheets are intercepted, followed by rapid carbide growth.
This is in contrast to the situation where the initial state is
a completely solutionized microstructure, where carbide nu-
cleation and growth occurs relatively slowly upon aging
at 650 ~ The situation after 1 hour at 650 ~ for these
two initial states can be seen by comparing Figure 9 to
Figures 7(a) and (b). This difference in behavior also ex-
plains the more rapid sensitization kinetics seen in Fig-
ure 1 for samples of alloy A which had been solutionized at
1100 ~ compared with 1190 ~ Once again, there is good
correlation between grain boundary carbide size, density,
and chromium depletion and the observed corrosion behav-
ior in nitric acid.
These results are quite consistent with previously pub-
lished studies, and can be used to explain some apparent
discrepancies. Scarberry e t a l . ~ have shown that for a
given solution-anneal temperature, samples with lower
carbon contents (and hence which are more likely to have
complete dissolution of carbides) have much slower carbide
precipitation and sensitization kinetics upon aging. Airey
and co-workers, in a number of investigations, 6'12'16'j8 have
found maximum attack in nitric acid tests for mill-annealed
samples after 1 hour at 650 ~ and healing after 10 to
20 hours. Solution-annealed samples (1093 ~ showed
much slower corrosion kinetics, with attack after 10 hours at
650 ~ and healing after 100 hours at 650 ~ Similarly,
Was e t a l . , 17 using samples solutionized at 1100 ~ saw
attack commencing at 0.5 hour at 700 ~ with maximum
attack and maximum grain boundary chromium depletion
after 10 hours and healing after 100 hours. These results,
combined with the present investigation, clearly show the
importance of the initial state of the material on the kinetics
of the grain boundary chromium depletion process upon
subsequent aging at 650 to 700 ~
1234--VOLUME 16A, JULY 1985
In summary, therefore, it can be seen that a solution-
anneal or mill-anneal treatment can leave the alloy in one
of three possible conditions: carbides present at grain
boundaries with chromium depletion along the boundaries;
intragranular carbides outlining prior grain boundaries; or
complete carbide solution. The result of a given SA or MA
treatment will depend upon the temperature and the alloy
carbon content. Only the first of these three possible condi-
tions will result in an alloy which is susceptible to corrosion
in oxidizing solutions in the MA or SA state. However, the
kinetics of grain boundary chromium depletion leading to
attack will be accelerated if intragranular carbides are
present compared with the completely solutionized alloy.
Alloys in one of the first two conditions listed above will
also heal and hence become immune to attack much more
quickly at temperatures of 650 ~ to 700 ~ Given the
variety of microstructures that could be produced by differ-
ent mill-anneal heat treatments, it is not surprising that the
reported effects of various heat treatments on corrosion sus-
ceptibility is somewhat confusing.l It would appear that a
clear understanding of the effect of various heat treatments
on stress corrosion cracking can be obtained only when
corrosion results are coupled with thorough microstructural
analysis.
Since the movement of grain boundaries away from and
to carbides is so critical to these processes, a study was
undertaken to determine the lowest temperature that would
cause boundaries to move away from the carbides in mill-
annealed samples of alloy A. It was found that at 950 ~
after 0.5 hour no boundary movement had occurred. How-
ever, after 0.5 hour at 1050 ~ the boundaries had moved
away from the carbides and significant grain growth was
seen.
As described above, the corrosion results presented in
this paper can be correlated with the occurrence of grain
boundary carbides and chromium depletion. However, it is
important to realize that impurity segregation to grain
boundaries occurs rapidly at 650 ~ and may play a role in
the corrosion process. Results that will be presented in a
companion paper 23 show that when grain boundary segre-
gation of phosphorus accompanies chromium depletion,
corrosion in the nitric acid test is increased. In the present
study, we found that at 650 and 700 ~ phosphorus segre-
gated very rapidly to the boundaries and appeared to reach
equilibrium within 24 hours. At 400 ~ equilibrium segre-
gation had not been achieved during the first 1000 hours of
aging. In the heats used in this study nitrogen was also found
to segregate and the kinetics of nitrogen segregation were
faster than those of phosphorus at 400 ~ These results are
in good agreement with previous studies of grain boundary
segregation in INCONEL 6 0 0 . 9'16-19'31'32
It is interesting to compare the kinetics and thermo-
dynamics of chromium depletion and phosphorus segre-
gation at various temperatures to emphasize whether one or
both of these effects are expected. During the mill-anneal
heat treatment, chromium carbides are often not completely
dissolved and if the grain boundaries do not break away
from the carbides, the carbides will grow during the slow
cool after the mill anneal and produce chromium depletion.
