This research was supported by the US-USSR Co- 1800

operative Research Program through the National Science

Foundation. The work benefited from facilities made avail- WOO
able by the NSF-MRL Program through the Center for
Materials Research at Stanford University. Dr. Hua received 1600
one year supplementary support from Stanford's Depart-
ment of Applied Earth Sciences, as a teaching assistant.
1500 I
1455 |t
1400 ,'7"', ,
REFERENCES
1. A.W. Cramb and G.R. Belton: Metall. Trans. B, 1981, vol. 12B, 1300
t~ 1500
pp. 699-704. Ix
2. C. H. Hua: Ph.D. dissertation, 1980, Stanford University, Stanford, CA.
3. C.H. Hua and N. A. D. Parlee: Metall. Trans. B, 1982, vol. 13B, ,~ 1200
pp. 357-67. ix 1148
4. C.H. Hua and N. A. D. Parlee: Stanford University, Stanford, CA, l,g
IlO0 Co4S3+_. Y
unpublished research, 1982. 1058
5. G.R. Belton: Metall. Trans. B, 1976, vol. 7B, pp. 35-42. t/.I
I,-
6. AIME Physical Chemistry of Steelmaking Committee, Electric Furnace I O00
Steelmaking, AIME Book, Interscience Publishers, 1963, vol. II,
pp. 125 and 134.
7. R.J. Fruehan and L.J. Martonik: Metall. Trans. B, 1980, vol. liB, 900
pp. 615-21.
600

I
Predominance Area Diagrams
of the System Co-S-O
700 -

I
0
Co
I0 20
u

30
L__Y__A:
Wt % S
40 50
'o

60

between 583 and 1148 K Fig. l - - T h e system cobalt-sulfur (after Chang and Sharma6).

N. JACINTO, H. Y. SOHN, and M. NAGAMORI
The thermodynamics of the system Co-S-O have been
studied by Ingraham. L2These thermodynamic studies, how-
ever, do not incorporate some of the sulfide phases the
thermodynamic stabilities of which are well-established. 3-6
This note presents new predominance area diagrams of the
Co-S-O system in the temperature range 583 to 1148 K,
including the stability zones of all known cobalt sulfides.
The Co-S phase diagram given by Hansen and Andereko 3
is essentially correct and has been updated by Elliott4 and
Shunck. 5 Chang and Sharma 6 calculated the phase diagram
of the Co-S system, as reproduced in Figure 1. There are
five known compounds for this system, namely, C09S8
(cobalt pentlandite), C03S4 (linnaeite), CoS2 (cattierite),
Co453--y, and CoSl+y. The Co453+y and CoSl+y phases have
a rather large range of nonstoichiometry and are stable only
at high temperatures.
Thermodynamics of the Co-S system have been studied
by various investigators. Rosenqvist, 7 Laffite, 8 Leegaard
and Rosenqvist, 9 Rau, ]~ and Chen and Chang ~ measured
the activity of sulfur as a function of temperature and
composition.
N. JACINTO, formerly Graduate Student in metallurgy at the University
of Utah, is now with the University of Oruro, Oruro, Bolivia; H. Y. SOHN
is Professor in the Department of Metallurgy and Metallurgical En-
gineering, University of Utah, Salt Lake City, UT 84112-1183; and
M. NAGAMORI, formerly Associate Professor of Metallurgy at the
University of Utah, is now with Centre de Recherches Minerales, Quebec
Government, 2700 Einstein, Ste-Foy, Quebec G1P 3W8, Canada.
Manuscript submitted November 29, 1982.
Since the existence of five cobalt sulfides is well-
established, as shown in Figure 1, the stability ranges of
these sulfides must be included in the predominance area
diagram. In this study, the following nine solid phases were
considered in constructing the predominance area diagrams:
CO, C0958, C0354, C052, C0453§ , CoSI+y , C0504, CoO,
and Co304.
The thermodynamic data for various solid cobalt sulfides
reported by Rosenqvist and Leegaard 7'9 were combined with
the free energy data ~2of the reaction H2 + 0.5Sz = H2S to
establish the free energy of formation data on the basis
of S2(g).
The free energy changes for the reaction C09S8 + H2S =-
9CoS~+y + H2 cannot be expressed as a linear function of
temperature, because the sulfur content of the C09Ss-satu-
rated monosulfide changes with temperature. 7 In the present
work, the following free-energy values were derived, based
on the work by Rosenqvist, 7 for the reaction C09S8 +
0.5S2(g) = 9CoSl+y:
Temperatu~ (K) ~G~
773 -54894
873 -54669
973 -57089
1073 -61533
Other selected thermodynamic data are listed in Table I.
The free-energy changes and the corresponding equi-
librium constants (Ke) for the bivariant and the univariant
reactions were calculated using the data listed in Tables I
to III.
Figures 2 to 6 show the predominance area diagrams
of the Co-S-O system at various temperatures. The partial

