CALPHAD Vo1.8, No.2, pp.

101-119,1984 0364-5916/84$3;00 * ;OO

Printedin the USA. (cl 1984 PergamonPress ttd;

Calcul.ation of the Ti-C, W-C and Ti-W-C Phase Diagrams.

BjGrn Uhrenius
Sandvik AB, Hard Materials
P 0 42056
S-126 12 Stockholm, Sweden

Abstract

The two binary W-C and Ti-C systems were analysed in thermodynamic
terms by using a thermodynamic model which allows for the use of
sublattices. Those carbides, which show some variation in their
Me/C-ratios, such as the Tic-carbide were treated as solution
phases using this model. As a result of this analysis the two
binary W-C and Ti-C phase diagrams could be calculated. By combin-
ing these results with the analysis of the Ti-W system presented by
Murray (1) a number of isothermal sections of the ternary Ti-W-C
system were calculated. These are in close agreement with the
experimental data according to Rudy et al (2).

The Ti-C system

Pure titanium exists in two allotropic modifications, a low tempera-

ture form (alpha) with an hcp (A3) structure which is stable up to
1155 K and a high temperature form (beta) stable to the melting
point of titanium, which is 1941 K. The beta-modification has a bee
(A2) structure and dissolves a maximum of N 0.6 at% carbon at
1923 K (3).

By adding carbon above this level the intermediate Tic-phase is

formed. This carbide has a fee (NaCl, Bl) structure but with a high
fraction of vacancies on the carbon sites at the lower carbon ac-
tivities.

The Tic-carbide formula should thus be written Ti (C,v) where

v stands for vacancies. There are consequently eq&al nu&ers of
sites for titanium atoms as for carbon atoms and vacancies togeth-
er. The two types of sites are arranged in two separate fcc-
lattices.

The Ti(C,v)-carbide participates in the formatipn of two eutectics,

one with the bee-titanium phase at 1933 K and x = 0.015 (4)
and one with graphite at 3049 K and x = 0.63 ($1. At 3340 K
the carbide melts congruently having G he composition at the maxium
of x = 0.44. According to Rudy et al (4) the carbon content of
the garbide varies from x, = 0.32 at 1923 K in equilibrium with
bee-titanium to xC=0.494 in equilibrium with graphite at 3049 X.
_--_-________-
Received July 11, 1983

101
102 BJORN UHRENIUS

A thermodynamic model for the description of solid solutions with

the atoms arranged in sublattices was developed by Hillert and
Staffansson (5). According to this model the following expressions
can be obtained for the description of the Gibbs energy of the
Ti(C,v)-phase:
C 0 2 Ti
GTi = GTiE + RT ln(l-yC) + yCLCv (la)
C
GC = 'GTi; - OGTi; + RT ln(yC/(l-yC)) +

(l-Zy,)L,$ (lb)

The expression OG .' - in eq (lb) can be identified

as the standard sTife $he Ti(C,v)-solution but the
individual parameters stand for the Gibbs energy
of the stoichiometric energy of pure titanium
in an fee-modification respkctively. InTihe latter case all carbon
atoms are replaced by vacancies. The L -parameter expresses
the interaction between carbon atoms aA8 vacancies when the other
lattice is completely filled by titanium atoms. The yC-variable
represents the site-fraction of carbon and is for the
Ti(C,v)-solution given by

yC = XC/(l_XC)
where x is the mole fraction of carbon in the carbide.
C
An ordinary subregular substitutional solution model was used for
the description of the liquid, the bee- and hcp-phases. The Redlich-
Kister notation was used and the following equation describes the
integral Gibbs energy of these phases.

Gm = xcoGC + xTioGTi + xCxTi(A+B(xC-xTi)) +

RT(xClnxC + xTilnxTi) (2)

The Ti(C,v)-phase
---- --
The Gibbs energy of formation of the stoichiometric "Tic" has been
tabulated by Hultgren et al (6). Although probably a Tic-carbide of
completely stoichimetric composition is not likely to be formed,
their tabulation was used for the evaluation of the Gibbs energy of
formation of "TilC1". The following expression was obtained by
fitting to their tabulation.

