Low Temperature Stress Corrosion

Cracking of Sensitized Inconel 600 in

Tetrathionate and Thiosulfate Solutions*

R. BANDY, * R. ROBERGE, * * and R. C. NEWMAN*

Abstract
This paper addresses some aspects of low temperature stress corrosion cracking (SCC) in In-
conel 600 steam generator tubing, a recent instance of which apparently resulted from the
contamination of the primary coolant by sulfur compounds. The low temperature SCC of sen-
sitized Inconel 600 was studied in concentrated and dilute solutions of tetrathionate and thio-
sulfate. The material tested was a tubing directly sensitized from the milt-annealed condition.
Tests were performed using U-bends, slow strain rate, and constant extension. The resuits
show that the propensity to SCC, especially its initiation, in thiosulfate is low and is much
lower than in tetrathionate. However, when slow strain rate was applied in thiosulfate, or
when the pH of the thiosulfate solution was lowered, the specimens cracked readily. Constant
extension tests, where the extension was applied using dynamic straining with the solution
present, caused cracking much faster than in U-bends, suggesting that U-bend cracking is
initiation controlled. Temperature accelerated the crack propagation significantly and
seemed to reduce the threshold stress for cracking. Flat coupons of the sensitized metal
developed pits in a short period of time in tetrathionate and low pH thiosulfate, but not in
neutral thiosulfate; pits sometimes act as precursors to SCC in this system.

Introduction ful effects, even at the ppm level, on sensitized stainless

The stress corrosion cracking (SCC) of sensitized Inconel 600
in dilute sulfur-bearing environments has recently become a
subject of much practical interest in view of the extensive
cracking of the Inconel 600 steam generator tubes in the Three
Mile Island Power Plant Unit 1. 1 Widespread tube cracking on
the primary coolant side of each of the two steam generators
was noticed in late 1981. 1 Most of the degradation occurred at
approximately the same level in both steam generators,
around the roll transition zone of the upper tube sheet. The
cracks are intergranular and penetrated either completely or
about 80 to 90% through the tube walls. During hot functional
testing of the unit in August, 1981, there was no indication of
leaks. Subsequent to this, the unit was maintained at a cold
shutdown temperature of around 40 C. It is therefore believed
that the cracking occurred at low temperature and propagated
very rapidly.'
The hypothesis that sulfur compounds might have caused
the damage is supported to the extent that sulfur bearing com-
pounds such as sulfuric acid and sodium thiosulfate have
been identified as likely contaminants of the reactor coolant
system. Sodium thiosulfate (used in the building containment
sprays) has been particularly implicated because of its harm-
*Submitted for publication July, 1982; revised November,
1982.
*Corrosion Science Group, Department of Nuclear Energy,
Brookhaven National Laboratory, Upton, New York.
"Permanent address: Institut de Recherche d'Hydro-Quebec,
Varennes, Quebec, Canada.
0010-93121831000135/$3.00/0
Vol. 39, No. 10, October, 1983 National Association of Corrosion Engineers
stee1.2,3 It is speculated that sodium thiosulfate leaked in
small amounts into the primary coolant system from time to
time. Also, sulfuric acid was once apparently introduced ac-
cidentally into the primary coolant stream. Sulfur-rich deposits
have been observed on the tube surfaces, and fractographs of
cracked surfaces show indications of sulfur, thus implying
some key role of sulfur in the cracking process. The relevant
level of sulfur in the primary coolant may have been as low as
0.7 ppm. It is speculated that some metastable form of sulfur
such as thiosulfate or polythionate was probably the
causative agent for cracking.
It has been known for several years that sensitized In-
conel 600 suffers SCC in polythionic acid 4 and concentrated
sodium tetrathionate. 5 However, its cracking in dilute sulfur
environments has not been studied systematically. Therefore,
this study was undertaken in order to understand more
thoroughly the role of sulfur compounds in the SCC of sensi-
tized Inconel 600. This paper describes the results of tests on
tubing that was directly sensitized following milt annealing.
The tubes in the once-through steam generators which failed
were sensitized after being rolled (part way) into the tube sheet
as a result of the post-weid treatment given the steam
generator vessel with the tubes in place. Therefore, the direct
sensitization treatment used in this study is believed to be
representative of the thermal treatment given the tubes that
suffered cracking in the steam generators. However, even
more highly sensitized materials, i.e., specimens sensitized
subsequent to solution annealing, have also been studied and
the environmental aspects of their cracking have been
reported elsewhere. 6
391
 Experimental
Commercially produced nuclear grade Inconel 600 tubing,
outside diameter 22 mm and wall thickness 1.24 mm, and of
the following composition (Wt%) was used for our investiga-
tion: 0.004 C, 0.17 Mn, 0.29 Al, 0.001 S, 0.32 Si, 14.61 Cr, 0.22 Ti,
0.40 Cu, 9.41 Fe, 0.02 Co, and balance Ni. The yield strength
and elongation were about 310 MPa and 40%, respectively.
The tubing was cut into small pieces and sensitized at 621 C
for 18 hours. There was very little change in the mechanical
properties following this heat treatment.