However, the temperature of the mill anneal is sufficiently
high to prevent phosphorus segregation and the cool-down
after the mill anneal is fast enough to avoid segregation. In
the temperature range of 650 to 700 ~ both processes
METALLURGICAL TRANSACTIONS A
occur rapidly. With sufficient time the chromium depleted
zone can be healed at these temperatures, but phosphorus
will remain on the grain boundaries. At low temperatures
near 400 ~ chromium carbides will not nucleate and
growth is slow. Phosphorus will still segregate at this tem-
perature, although the time required to reach equilibrium
may be very long.
Finally, the result that different types of grain boundary
precipitates occur during isothermal annealing of fully so-
lutionized INCONEL 600 at 650 ~ is interesting and
deserves further investigation. Previous work by Fell 33
determined that in Ni-Cr-C alloys, M7C3 is formed at
temperatures above 1000 ~ but that below this tem-
perature, MTC 3 may form initially but should transform with
increasing annealing time to M23C6. In the present in-
vestigation, M7C3 was found exclusively in mill-annealed
specimens, most likely formed at high temperatures. For
mill-annealed samples heated at 650 ~ M23C6 precipi-
tated, consistent with Fell's findings. However, upon aging
fully solutionized material, both M23C6 and M7C3 w e r e
found at grain boundaries and in the matrix along dislocation
lines. The type of carbide formed is important since it will
affect the magnitude of the chromium depletion (Table III).
The effect of the presence of Ni-rich Cr-depleted M23(B,C)6
is also not clear.
V. CONCLUSIONS
1. Samples of INCONEL 600 which had nominally re-
ceived the same mill-anneal treatment were found to have
very different microstructures and corrosion properties.
In some cases the grain boundaries were found to be
covered with Cr-rich M7C3 carbides; in other cases the
grain boundaries had moved away from the carbides,
leaving sheets of intragranular carbides.
2. A solution anneal at 1190 ~ was found to dissolve all
carbides in all mill-annealed samples. A solution an-
neal at 1100 ~ either dissolved all carbides or caused
the grain boundaries to break away from the carbides,
depending upon the alloy carbon content and the micro-
structure in the mill-annealed state.
3. Low-temperature aging at 400 ~ of fully solution-
ized samples caused no microstructural changes. Low-
temperature aging of samples with rows of intragranular
carbides present caused grain boundaries which were
free of carbides to move until they intersected or were
adjacent to the carbides.
4. Isothermal annealing at 650 ~ of fully solutionized sam-
ples caused carbide precipitation at grain boundaries to
occur, Carbides were observed after 0.5 hour, increasing
in size and density with increasing time. After 5 hours,
nearly continuous grain boundary coverage was seen,
and precipitation had begun along dislocation lines. Both
MTC 3 and M23C6 carbides were observed, with both car-
bides rich in Cr.
5. Composition profiles across grain boundaries in samples
isothermally annealed at 650 ~ showed significant chro-
mium depletion at the boundary in the vicinity of car-
bides for annealing times of 3, 5, and 23 hours. The
width of the chromium-depleted region increases with
increasing time. The minimum chromium level was mea-
sured to be 6 wt pct and occurs after 5 and 23 hours of
METALLURGICAL TRANSACTIONS A
annealing. After 100 hours healing has occurred, with
12.5 wt pct Cr found at the grain boundary. The corrosion
behavior of the samples correlates well with the occur-
rence of chromium depletion.
6. When samples which contain sheets of intragranular car-
bides after solutionizing are annealed at 650 ~ the
boundaries move back to the carbides and rapid carbide
growth is seen. This can be correlated with more rapid
corrosion kinetics for these samples compared with fully
solutionized samples.
7. Thermodynamic analysis of the chromium depletion pro-
cess shows that significantly more Cr-depletion occurs
in the vicinity of M7C3 carbides compared to M23C6.
Reasonable agreement is found between measured and
calculated grain boundary chromium concentrations
and chromium depletion profiles.
8. Auger electron spectroscopy showed that phosphorus,
boron, and nitrogen segregated to grain boundaries in
mill-annealed samples during heat treatment. In the mill-
annealed samples, phosphorus and nitrogen segregated
extensively during low temperature aging (400 ~
or isothermal annealing at 650 ~ with the kinetics
of segregation much slower at 400 ~
ACKNOWLEDGMENTS
The authors would like to acknowledge the assistance
of the following: Ms. C.S. O'Toole, General Electric
Company, San Jose, CA, who provided samples and some
corrosion data; Mr. N. Lewis, General Electric Corporate
Research and Development, who assisted with the AEM
experiments; and Dr. R . L . Fullman, General Electric
Corporate Research and Development, who provided assis-
tance with the thermodynamic data.
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METALLURGICAL TRANSACTIONS A