OG c _ OGTyCP- O,$’ = -184640 + 11.058T J (3)

TiC

Storms (7) determined the vapor pressure of Ti(g) over Ti(C,v)-

carbides of compositions varying from x =0.35 to x =0.48 at
1900 K. From his measurements-end the v Spor press&e over pure
bee-Ti at 1900 K, pTi=3.11 10 $1" as given by Hultgren et al
raction parameter L as well as the quantity
A;',$ h:o;;!& were evaluated byCYnserting in eq. (la). The result of
Tiv
that evaluation is presented in Fig 1. It is evident that the
concentration dependence of the thermodynamic properties of the
carbide can not be represented by one single parameter or, that at
least one of the data points are in error. In view of the limited
number of data available it was decided to rely upon the simple
description represented by the line in Fig 1. This is equivalent to
the following choice of parameters
 CALCULATION OF PHASE DIAGRAMS 103

Ti -173640 J (41
Lcv =
'GTi; - OGTT = -151600 3 (5)

0 Storms (5)

05

Fig 1. Evaluation of the interaction parameter,

LC.,, for the Ti(C,v)-carbide from data
on the vapor pressure of Ti over carbides
of varying composition, according to
Storms (7).

The thermodynamic properties of the Ti(C,v)-phase has also been

investigated by other methods. Alekseev et al (8) equilibrated
Ti-g-specimens with CH /H - mixtures at temperaturesTketween
700 C and 1000°C. Thei! data were also used and an LCv Tparameter
of -42000 J could be evaluated, but the corresponding Gibbs energy
of formation of TiC was far too positive as compared to the values
accepted by Hultgren (6). By using the mean value of their data for
carbides of compositions close to x =0.45 and by neglecting the
carbides of other compositions and fiy combining with the Gibbs
en$,pgy of formation of stoichiometric TiC according to eq. (31, an
-parameter of -200 kJ was obtained, in close agreement
h Storms' data.

Emf-measurements made by Malkin and Pokidyshev (9) inTfhe tempera-

ture range 1045 K to 1135 K are consistent with an LCv -value

of -170 kY and a Gibbs energy difference of OGTiz - 'G T1

hcp= +74 kJ
104 MORN UHRENIUS

Q-;’
1700
Llqutd /
i / ?’ I

Fig 2. The solubility of carbon in hcp- and

bee-Ti as given by various authors (from
Storms (7)).

0.007 1195 K

a -Ti + TIC

r
0 .02 04 .06 .08 0.10
Ti MOLE - FRACTION CC

Fig 3. The solubility of carbon in titanium as

calculated on basis of the present
evaluations.
 CALCULATION OF PHASE DIAGRAMS 105

3250

liqutd i graph.

0.65 : 3054

2750

z
5
= 2500
Y
TE + graphite
E
2 2250
s
E
I TiC
fJ 2000
1927 : 0 013
I.32

1750

fl - TI + TiC
1500

1250 1195

a - TI - TIC
,
0.40 0.60 0.80 1 .m
MOLE - FRACTION CC

Fig 4. The calculated Ti-C phase diagram.

Table I. Comparison between ca .culated equilibria and the experimen-

tal data according to Rudy (4) on the Ti-C system.

Phase Phases Composition,xC Temperature, K

equilibria talc. exp. talc. exp.

eutectic bee-Ti 0.007

bee-Ti/l/Ti(C,v) liquid 0.013 0.015 1927 1923
Ti(C,v) 0.32 0.32

congruent
melting liquid/
Ti(C,v)/iiq. Ti.(C,v) 0.44 0.44 3340 3340

eutectic Ti(C,v) 0.48 0.49

3054 3049
Ti(C,v)/liq./ liquid 0.65 0.63
graphite.
106 BJORN UHRENIUS

Furthermore, emf-measurements made by Koyama and Ha&imoto (10) at

853 K, are consistent with an even more negative L -value
of -500 kJ and a corresponding Gibbs energy differ gXce of

OG hcp = +250 kJ
' - OGTi
Tiv
Grievson (11) presented results from eqyilibrations with CH4/H2-
mixtures giving a far more positive LCv -value of -4 kJ.

Lacking more reliable information, it was decided to rely upon the

evaluation based on the data according to Storms (7).

By combining with the lattice stabilities of carbon and titanium

according to Kaufman (12) presented in the appendix the following
parameters were obtained for-the description of the Ti(C,v)-phase
OG hcp = 46030 3 (6a)
OGTi.t - Ti

‘G ’ _ ‘GTFCP_ ‘Gzr = -184640+11.058T J (6b)

TiC

Ti
- 173640 J (6~)
Lcv =
The liquid
--- ----phase
No thermodynamic information could be found for the description of
the liquid and the parameters describing the properties of this
phase were evaluated from the phase diagram information as pre-
sented by Rudy (4) and from the data on the carbide presented
above.