U -Bend Tests
Reverse U-bends were prepared using methods described
elsewhere. 7 The bolts of the U-bends were spot-welded to 2
mm diameter rods which served as specimen holders. The
U-bends were ultrasonically cleaned in detergent solution,
rinsed in distilled water, cleaned in acetone and methanol, and
air dried. The specimen holder, the two ends of the U-bend, and
the bolting device were masked with a thin film of lacquer. The
above specimen configuration allowed electrochemical
monitoring of the U-bends. The uncoated area of the U-bend
was immersed in the appropriate environment prepared from
deionized water (conductivity <0.1 µS/cm) and either sodium
thiosulfate or sodium tetrathionate. The environments
generally contained 1.3% boric acid to simulate the conditions
in the TMI-1 primary coolant. However, to study the effect of
boric acid, some tests in tetrathionate were conducted without
any boric acid addition. Unless otherwise mentioned, all tests
were conducted at a room temperature of 22 C. Higher
temperatures, when required, were maintained by an infrared
lamp in conjunction with a temperature controller. Tests were
generally carried out in air saturated environments. Deaera-
tion, when necessary, was achieved by continuously bubbling
high purity (99.999%) nitrogen gas through the test solution.
Some tests were conducted in a low pH (-3) environment ob-
tained by adding an appropriate amount of 1 N sulfuric acid to
the solution. The specimen potential was measured with
respect to a saturated calomel electrode via a Luggin probe.
The potential was monitored with a PARC Model 173 potentio-
stat and a HP strip chart recorder. Potential control, when
desired, was applied with a PARC Model 350 Corrosion Meas-
urement System.
The U-bends were generally withdrawn every 24 hours for
examination under a low power microscope. Specimens which
were electrochemically monitored or controlled were not with-
drawn until the monitoring or control was discontinued. The
specimens in some of the concentrated environments cracked
very rapidly. They were withdrawn and examined whenever
possible at the earliest indication of cracks. The time to crack-
ing reported is the total time elapsed before a through-wall
crack was observed. In some of the low pH tests with thiosul-
fate, the pH drifted to higher values because of the develop-
ment of a bisulfite/sulfurous acid buffer. In these cases, fresh FIGURE 1 — Microstructure of Inconel 600 tubing: (a) as-
test solution was prepared every 100 hours. received, phosphoric acid etch, 400X; and (b) as-received
+ 621 C for 18 h, 400X.

Constant Extension and Slow Strain Rate Tests

These tests were conducted on a slow strain rate testing
machine, using curved tensile specimens of 12.7 x 2.7 mm
gage. Before testing, the gage section was abraded to a
600-grit finish. The specimen was ultrasonically cleaned in
detergent solution; rinsed in distilled water, acetone, and
methanol; air dried; and mounted on the loading fixture. Slow
strain rate testing was carried out at a strain rate of 3 x
10 -6/s. For the constant extension test, the specimens were
pulled in the desired test solution at a relatively rapid strain
rate of 3 x 10 -5 /s to the desired stress level, and the straining
was then discontinued. The specimen was thus held at a con-
stant extension. The load was monitored on a strip chart
recorder. After an initial creep, the load leveled off. However,
as the crack eventually initiated and grew, the load relaxed fur-
ther and dropped to zero in case of complete fracture.
Resuits and Discussion
Microstructure of Material
The microstructure of the milt-annealed (as-received)
material is shown in Figure la after an electrolytic phosphoric
etch. Clearly, there is considerable grain boundary and intra-
granular carbide precipitation in the milt-annealed condition.
Figure lb shows the microstructure after the 621 C, 18 hour
sensitization treatment. The grain boundary carbides seem to
be larger and more continuous in the sensitized structure.
U -Bend Tests
Effects of Solution Composition and pH. Table 1 de-
scribes the exposure time and time to cracking for some
selected U-bend tests. The results for the remaining U-bends

392 CORROSION—NACE
 TABLE 1 — Results of Selected U•Bend Tests
Sample Time to
Number Environment Time of Exposure, h Cracking, h