506--VOLUME 14B, SEPTEMBER 1983 METALLURGICAL TRANSACTIONS B

 Table I. Selected Free Energy Data for the Co-S-O System

Reaction AG~ (J)* Reference

H2(g) + 0.5Sz(g) = tt2S(g) - 8 4 1 2 1 + 1 5 . 1 8 T log T - 2 . 5 3 T 12
Oz(g) + 0.5S2(g) = SO2(g) -362427 + 72.43T 12
1.502(g) + 0.5S2(g) = SOs(g) - 4 6 6 9 8 8 - 2 3 . 2 6 T log T + 2 4 1 . 8 8 T 12
Co(s) + 0 . 5 0 2 ( g ) = CoO(s) -233891 + 70.71T 12
3Co(s) + 202(g) = Co30,(s) -884937 + 360.25T 12
Co(s) + 202(g) + 0.5S~(g) = CoSO~(s),, - 9 6 1 8 0 8 - 8 6 . 0 3 T log T + 7 0 0 . 8 1 T 1
Co(s) a_ 2Oz(g) ~- 0.5S~(g) = CoSO~(s)~ - 9 5 7 6 8 6 - 6 7 . 7 2 T log T + 6 3 9 . 4 0 T 1
9Co(s) + 4Sz(g) = Co9S8(s) - 1 2 7 6 7 8 7 + 121.34T log T + 2 5 0 . 8 8 T 7, 12
3Co(s) + 2Sz(g) = Co3S4(s) - 5 6 1 1 3 4 + 6 0 . 6 7 T log T + 1 0 9 . 3 2 T 7, 9, 12
Co(s) + Sz(g) = CoS:(s) - 2 6 3 3 6 6 + 3 0 . 3 3 T log T + 7 5 . 2 0 T 7, 9, 12
4Co(s) + 1.5Sz(g) = Co4S~.~. - 3 6 9 9 9 2 + 4 5 . 5 0 T log T - 9 . 6 0 T 7.12
*For temperature ranges of validity, see the references cited.

Table II. Equilibrium Constants for Bivariant Equilibria in the Co-S-O System

log K ,
Reaction 583 K 783 K 883 K 983 K 1113 K
2 C o + Oz = 2CoO 34.528 23.822 20.287 17.472 14.568
6 C o O + O2 = 2Co304 17.368 8.979 6.209 4.003 1.728
~ o + SO2 = iCo,~S8 + ()2 - 18.221 - 13.679 - 12.889 - 11.005 --
CO354 ~- 7Oz = 3CoSO~ 4 SOz 179.478 120.033 100.545 -- --
,JCooSs + SO2 = 4~Co~S,, * 0 2 - 22.781 - 16.914 - 14.985 - --
2Co958 4- 2 5 0 2 = 18COO + 16SO2 602.286 433.747 377.604 333.324 --
Co:~$4 + 2 S O : = 3CoS2 + 2 0 , - 47.335 - 36.185 - 32.520 - 29.609 --
CoSO~ = C o O + S()2 + 2aO: - 16.241 - 8.423 - 5.877 - 3.877 - 1.13
3CosS4 + "~0,_ = 9 C o O + 12SO2 392.268 284.294 . . . .
CoS2 + 3 0 2 = C o S O , + SO2 75.604 52.073 44.355 38.106 31.848
Co304 -~- 3S0~ + 0 2 = 3CoS04 40.038 20.779 14.526 9.215 4.274
Co958 + SO~: = 9 C o S l + y -~ 0 2 -- - 16.746 - 14.417 - 12.425 --
C o 3 5 4 -~- 0 2 = 3 C o S ~ , , . - t SO2 -- 17.159 15.843 14.799 --
2CoO + 2SO: = 2CoS~+,. + 302 -- - 51.863 - 45.160 - 39.797 --
COSO4 = CoS,+y + 2 0 2 -- -- - 28.234 - 23.232 -18.447
CoS I ~ • SO2 = CoS2 -:- 02 . . . . . 13.401
.4~-Co + SO2 = :~Co~S~_~ ~ 0 2 . . . . . 9.684
4COS.,;. + O2 = CO453+:. -}- S O 2 . . . . 10.304