By combining eqs. (K4, KS and K6) and the data on the carbide given
by eqs. (6) with the phase diagram information at the invariant
equilibria i.e. the eutectic at 1923 K, the melting point maximum
of Ti(C,v) and the eutectic at 3049 K, the following parameters
were obtained for the description of the excess Gibbs energy of the
liquid.
Al = -177100 - 22.384T 3 (7)
Bl = -95400 + 48.120T J (8)
The solid solutions of hcp-Ti and bee-Ti
_-----__------------
The reported solubility of carbon in hcp-Ti and bee-Ti is subject
to.some scatter as related by Hansen (13-15) and supplements. In
the present analysis the values given by Bickerdike and Hughes (3)
and by Wagner et al (16) were used to evaluate the interaction
parameters describing the Gibbs energy of the hcp- and bee-phases.
By combining eqs. (6, K4-K6) and the phase boundaries as related by
Storms (7) (see Fig 2) the following parameters were obtained.
Abcc -_ -301000 + 8.58T J (9)
Ahcp = -388000 + 64.60T J (10)
The titanium rich part of the phase diagram was calculated back
using these parameters and the result is presented in Fig 3. The
agreement with the data given in Fig 2 is within the experimental
errors. The calculated diagram in Fig. 4 reproduces the invariant
equilibria within the errors of the experimental data as estimated
by Rudy, compare Table I.
 CALCULATIONOF PHASE DIAGRAMS 107

The Ti-C diagram is rather uncertain in many aspects. Titanium as

well as its carbide readily dissolves oxygen and nitrogen and small
amounts of dissolved oxygen is known to cause pronounced changes of
the phase diagram.

Thus the eutectic at 1927 K can be raised and changed into a

peritectic due to contamination by oxygen. It is furthermore known
that the solubility of carbon in the hcp- and bee-phases as well as
in the carbide is increased by the presence of oxygen and thus only
the lower values reported in the literature should be used (7). For
this reason the lower carbon content of the eutectic at 1927 K
according to Rudy is preferred to that given by Bickerdike (3).

The calculated liquidus curve of Ti(C,v), at higher temperatures

(see Fig 4), is at much lower carbon contents than the one given by
Rudy (4) in Fig 5. However, Rudy does not give any experimental
evidence supporting the the liquidus curve given and this is a part
of the diagram which must be considered as rather uncertain at the
moment.

v2600- 63kl _

I I
0 10 20 30 40 60 60
11 - ATOMIC % CARBON -

Fig 5. The Ti-C phase diagram according to Rudy (4).

108 EiJORNUHRENIUS

The W-C system

The binary W-C phase diagram has been subject to a number of inves-
tigations and it is obvious from the reviews by Hansen and supple-
mentary work (13-15) that much of the information on the system is
contradictory. Later work by Rudy et al (17) has resolved some of
the uncertainties, and the present calculations are mainly based on
the results of his work. It seems safe to conclude that tungsten
forms three different compounds with carbon, a simple hexagonal
carbide, WC which is almost stoichiometric, a cubic carbide which
is often referred to as WC and a second hexagonal carbide
W C which is shown to havelaxklightly varying carbon content. The
hzxagonal WC-carbide is stable from temperatures below room
temperature up to 3049 K where it decomposes into liquid and
graphite. This carbide has been investigated by thermochemical
methods and its heat of formation, entropy of formation and heat
capacity have been determined. An assessment of this information
has been presented earlier (18) and the result of that work was
used here to describe its Gibbs energy of formation as a function
of temperature.

..... lkhogeneou~ ordering in W,C

3600 -- -- Dispfacive transformation
- .-.. Change of sublattice order 1
If

4 _-3423f26
L + c,,
(I atm)
2720*
41
274;7$ 12”.

27352 12” ’ L+C

36.5 ’
\\ 2776 f 12”
\ -31 \
27762 lo”

w,w ’

A
I 1

10 20
W(a) - I .N.

I
30
w,c + WC

40
-ATOMIC % CARBON- !

Fig 6. The W-C phase diagram according to

Rudy et al (17).
 CALCULATION OF PHASE DXAGRAMS 109

The W C-carbide has not been subjected to any extensive

therm i;
chemical investigations and all the data available are rough
estimates except for the determination of the heat of combustion
made by Mah (19) on a sample quenched to room temperature. For the
present thermodynamic description of this carbide it was thus
necessary to rely upon the phase diagram information and the
thermochemical information available on the phases in equilibrium
with W C. However, no thermochemical information could be found
for th8 WC -carbide and the liquid-phase. Thus the present
results mu BcXonly be considered as a rough estimate of the thermody-
namic properties of the system.