1 0.1 M thiosulfate 1000 NC^1I

2 0.1 M thiosulfate + 1.3% boric acid 1000 NC
3 0.1 M thiosulfate + 1.3% boric acid, up to 80 C 72 h each at 40, 60, 80 C NC
4 0.1 M thiosulfate + 1.3% boric acid, held potentio-
statically at -100, -50, 0, +50, +100 mV SCE 24 h at each potential NC
5 0.1 M thiosulfate + 1.3% boric acid, notched specimen 1000 NC
6 0.1 M tetrathionate, continuously purged with 99.999%
pure nitrogen 48 <48
7 0.1 M thiosulfate + 1.3% boric acid at an initial pH 3
and continuously purged with 99.999% nitrogen 100 NC
8 0.1 M thiosulfate + 1.3% boric acid at an initial pH
-1.8 200 NC
9 (2) 0.1 M tetrathionate 120 NC
10(2) 0.1 M tetrathionate 18 <18

( ' ) NC = No cracking.
(2) Sample No. 9 from milt-annealed tubing; No. 10 mill annealed +621 C for 6 h; all other samples from mill-annealed
+621Cfor18h.

m
WITH 1.3% BORIC
ACID

ó 10-2 10-I
ut
0
z z
w 0
0 WITHOUT BORIC ACID
z z
0 2 10 - 2
á 10-3 a
1- 1-
1-
z
• z
• w
w
v z
z 0
0 v
v
a 10 -3
ó 10 -4 b
o

10 -4
10-5 1 10 100 1000
10 100 1000 TIME , h
TIME ,h

FIGURE 2 — Effect of concentration on cracking time FIGURE 3 — Effect of concentration on cracking time
for U-bends in sodium tetrathionate (Na 2 S 4 O 6) with and for U-bends in sodium thiosulfate (Na 2 S2 O 3 ) containing
without 1.3% boric acid. 1.3% boric acid and initial pH adjusted to 3.

showing detailed relationships between the time to cracking
and the concentration of the environments are illustrated in
Figures 2 and 3. It is of interest to note (Table 1) that none of
the specimens cracked in 0.1 M thiosulfate, whereas tetra-
thionate caused cracking down to 10 -5 M concentration
(Figure 2). Since thiosulfate was not an effective cracking
agent, efforts were made with higher temperature and poten-
tial control to accelerate the process. Attempts to initiate the
cracking were also made with a specimen that was notched
with a jeweler's saw, speculating that a crack might start
propagating from the notch, but no cracks were observed in
any of the above specimens during the test span used.
However, the specimens cracked rapidly when the pH of the
thiosulfate solution was reduced to 3 by adding an appropriate
amount of sulfuric acid (Figure 3).
Figure 2 shows the relationship between the cracking
time and tetrathionate concentration with and without 1.3%
boric acid. At 0.1 M concentration, the cracking was very rapid
and it was rather difficult to determine the time to cracking ac-
curately. Therefore, the time reported in Figure 2 at this con-
centration may be in error by 50% or more. At lower concentra-
tions, however, it was possible to monitor the cracking with
better accuracy. The relationship between log concentration
and cracking time is fairly linear between 10 -2 and 10 -4 M,

Vol. 39, No. 10, October, 1983 393

 and at 10 -5 M concentration there is a departure from lineari- ^Z•Z•,
ty, thus implying a possible threshold sulfur concentration for
/1C3M Na 2 S4 0 6
SCC. With boric acid, tests were conducted down to 10 -4 M 100
concentration of tetrathionate and a linear relationship be-
tween time and log concentration was observed. The cracking ' 0
is much faster without the boric acid, especially at lower con-
centrations of tetrathionate. Thus, at a concentration of 10 -2 á -100
M tetrathionate, the cracking time with and without boric acid
differs by a factor of 2, whereas at 10 -4 M tetrathionate the w -200
difference is about a factor of 6. This is expected, however, 1-
0
because at a fixed concentration of boric acid (1.3%) its in- - -300 10 M Na 2 S4 06
hibitive power will be more pronounced at a lower concentra-
_400
tion of tetrathionate. The inhibiting effects of boric acid were 1 1^I 1 1 11111111 ^ 1 1 1