Table II1. Equilibrium Constants for Univariant Equilibria in the Co-S-O System

log K,
Point Reaction 583 K 783 K 883 K 983 K 1113 K
A 8z~Co + SO., " 2 C o O ~- 8q2o9S8 16.308 10.142 8.098 6.467 --
B 4Co3S4 + 6 C o O - 2Co9S8 4- 3 0 2 79.262 . . . .
B' 2Co958 + 0 2 16CoS~.v * 2 C o O -- 18.371 16.326 14.948 --
B" 10COS1 ~. ~- 2 C o O = 3C04S3+y q'- 5 0 2 . . . . . . 3.337
C 2CosS4 + 2 C o 0 - 8 C o S ~ , . ~ . + 02 -- - 17.420 -- -- --
C' 4 C o O + 4SO2 3COSO4 + CoS i,y -- -- - 4.726 8.276 -11.597
D C o O ~- C0354 4- 12-~2 " 4COSO4 195.718 157.082 -- -- --
D' 2C0354 + CoSO,t = 7C081%. + 2SO2 -- -- 3.453 m __
E C03S~ -~ 40_, - C 0 5 2 -}- 2 C 0 5 0 4 103.873 67.960 56.190 -- --
E' 3CoS~-~ + 2 S 0 2 = 2COS2 + COS04 . . . . 58.641 -75.184
F 2 C o O + CoSO4 - C 0 3 0 4 -I- 5 0 2 7.557 - 3.933 - 2.772 - 1.737 --

p r e s s u r e s o f SO2 a n d 0 2 a r e e x p r c s s e d in t e r m s o f a t m
(1 a t m = 1 0 1 . 3 k P a ) .
T h e p r e d o m i n a n c e d i a g r a m at 5 8 3 K is s h o w n in F i g -
u r e 2. T h e s t a b l e s u l f i d e p h a s e s at t h i s t e m p e r a t u r e a r e
Co9S8, Co3S4, a n d C o S z . T h e c o n f i g u r a t i o n o f t h i s d i a g r a m
is v a l i d o n l y u p t o 7 3 3 K . A b o v e t h i s t e m p e r a t u r e ,
t h e C o S ~ , y p h a s e m u s t b e i n c l u d e d in t h e p r e d o m i n a n c e
area diagram.
F i g u r e s 3 a n d 4 s h o w t h e p r e d o m i n a n c e d i a g r a m at 7 8 3
and 883 K, respectively. The configuration of these dia-
g r a m s is v a l i d b e t w e e n 7 3 3 a n d 9 3 0 K , w h e r e t h e s t a b l e
s u l f i d e p h a s e s a r e Co9S8, C o S , ,y, Co3S4, a n d COS2.
A t 7 8 3 K ( F i g u r e 3), t h e s t a b i l i t y z o n e o f C o S ~ y in t h e
p r e d o m i n a n c e d i a g r a m is t h e n a r r o w a r e a t h a t l i e s b e t w e e n
t h e Co354 a n d C o g S s p h a s e s . It is n o t e d t h a t C o S ~ , y c a n -
n o t b e in e q u i l i b r i u m w i t h C o S O ~ at t h i s t e m p e r a t u r e . A s

METALLURGICAL TRANSACTIONS B VOLUME 14B, SEPTEMBER 1983 - 507

 O ~ 4

-2
CoSO4
CoSz
CoS2 COS04

-2

Od F
~ ~-4
f,/)
Q.
0
J -I0 0
._1 -6
CoO

-12
CoO -8

Co304 Co304
-14
-IOl-// 1A

-16
-12

- ,!8 " -24 ~ -20 ~ -16 4 -12 -8

-38 - 3 4 - 3 0 - 2 6 - 2 2 -18 -14 Log P02
Log POp_
Fig. 3 - - Predominance area diagram of the Co-S-O system at 783 K.
Fig. 2--Predominance area diagram of the Co-S-O system at 583 K.