Thermodynamic models
----------
To describe the Gibbs energy of the liquid- and the W(bcc)-phases
the subregular solution model described earlier was applied, and
the following expression was used:
= XWOG~ + XCo~C + ~~(xWlnx~ + xClnXC)
Gm
+ xWxC(A + B(XC-XW) + c(xC-Xw)*) (11)

-4

3049KO42

1500 ‘i_:,
0
1523K

020

MOLE
4
FRACTION
060

CC *
0 60 t

Fig 7. The calculated W-C phase diagram and

the experimental information on the
solubility of graphite in the liquid
according to Rudy et al (17).
110 BJORN UHRENIUS

The WC(hex)-carbide was treated as a stoichiometric compound, but

the W C- and WC (cub.)- carbides are known to have some
varia $.
ion in th&rl! W/C-ratios and these phases were consequently
treated as solution phases. The graphite phase was considered as
consisting of pure carbon only, neglecting any solubility of tung-
sten.

The W C-carbide has been investigated by neutron diffraction

technfques by Hdrsta et al (20). Their results are in agreement
with other X-ray data (21), and it is known that the hexagonal
structure is isomorphous with that of epsilon-Fe N. Their investi-
gations revealed, that there are at least two di.$ferent types of
positions for the carbon atoms and one for the tungsten atoms. Some
of the carbon sites are however, vacant and furthermore each carbon
atom added excludes a carbon atom on a neighbouring site, which
then becomes forbidden for new carbon atoms. A thermodynamic treat-
ment of such compounds has been presented by Hillert and Jar1 (22).

However, a somewhat simplified treatment was used here, which can

be represented by the following formula

where the type-1 position according to Harsta et al (20) is com-

pletely filled by carbon atoms and from the exclusion rule thus an
equal number of neighbouring sites of that type must be vacant. On
the type II-sites only a part of the number of sites available were
occupied leaving some holes available for additional carbon atoms.
However, these sites can never be occupied to more than 50 % be-
cause of the exclusion rule and in order to have the correct upper
limit and making the positional entropy in agreement with that, it
was chosen to reduce the total number of sites of that type by a
factor of two. This can only be done if the exclusion principle now
is omitted for this lattice. Thus the carbide formula should now be
written
W& (C,v) 2

where a complete exchange of carbon atoms and vacancies is allowed

in the type-II lattice.

By using the thermodynamic model presented by Hillert and

Staffansson (5) the following expressions were obtained for the
partial Gibbs energies of W6C1(C1v)2:

G = OG + yfLFv + ZRTln(l-yC) (12a)

W6F:lV2 W6 c, v2
OG + (1-Yc)2 LEv + 2RTlnyC (12b)
GW&c, = '6'3

By combining eqs (12a) and (12b) the following equations were

obtained for the description of the carbon and tungsten potentials.

GC = f("Gw6C3- 'GW6 c 12.

v) ++(I-2yc) L;, +

RTln (y,/ (l-ye) 1 (13a)

= 1/4(OG - 1/3OG
GW W6Ci v2 W&C! +
W
1/12(2yc(yc+1) - 1)L Cv +

l/6 RTln((l-yc)3/yC) (13b)

 CALCULATION OF PHASE DIAGRAMS 111

The LW -parameter denotes the interaction between carbon

atomsCxnd vacancies but this was put equal to zero in the present
case and the carbide was thus treated as an ideal solution of the
two species W6C3 and W6C1.

-carbide has a simple cubic structure of NaCl-type and

The WC13
is isomo ohous with the Tic-carbide. The I?,(C.v),-formula could
thus be used to represent this carbide. Usfng.th& same model as
used for Ti(C,v) the following expressions are obtained for the
partial Gibbs energies of Wl(C,v)l

+ RTln yC (14a)
OGWE + (1-Yc)2L&
GW; =

G c = OGw; + yfL;v + RTlnfl-yC) (14b)

WV
by combining eqs (14a) and (14b) the following expression for the
carbon potential was obtained:

GE = 'Gw; - "Gw; + (1-2yC)L;v

+ RTln(yC/(l-y,)) (14c)
Thermodynamic evaluations
_--------- --- - -

On basis of the thermodynamic evaluation of the hexagonal WC-

carbide (18) the following equation can be used for the Gibbs
energy of formation of WC
OC oGbcc _ oGg; = _ 38030 + 2.615T J (15)
GWC
- W
According to Rudy et al (17) there is a peritectic equilibrium at
2776OC between liquid, WC and graphite, see Fig 6. The same
authors also give experimental data on the solubility of graphite
in the liquid at higher temperatures, Fig 7.