also observed recently in the SCC of sensitized stainless steel 0 20 40 0.1 10 100
SECONDS
in sodium thiosulfate solutions. 2 Lithium hydroxide also in- HOURS
TIME
hibits cracking of Inconel 600 in borated sulfur environments,
as reported recently elsewhere 6
FIGURE 4 — Variation of corrosion potential of U-bends
Cracking time is plotted against the concentration of low with time in two different concentrations of sodium
pH sodium thiosulfate (containing 1.3% boric acid) in Figure 3. tetrathionate.
The pH of the solution was lowered to 3 at the commencement
of the test. At 0.1 M thiosulfate concentration, the cracking
was again very rapid (Figure 3), and it was difficult to deter-
mine the exact cracking time. Figure 3 also shows a w
r•el (a) 1.3% H+0.1
3 80 3 M Na 2 S Z 0 3
reasonably linear relationship between cracking time and log 100 (b) 1.3% H 3 80 3 +0.1 M Na 2 S 2 3 at pH3
(thiosulfate concentration). The time to cracking against con- (c) 1.3% H 3 B0 3 +10Íu1 Na 2S 2 0 3 at pH3
centration relationship shown in Figures 2 and 3 follows a very 0
similar course to that of sensitized stainless steel in
tetrathionic acid, as observed by Dravnieks and Samans, 8 ex- ._E 100
-
•1\ ------
cept that the stainless steel cracks even more rapidly than In-
conel 600. It is rather interesting to note that in borated
thiosulfate and tetrathionate of identical sulfur concentra-
w 200
-

tions, the time to cracking is very similar. Thus, at 10 -4 M a -300

tetrathionate (Figure 2) and 2 x 10 -4 M thiosulfate (Figure 3),
the time to cracking is about 500 hours. The major portion of
the cracking time, especially in dilute solutions, involved crack
initiation. When the initiation time, as determined by the first
sign of the crack under a low power microscope, is subtracted
from the total time to cracking reported in the figures, one ob-
tains an average crack propagation rate of approximately 5 to
10 nm/s in the most dilute solutions tested, and about 20 to 30
nm/s in 10 -2 M concentrations of both thiosulfate and
tetrathionate.
Although the sensitized specimens did not crack in any of
the tests in neutral 0.1 M thiosulfate (Table 1), they cracked
rapidly in very dilute solutions of both tetrathionate and low
pH thiosulfate (Figures 2 and 3). This implies that the material
was highly sensitized, but its susceptibility to crack initiation
in neutral thiosulfate solution was very low. However, once the
pH of the thiosulfate solution is lowered to the right level, the
initiation process appears to accelerate drastically and rapid
cracking results.
The following reaction, among others, takes place on
acidification of a thiosulfate solution: 9
20 40 0.I 1 in in
SECONDS HOURS
TIME
FIGURE 5 — Variation of corrosion potential of U-bends
with time in borated sodium thiosulfate solutions with
and without pH adjustment.
quickly precipitates. In contrast, one has to add a much
smaller amount of sulfuric acid to lower the pH of the 0.1 M
thiosulfate to 3, and the resulting sulfur remains in the form of
a colloidal suspension for a long time, and may even attack
the metal. It is not known at present whether an excess of
sulfate !ons thus generated actually hinders the cracking proc-
ess, but this is currently being investigated. However, the
results confirm that cracking in thiosulfate is very pH sen-
sitive. Studies on sensitized stainless steel in tetrathionate
also show that pH significantly influences the cracking at all
concentrations tested. 16 • 17

Corrosion Potentials and Thermodynamic Considera-

2S 2 0 3 2- + 3H+ = 2S + S0 2 + HSO 3 - + H 2 O. (1)
Apparently, all three sulfur species generated from the above
reaction are aggressive to sensitized stainless steel and
possibly Inconel 600. 10 Thus, sulfur dioxide was identified as a
potent cracking agent for sensitized Type 304 stainless steelt'
and cast Fe-Ni-Cr alloys of various compositions. 12 It is also
well known that wet elemental sulfur significantly increases
the corrosion rate of iron and mild steel 13 • 14 and chemisorbed
sulfur catalyzes the active dissolution of nickel in sulfuric
acid. 15 Interestingly, if the pH of the thiosulfate solution is
lowered too much, the cracking does not occur, as can be seen
from Table 1, Specimen 8, which was tested at an initial pH of
1.8. Because of the bisulfite/sulfurous acid buffer that is
operative in this system, one needs to add sulfuric acid to the
extent that the ratio of thiosulfate and sulfate ions ap-
proaches unity in order to lower the pH to about 1.8. Most of
the thiosulfate reacts with the acid, and the resulting sulfur
tions. The variation of corrosion potential with time for some
of the U-bends is shown in Figure 4 for concentrated and dilute
tetrathionate, and in Figure 5 for borated thiosulfate with and
without pH alteration. In all cases, the potential shifted to the
negative direction within a few seconds after immersion, ex-
cept for the dilute tetrathionate solution where the transition
was much slower. Note that the potential trend in 0.1 M
tetrathionate and 0.1 M thiosulfate at low pH is very similar. In
0.1 M thiosulfate (without pH reduction) where the specimen
did not crack, the potential moved back in the positive direc-
tion very quickly. In the dilute thiosulfate at low pH, a similar
trend occurred, but the potential shifted to negative values
again and then slowly moved toward positive values. The
potential monitoring was discontinued after about 70 hours.
However, the potential in all dilute environments was in the
range of -50 to - 100 mV vs SCE at the time of cracking. The
potential excursions in Figures 4 and 5 are perhaps indica-
tions of film formation on the specimen surface and possibly