4 ~
2 ~ C~

CoSO 4
J ' CoO
CoS z -4

-21- // iB'
,.F
o(D -8 r g I Ii i i i i i i i i i i i i
O. "21 -19 -17 -15 -13 -II "9 -7 -5 -3
-4 L o9 POz
O Fig. 5 - - Predominance area diagram of the Co-S-O system at 983 K.
..J

-6 temperature increases, the stability zone o f CoS~+~. be-

CoO comes wider, as seen in Figure 4, coming into equilibrium
with COSO4.
-8~ / / " / /~ co3o, The Co3S4 is stable only up to 930 K. On the other hand,
the Co~$3_~ phase is stable above 1058 K. Therefore, in the
temperature range 930 to 1058 K the stable sulfide phases
are Co9S8, CoS~+y, and COS2. An example o f this configu-
-IO ration is shown in Figure 5.
F i g u r e 6 s h o w s the p r e d o m i n a n c e a r e a d i a g r a m at
1113 K. At this temperature, the stable sulfide phases are
- 1 2 ~ , and CoSz. The CogSs phase is unstable at
-26 -22 -18 -14 -I0 -6 -2 Co453+_y , CoSl+y

temperatures above 1107 K.

Log P02
At 1148 K, a liquid phase appears as a result of the eu-
Fig. 4--Predominance area diagram of the Co-S-O system at 883 K. tectic reaction between Co and Co4S3_.~.. The predominance
508--VOLUME 14B, SEPTEMBER 1983 METALLURGICALTRANSACTIONSB
 , v , , , , , ,
4 E' C
2. CoS2 ~'
,n
o~ / / coo
.~-rjc, o reported significant solubilities and diffusivities for fluorine
-4
0 have observed the internal fluoridation of a Ni-5.6 at. pct
_6~ A Cr alloy. 6 Likewise, the internal chloridation of a base metal
I t"
-16 I I I
-14 I I
-12. -tO
I I I [
-8 -6
I I
LO0 p02
Fig. 6--Predominance area diagram of the Co-S-O system at 1113 K.
area diagrams above 1148 K should therefore include a sta-
bility zone for the liquid phase.
The predominance area diagrams of the Co-S-O system
reported by Ingraham ~'2 included only the Co9S8 and CoS2
solids at 950 and 1200 K. The results of the present study
indicate the stable sulfide phases at 950 K are Co9S8,
CoSl+y, and COS2, whereas those at 1200 K are liquid
phase, C0453+y, CoSl+v, and COS2.
One of the authors (N. J.) expresses his gratitude to the
LASPAU (The Latin American Scholarship Program of
American Universities) for the scholarship which allowed
him to carry out this research.
REFERENCES
1. T.R. Ingraham: Can. Met. Quart., 1964, vol. 3, pp. 221-34.
2. T.R. Ingraham: Proceedings of the First International Meeting
on Applications of Fundamental Thermodynamics to Metallurgical
Processes, G.R. Fittered, ed., Gordon & Breach Sci. Pub. Inc.,
New York, NY, 1967, pp. 179-97.
3. M. Hansen and K. Andereko: Constitution of Binary Alloys, 2nd ed.,
McGraw-Hill Book Co., New York, NY, 1958, pp. 497-99.
4. R.P. Elliott: Constitution of Binary Alloys, Ist Supplement, McGraw-
Hill Book Co., New York, NY, 1965, p. 332.
5. F.A. Shunck: Constitution of Binary Alloys, 2rid Supplement,
McGraw-Hill Book Co., New York, NY, 1969, p. 263.
6. Y.A. Chang and R. C. Sharma: Calculation of Phase Diagrams and
Thermochemistry of Atloy Phases, Y. A. Chang and J. F. Smith, eds.,
TMS-AIME, Warrendale, PA, 1979, pp. 145-74.
7. T. Rosenqvist: J. Iron Steel Inst., 1954, vol. 176, pp. 37-57.
8. M. Laffite: Bull. Soc. Chim. France, 1959, pp. 1223-33.
9. T. Leegaard and T. Rosenqvist: Z. Anorg. Chem., 1964, vol. 328,
pp. 294-98.
10. H. Rau: J. Phys. Chem. Solids, 1976, vol. 37, pp. 931-34.