By combining this information and that on the eutectic at 271O'C

with the expresssions for the Gibbs energy of melting of graphite
and bee-W according to Kaufman (12), (eqs.Kl and K3) it was possi-
ble to estimate the subregular parameters for the liquid. The
following parameters were obtained:

A1 = 41420 - 32.09 T J (16a)

B1 = 82800 J (16b)

Cl = 115140 J (16~)

A thermodynamic description of the "W C"-carbide was now possible

by using the model presented above an 2 by combining with the phase
diagram information given in Fig 6 and the parameters for the
liquid. It is known (13-15) that the W2C-carbide decogposes
eutectoidally into WC and bee-W at approximately 1250 C. This
informagion was also considered, as well as that on the eutectics
at 2710 C and 2735 C, see Fig 6.

However, the ordering transformations indicated by Rudy et al (17)

were neglected in the present analysis. This has probably only a
minor influence on the final result. The parameters obtained are
given by eqs. (17a and b).
112 BJORN UHRENIUS

OGC _ fjOGbc; _ jOGg; = -35640 - 39.62T J (17a)

w6c3
OGC _ 6’Gbc; _ ‘Gg; _ 2’GVa; =
w6c,vZ
11930 - 4.56T J (17b)
oGvac
where = 0 by definition. The properties of the cubic
W (C,") -"carbide were evaluated in a similar way, but At_was
dlff& cu $t to reproduce both of the two eutectica at 2735 C and
2720 C with a simple set of parameters. Thg choice made finally
describes fairly well the eutectic at 2735 C but gives a
peritectic equilibrium instead of the second eutectic. The
resulting parameters are given by eqs. (18a-c).
o(;bcc._ ‘Ggr = 9630 - 3.05T J
OGC (18a)
WC - W C
oGc _ oGbcc _ CVa; = 10460 J
WV W (18b)
W J
- 15060 (18~)
Lcv =
The solubility of carbon in bee-W as given by Hansen and supple-
ments (13-15) could be reproduce&By introducing an interaction
parameter for the bee-phase of A = 8400 J.

On basis of the analysis presented above the phase diagram was

calculated back and the result is given in Figs 7 and 8. A compari-
son between the calculated results and the experimental data accord-
ing to Rudy et al (17) is also given in Table II.

Iliquid

I I graphite
+ liquid

MOLE. FRACTION CC

Fig 8. The carbide-liquid equilibria as

calculated using the results of the
present evaluations.
 CALCULATION OF PHASE DIAGRAMS 113

Table II. Comparison between the calcualted phase diagram and

the experimental data according to Rudy et al (17) on the invariant
phase equilibria in the W-C system.

Phase Phases Composition,xC Temperature,K

equilibria
talc. exp. talc. exp.

Eutectic bee-W 0.002 0.002

bee-W/l/"W C" liquid 0.22 0.22 2994 2983
2
W6Cl(C,V)2 0.28 0.26 -
+12

Congruent liquid/
melting
l.fW,C W6C1(C,V)2 0.31 0.31 3049 3049
+12
-

Eutectic W Cl(C,V)2 0.32

"W2C"/l/W(C,v) ltquid 0.37 0.37 3014 3008
W(C,V) 0.39 +12
-

Eutectic (exp)
W(C,v) /l/MC liquid 0.40 0.41 3019 2993
peritectic (peritectic) (eutectic) +12
-
(calcf

Peritectic
liq./WC/graphite liquid 0.42 0.42 3049 3049
-+12

Eutectoid 0.32 0.33

"W2C"/W(C,V) / 0.39 0.38 2808 2803
WC +30
-

Eutectoid
bee-W/*w2C"/WC W6C(C,VJ2 0.30 0.33 1524 1500

The Ti-W-C system

The binary Ti-W system was recently assessed by Murray (1) using a
subregular solution model. The result of her analysis was combined
with the present analysis of the two W-C and Ti-C binaries in order
to make a description of the ternary system possible. The parame-
ters for the Ti-W system as evaluated by Murray are given in the
appendix, eqs. (Ml-M5).