394 CORROSION—NACE
 2N1203 + HSO3---Ni + HS0
111304 +
.8
Ni ++ + H2S03 HS03
Ni ++ + HSO-3
.4 Ni +++ Ni* N0
06
HSO3
0 NI+** 5 2 0 3
NiO + S 2 03
x 4NiS
W -0
-0 .8
Ni + H 2 S
Ni + HS -
-1 2
4 6 8 10
pH
FIGURE 6 — Potential-pH diagram for Ni-S-H 2 0 at 298K,
not considering SO 42 . All equilibria for dissolved
-
species are drawn for unit activity; equilibria involving
H 2 S are for 1 atmosphere gaseous H 2 S. L\G (NIS) =
-26 kcal/mole. Other values from Pourbaix Atlas; 19
Ni 3 S 2 not considered.
its localized breakdown. The corrosion potential of sensitized
stainless steel in polythionic acid also shows rapid transition,
and the behavior is ascribed to the formation of a sulfide film
on the specimen surface. 18
Recently, the thermodynamic basis of SCC of sensitized
304 stainless steel in sulfur compounds has been rationalized
from the composite potential-pH diagram for the Fe-S-H 2 0
system. 9 ' 10 From this diagram, the potential range of cracking
can generally be correlated to the expected potential range for
active iron dissolution and elemental sulfur formation. A
similar composite potential-pH diagram for the Ni-S-H 2 0
system has been constructed in Figure 6, generally based on
data provided by Pourbaix. 19 In this diagram, the NiS stability
field contains the open circuit potential range of SCC at pH
-3, i.e., - 50 to - 100 mV vs SCE (Figure 4). In the presence of
a NiS film, oxide passivation is not possible, and when the film
is ruptured, metal can dissolve to a considerable depth. In
borated thiosulfate of 0.1 M concentration with a pH of about
5.2, the U-bends did not crack until the pH was reduced to 3,
promoting the formation of S, S0 2 , and HS0 3 , according to
Equation (1). In this case, the susceptibility to cracking may be
ascribed to a combination of lower pH and aggressive decom-
position products. Tetrathionic acid might have been pro-
duced by the same process as was observed with sensitized
stainless steel in the presence of an oxygenated solution of
sulfur dioxide in water. 20
Effect of Oxygen Concentration. Results of tests on
Samples 6 and 7 in Table 1 in deoxygenated 0.1 M tetra-
thionate and borated 0.1 M thiosulfate at pH 3 show that while
the specimen in thiosulfate did not crack in 100 hours, the one
in tetrathionate cracked in less than 48 hours, although the
cracking was much less severe than that in the aerated solu-
tion of the same strength. In a separate experiment in deox-
ygenated 0.1 M tetrathionate, the specimen was withdrawn
after about 18 hours and no cracking was observed. No at-
tempt was made to measure the actual oxygen level in the
above test solutions. However, the results indicate that ox-
ygen influences the cracking process significantly. The results
also imply that the cracking mechanisms in tetrathionate and
low pH thiosulfate are probably somewhat different. In low pH
thiosulfate, nitrogen not only prevents oxygen from getting in,
but also purges sulfur dioxide generated from acidification
described previously in Equation (1). The sulfur dioxide may
play a role as an oxidizing agent in the cracking of Inconel 600
in low pH thiosulfate.
Vol. 39, No. 10, October, 1983
Ni02 + S03 -
111203 + 503 -
111304 + S03
Ni0 + SO3
12 14
°
FIGURE 7 — Macrograph of typical cracked U-bends: (a)
0.1 M thiosulfate + 1.3% boric acid at pH 3; and (b) 10 -
M tetrathionate.
Fractography. A typical cracked U-bend in borated thio-
sulfate (0.1 M) at pH 3 is shown in Figure 7a. Specimens
cracked in 0.1 M tetrathionate appeared very similar. The
stress pattern of the sample is clearly delineated. Since thio-
sulfate is cheaper than tetrathionate and is more readily
available in pure form, the 0.1 M thiosulfate at low pH might be
used as a test solution for detecting susceptibility to SCC and
studying residual stresses in sensitized Inconel 600. In dilute
solutions of thiosulfate and tetrathionate, however, the cracks
do not always seem to follow all of the stressed regions, as is
- evident from Figure 7b, which shows a specimen tested in
10 -3 M tetrathionate.
Figure 8a shows a typical scanning electron fractograph
of a U-bend cracked in tetrathionate (10 -4 M in this case). The
cracking is clearly intergranular. An energy dispersive X-ray
analysis (EDAX) of the fracture surface is shown in Figure 8b,
which reveals a prominent sulfur peak, apparently from tetra-
thionate or some of its reduced species. The EDAX scan of the
specimen cracked in pH 3 thiosulfate also revealed a promi-
nent sulfur peak.
Constant Extension and Slow Strain Rate Tests
Figure 9 shows a typical load (nominal stress based on
original cross section of the gage) against time plot for a
specimen undergoing SCC in borated 0.1 M thiosulfate at an
initial pH of 3. After an initial creep, the load levelled off and re-
mained relatively steady for about 4 hours, which is probably
the crack initiation period or a period of very slow crack
growth. This period is followed by an abrupt relaxation of load,
thus indicating the beginning of rapid crack propagation. The
load then decreased rapidly and eventually dropped to zero at
the end of complete cracking across the cross section of the
gage. The complete separation shows that very low stress in-
tensities are required for SCC in this system. The load relaxa-
tion at the onset of the apparent rapid crack propagation was
not always as abrupt as in Figure 10, but there was always a
395