11. Y.O. Chen and Y.A. Chang: Metall. Trans. B, 1978, vol. 9B,
pp. 61-67.
12. O. Kubaschewski and C. B. Alcock: Metallurgical Thermochemistry,
Pergamon Press, New York, NY, 1979, pp. 278-84.
METALLURGICALTRANSACTIONS B
, , , , i , 1 ,
Internal Chloridation
COS04 of Dilute Ni-Cr Alloys
YONG-KUN LI and ROBERT A. RAPP
i 84
The phenomena and kinetics of the internal oxidation of
dilute alloys are well established. ~'2'3 Reddy and Rapp have
in solid copper and nickel at elevated temperatures, 4'5 and
Co3(
alloy containing a small concentration of a more reactive
I I
-4
I I
-2 I
0
I
solute is expected if the base metal exhibits a substantial
solubility and diffusivity for elemental chlorine. No prior
determinations of solubility or diffusivity data are available
for chlorine in any metal. In this study two solid solution
Ni-Cr alloys (0.56 and 2.0 at. pct Cr) were internally chlo-
ridated by an experiment similar to that of Reddy and Rapp. 6
Small annealed alloy coupons were polished on 600 grit
paper and ultrasonically cleaned in acetone. These speci-
mens were surrounded in an A1203 crucible by a mixture of
Ni + NiC12 powders (1 : 2 volume ratio) and covered by a
tight A1203 lid. Such crucibles were sealed into an evacuated
quartz tube and exposed for desired times (two or four days)
at a given temperature (700, 800, 900 ~ After exposure,
the specimens were examined in the SEM and metallo-
graphic microscopes; the depths of internal precipitation
were measured using a calibrated ocular lens. To substan-
tiate the identity of the precipitates, one specimen was
examined by Auger analysis.
Zones of internal chloridation were observed for each
experiment. The assumption of CrC12 solid precipitates was
supported by Auger analyses where prominant peaks for
chlorine (but not oxygen) correlated with peaks for chro-
mium upon sputtering beneath the contaminated surface
layer. CrC13 is not thermodynamically stable at Pc~
(Ni + NiCl2). The precipitation front was farther advanced
along the alloy grain boundaries than the uniform depth
within the grain interiors, suggesting more favorable grain
boundary nucleation of precipitates. Figure 1 shows a repre-
sentative microstructure for internal chloridation. The
uniform depths of internal chloridation were measured and
are plotted in the parabolic plot of Figure 2. The slopes of
the lines were interpreted in terms of the following Eq. [1]
to provide data for the permeability product N~Dc~ in nickel:
~2 - - U~])clt [1]
where ~ is the depth of internal chloridation, Nb~ is the
solubility of chlorine (for Ni + NiC12 equilibrium), Dc~
the chlorine diffusivity, N~c~~the Cr atom fraction in the bulk
alloy, and t the experimental time. The derivation of Eq. [1]
assumes that the precipitate is very stable, and therefore has
a solubility product of virtually zero.
In Figure 3, the product N~c~Dc~ is plotted vs 1/T; the
best-fit line for these data gives:
YONG KUN LI is Lecturer, Corrosion Section, Beijing University
of Iron and Steel Technology, Beijing, People's Republic of China.
ROBERT A. RAPP is Professor, Department of Metallurgical Engineering,
The Ohio State University, Columbus, OH 43210.
Manuscript submitted January 10, 1983.
VOLUME 14B, SEPTEMBER 1983--509