Rudy et al (2) made an extensive experimental investigation of the

Ti-W-C system. They presented isothermal sections on the system at
1500°C and 2500°C. See Fig 9 and 10. Their data show a slight
solubility of Ti in the W C-carbide and parameters for the de-
scription of the hypothetical Ti C-carbide were evaluated in
order to reproduce this solubili,$y.
114 EJORN UHRENIUS

Fig 9. An isothermal section of the

Ti-W-C system at 1500°C, according
to Rudy et al (2).

Using this information and the one previously obtained on the

binary systems, a number of isothermal sections on the Ti-W-C
system were calculated. The results shown in Figs 11-13 are in
close agreement with the data according to Rudy et al (2). However,
the ternary liquid is somewhat more stable in the diagrams drawn by
Rudy but the experimental information is not very decisive in that
respect and allows for both diagrams. Thus, it does not seem justi-
fied to add any ternary parameters for the liquid on basis of the
experimental information available so far. Tungsten is readily
dissolved in the cubic Tic-carbide at high temperatures and this
carbide is thus to be considered as a ternary phase at these tempe-
ratures. However, the equilibria involving this phase could also be
described fairly well without introducing any ternary interaction
parameters. This lends some support to the present analysis.
 CALCULATION OF PHASE DrAGRAMS 115

A* L
Ti

Fig 10. An isothermal fjection of*the Ti-W-C

system at 2500 C, according to
Rudy et al 121.

W MOLE-FRKTIONCC c
Fig 11. A calculated isothermal section of
the Ti-W-C system at 1500 C,
116 BJORN UHRENIUS

w MOLE - FRACTION CC C

Fig 12. A calculated isothermal sption af

the Ti-W-C system at 2500 C.

w MOLE - FRACTION CC c

Fig 13. A calculated isothermal sgction of

the 'Pi-W-Csystem at 2800 C.
Appendix

Parameters used for the description af the Ti-C, W-C, Ti-W and
Ti-W-C systems.

The excess Gibbs energy is expressed by

E
G = XiXj [A. I + B. .(Xi--Xjf + c..(Xi-xjf2t
13 =3 11
liquid
01 oG9r = 114220 - 27.19611 J (Kl)
GC- C
-1
- OG
OGTi Tr
hop = 20585 - 12.133 T J fK2t
01 oGbcc J
= 30540 - 8.368T $K3f
Gw- W
-177100 - 22.384T J (Ul)
ACTi =
-95400 + 48.120T J (U21
BCTi =
A = 41420 - 32.09T 3 U.S)
CW
= 82800 J (U4)
BCw
= I.15140 J (U5)
ccw
= I.24120 - 41.890T J (Ml)
ATiW
= 41240 - 19.874T 3 (M21
'TiW
BCC
oGbcc _ 'Gzr = 146855 - 14.644T J
_ L

oGLbcc . QG hcp = 4351 J

3.766T
Ti Tl
A -301000 + 8.58T J
CTi =

A = 8400 J
cw
=: 14640 + 4.322'1' J
ATiW
-946 + 5.3681' J
'TiW =
HCP
oGhcp _ 'Gy = 114220 - 14.644T J
C
oGhcp _ oGbcc 3
= 8370
W W
= 388000 c 64,6OT J
ACTi
= 41550 J
ATiW
118 BJORN UHRENIUS

WC(hex)
OGW; _ OG;' - OGzr = -38030 + 2.615T J (U9)

w6c1(c,v)2: "W2c"

o bee _ oGgr _ 20Gvac =

OG '-6Gw C V
‘6 ‘1 vi
11930 - 4.561T J (UlO)

OG _ 6oG;cc - 30G4Cr= 35640 - 39.622TJ (Ull)

WCC3

OG ' - 6o GTi
hcp OGgr - 20GVaC = 41840 J (U12)
Ti, C,va C V

hcp _ 3OGg' = -460200

'G . ' - 60GTi J (Ul3)
T16 ‘3
C
(W,Ti)l(C,v)l

'G hCp _ oGvac

v = 46030 J (Ul4)
OGTiz - Ti

oGgr = 184640 + 11.058T J (Ul5)

'G

o bee _ oGvac J
"Gw; - GW = 10460 (Ul6)
V

OGw; _ OGkcc - OGzr = -9630 - 3.05T J (Ul71

LTi - 173640 J (Ul8)
cv =

LW = - 15060 J (Ul9)
cv

References
-----
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