FIGURE 8 — (a) Scanning electron micrograph of U•bend
fracture in 10 -4 M tetrathionate, and (b) EDAX scan of
the typica1 fracture surface shown in Figure 8a.
distinct change in the slope of the load relaxation curve to in-
dicate the onset of rapid crack growth and shortly afterwards
(1 to 2 hours), cracks were generally visible under the naked
eye or a low power microscope.
In Figure 10, the crack propagation rate in the pH 3 thio-
sulfate at 22 Cis plotted against the initial nominal stress with
a single test point at 60 C. The crack propagation rates in
Figure 10 and in subsequent figures were generally calculated
on the basis of the total time to failure from the commence-
ment of the application of the load. The crack propagation rate
decreases with stress, and at about 152 MPa initial stress no
crack propagation was noticed in 100 hours at 22 C, thus im-
plying a threshold stress level, similar to the ones observed in
polythionic acid and tetrathionate for sensitized Inconel 600
by other authors. 4' 5 At 60 C and 152 MPa, however, the speci-
men suffered some cracking within 24 hours. The crack,
however, developed toward the base of the gage and
perhaps because of the larger cross sectional area there, the
crack did not proceed any farther in 100 hours, as determined
by any absence of load relaxation. The propagation rate
shown in Figure 10 at 60 C is based on the length of the crack
in the first 24 hours. The result indicates that higher tempera-
396
0
a
ui
w
U)
J
Z
Z_
Z
Z
TIME, h
FIGURE 9 — Variation of load (nominal stress) with time
for a tensile specimen undergoing SCC in borated
(1.3%) 0.1 M thiosulfate at pH 3. Specimen held under
constant extension at an initial stress of —90% of yield
strength.
400
*0 DID NOT CRACK IN IOOHOURS
o TEST AT 60°C
0
a
300
1-
J
Z
5 200
O
Z
IOOL
0 20 40 60 80
CRACK PROPAGATION RATE, nm/s
FIGURE 10 — Crack propagation as a function of initial
nominal stress in constant extension tests in borated
0.1 M thiosulfate at pH 3.
ture reduces the apparent threshold stress for cracking. The
effect of temperature on crack propagation was studied in
more detail and the result is shown in Figure 11, which gives
an apparent activation energy of 3.5 kcal/mole. This shows
that temperature significantly accelerates the cracking pro-
cess. The specimens in Figure 11 were all held at an initial
stress equal to the yield strength.
The crack propagation rate at different concentrations of
thiosulfate, all at an initial pH of 3 and held initially at yield
stress, is shown in Figure 12. The rate seems to level off at
lower concentrations, especially when one considers the ap-
parent net propagation time, as shown in the dashed curve in
the figure. At 10 -4 M thiosulfate, the specimen did not crack,
although the U-bend in the same environment cracked in about
800 hours (Figure 3). This demonstrates that long term U-bend
tests may often provide information that one may miss in short
term loading or straining tests. Unlike the U-bends, however,
the rapid cracking time in Figure 12 down to 10 -3 M thiosul-
fate indicates that the crack initiation time is significantly
reduced in these cases owing to the surface film rupture
caused by the initial straining in the environment. Also, it ap-
pears that this initial straining was sufficient to initiate the
cracking process even when the nominal stress applied was
much below the yield stress, as can be noticed in Figure 10
where the specimen readily cracked at 22 C when strained up
to about 193 MPa, i.e., approximately 62% of the yield
strength. Once again the crack was completely intergranular.
The role of dynamic straining in crack initiation was also
noticed in our slow strain rate tests. 6 Thus, while none of the
U-bends cracked in pure or borated thiosulfate solution, slow
CORROSION-NACE
 TEMPERATURE,°C
60 40 20
500 30

E
c
n- 2 a 1.~ /_..I_.

W
1-
200
Z
0
1-

0
0
w
100

50 1
2.8 3.0 3.2 3.4
10 3 /T°K

FIGURE 11 — Crack propagation rate as a function of

temperature in borated 0.1 M thiosulfate at pH 3; speci-
mens held at an initial stress = yield strength.

JU 1 1111111 IIui 11111

a BASED ON TOTAL FAILURE TIME

BASED ON TOTAL FAILURE-APPARENT
90 INITIATION TIME
DID NOT CRACK IN IOOHOURS

E 80
c
W

70
z
0

60
0
a
50 -
U
0
U
40

30 10 -2 10 310'
MOLAR CONCENTRATION OF Na 2 S 20 3

FIGURE 12 — Crack propagation rate as a function of

concentration of borated thiosulfate at pH 3, based on
two different considerations of crack propagation time;
specimens held at an initial stress - yield strength.

strain rate specimens cracked readily down to 10 -2 M and

minor cracking was noticed at 1.1 x 10 -3 M thiosulfate. The
straining causes continuous emergence of slip steps, and by
frequently rupturing the oxide film promotes a low pH environ-
ment conducive to cracking. Additionally, if a crack was
initiated by slow straining in neutral 0.1 M thiosulfate, it con-
tinued to grow at constant extension even when the solution
was progressively diluted to 10 -5 M. This establishes the
special significance of initiation in thiosulfate solutions.
FIGURE 13 — (a) Nature of pits developed on flat
coupons in 0.1 M tetrathionate in -150 hours; (b) SEM
micrograph of pits of Figure 13a showing deposits
around pits; and (c) EDAX scan of deposits shown in
Figure 13b.

Vol. 39, No. 10, October, 1983 397


FIGURE 14 - Localized attack on flat coupon exposed
to borated 0.1 M thiosulfate at pH 3 for -400 hours.
Original surface was abraded to 600 grit finish. 200X.
Immersion Tests
In order to understand the possible role of localized corro-
sion in SCC, 1 cm 2 corrosion coupons of the milt-annealed/
sensitized material were immersed in 0.1 M tetrathionate and
borated 0.1 M thiosulfate with and without pH reduction. The
tetrathionate caused localized attack within 48 hours and after
about 150 hours, deep pits, as shown typically in Figure 13a,
were observed. The attack seemed to occur under the passive
oxide film, and was usually near a grain boundary. Figure 13b
shows a SEM micrograph of the same pit showing corrosion
products which gave a large sulfur indication in the EDAX scan
of Figure 13c. While the specimen in borated thiosulfate did
not suffer any localized attack, the one in pH 3 thiosulfate was
readily attacked within a few days. Figure 14 shows the form
of the attack after 400 hours: there is a general grain boundary
attack in addition to a single deep pit. These results suggest
that localized corrosion might nucleate SCC in the tetra-
thionate and 1ow pH thiosulfate solutions. Also, SCC on
U-bends in dilute tetrathionate and low pH thiosulfate
nucleated from pits. In concentrated solutions, however, no
pits were noticed on U-bends, perhaps owing to the very rapid
cracking process.
Possible Mechanisms of Low Temperature SCC
in Sulfur-Contaminated Nuclear
Steam Generators
We now discuss possible mechanisms of SCC in steam
generator tubing material similar to that used in this investiga-
tion, having determined that thiosulfate per se is not very ag-
gressive for this condition of sensitization. Naturally, some
steam generator tubes could be more severely sensitized,
depending on their carbon content and milt history, and would
therefore be susceptible to direct SCC by thiosulfate.
1. S2 0 32 is metastable in aqueous solutions and can
readily release sulfur or produce unstable 1ow valence sulfur
compounds by disproportionation or redox processes. 10 This,
at the high operating temperature, could lead to the formation
of metal sulfides MS x. The sulfides could have remained as
scales on the metal surface until after shutdown, when oxygen
entered and reacted with them to produce thionic acids by a
mechanism similar to the one suggested for iron sulfide
scales by Brophy 2 1
MSx + 0 2 + H 2 O - M xOy + H 2 S X O 6 (2)
The thionic acid, thus produced, could then cause the crack-
ing.
2. Another possibility is the effect of low pH that one
might expect to exist in an occluded area, e.g., under a loosely
adherent surface deposit. In the presence of thiosulfate, the
low pH solution could promote SCC initiation.
3. Accidental ingress of sulfuric acid into the primary
coolant may cause localized disproportionation of thiosulfate
398
(already present owing to leakage). Sulfide formation is there-
fore possible in localized areas that see a relatively high con-
centration of sulfuric acid. These sulfides could then react ac-
cording to Equation (2).
Conclusions
1. The propensity to initiation of SCC of sensitized In-
conel 600 in sodium thiosulfate is much lower than that in
sodium tetrathionate.
2. Sodium thiosulfate at low pH (-3) is a very potent
cracking agent for sensitized Inconel 600, and can be used as
an inexpensive test solution for sensitization.
3. Temperature significantly accelerates the cracking
and perhaps also decreases the apparent threshold stress for
cracking.
4. Boric acid inhibits or retards SCC in the tetrathionate
environment.
5. Although dynamic tensile straining produces much
faster crack initiation than a U-bend, long term U-bend tests
provide significant information regarding SCC initiation.
6. There is evidence that localized attack such as pitting
near grain boundaries may precede polythionate SCC.
Acknowledgment
This research was carried out under the auspices of the
U.S. Nuclear Regulatory Commission under FIN A-3380. Ex-
perimental assistance was provided by C. Schnepf, T. Roberts,
and J. Svandrlik. The potential-pH diagram (Figure 6) was con-
structed by B. Alman. Discussions with J. R. Weeks and D. van
Rooyen are gratefully acknowledged.
References
1. Newsletter on Three Mile Island Unit 1, Nuclear News,
Vol. 25, p. 47 (March, 1982).
2. Isaacs, H. S., Vyas, B., and Kendig, M. W., Corrosion, Vol.
38, p. 130 (1982).
3. Dhawale, S., Cragnolino, G., and MacDonald, D. D., EPRI
Progress Report RP1166-1, July-December, 1980.
4. Scarberry, R. C., Pearman, S. C., and Crum, J. R., Corro-
sion, Vol. 32, p. 401 (1976).
5. Berge, Ph. and Donati, J. R., Nuclear Technology, Vol. 55,
p. 88 (1981).
6. Newman, R. C., Roberge, R., and Bandy, R., Environment-
Sensitive Fracture: Evaluation and Comparison of Test
Methods, accepted for publication in ASTM proceedings,
1983.
7. Bulischeck, T. S. and van Rooyen, D., Corrosion, Vol. 37,
p. 599 (1981).
8. Dravnieks, A. and Samans, C. H., J. Am. Pet. Inst., Vol. 37,
No. 3, p. 100 (1957).
9. Newman, R. C. and Sieradzki, K., Corrosion Science (in
press).
10. Cragnolino, G. and MacDonald, D. D., Corrosion, Vol. 38,
p. 406 (1982).
11. Piehl, R. L., J. Am. Pet. Inst., Vol. 44, No. 3, p. 189 (1964).
12. Hart, A. C., Br. Corrosion J., Vol. 6, p. 164 (1971).
13. Farrer, T. W. and Wormwell, F., Chem. Ind., Vol. 5, p. 196
(January, 1953).
14. MacDonald, D. D., Roberts, B., and Hyne, J. B., Corrosion
Science, Vol. 18, p. 411 (1978).
15. Oudar, J. and Marcus, P., Appl. Surface Sc., Vol. 3, p. 48
(1979).
16. Zucchi, F., Frignani, A., Trabanelli, G., and Zucchini, M.,
La Metallurgia Italiana, No. 2, p. 49 (1979).
17. Zucchi, F., Frignani, A., Zucchini, M., and Trabanelli, G.,
La Metallurgia Italiana, No. 4, p. 188 (1976).
18. Kowaka, M. and Kudo, T., Nippon Kinzoku Gakkaishi,
Vol. 43, p. 595 (1979).
19. Pourbaix, M., Atlas of Electrochemical Equilibria in Aque-
ous Solutions, Pergamon Press (1966).
20. Ahmad, S., Mehta, M. L., Saraf, S. K., and Saraswat, 1. P.,
Corrosion, Vol. 37, p. 412 (1981).
21. Brophy, A. J., Materials Performance, Vol. 13, p. 10 (1974).
CORROSION-NACE