CALJ’HAD Vol. 12, No. 2, pp. 177-184, 1988 0364-5916188 $3.00 + .

OO
Printed in the USA. (c) 1988 Pergamon Press plc

CALCULATED PHASE DlAGFtAMS OF

Cu-W, Ag-W and Au-W BINARY SYSTEMS

H.Vijayakumar, A.H.Sriramamurthy and S.V.Nagender Naidu

Defence Metallurgical Research Laboratory
Kanchanbagh, HYDERABAD-500 258, INDIA.

ABSTRACT

Phase diagram6 for Cu-W, Au-W systems have been calculated based on
available thermodynamic data. It was SssLused that there is no mutual solid
solubility in all the cases. Liquid phase equilibria were calculated on the
basis of sub-regular solution model using kliedema's interaction parameters.
Vapour phase boundaries have also been determined.

INTRODUCTION

cu-w, Ag-W and Au-W are three important systems for which meagre data on
phase diagram6 exist. Cu-W system has been studied extensively as an ideal
fibre reinforced composite due to the absence of interaction between Cu and W,
while Ag-W is considered a6 good electrical contact material. No phase
diagram6 are available for these systems, therefore, it will be useful to have
calculated phase diagrams. In thi6 paper an attempt is made to calculate phase
diagram6 upto the vapour state based on the available thermodynamic data.

According to the earlier compilation6 (11, the component elements are

essentially immiscible even in the liquid state. There is no experimentally
deten6ined thermodynamic data on these systems. However, Wiedema (2) has
calculated interaction energies in liquid otate between the component
elements. The two interaction energies given by Wiedema at both extremities of
COmpOSitiOn allow6 us t0 formulate an analytiCa description Of excess free
energy of liquid solution which is given as
ex
F = x (1-x) (Ml (1-x) t M2 x) :x1

where x is the atom fraction of the solute, I4 and H2 are Miedema's

'interaction parameter6 at x = 0 and x = 1 respectiv & ly. This equation is in
the form of excess free energy for subregular solution model which may be
rewritten a6
ex
F = x (1-x) [Ml + (HZ'Ml) xl

= x (1-x) (Ll + L2 XI (2)

where Ll and L2 are interaction parameter6 for subregular solution model.

Cu-W
m-
SYSTEM

Baaed on existing literature, it i6 a66Wed that there i6 no mUtU61 solid

Solubility (11.

The equilibria with the liquid state were calcu&jted using the
interfctfon parameters given by Miedema viz. M - 107 kJ mole and W2 = 86 kJ
mole . The exce66 free energy of formation thas obtained is

Fex - x (1-x) (107 - 21x1 kJ mole-' (3)

where x is the atom fraction of W.

Received 26 June 1987 . This paper was published in CALPHAD

11 369-76 (1967) without the figures. It is printed here in
ES entirety.

177
178 M. VIJAYAKUMAR, A.M. SRIRAMAMURTHY and S.V. NAGENDER NAIDU

Liquid cquilibriar
Taking pure liquids as standard atatea , the partial molar free energy of
W in the liquid is given by
EW = RT In x + Ll (l-x)2 + 2 L2 x (l-x)2
-1
- kT ln x + 107 (1-X)’ - 42 x (l-X)2 kJ mole (4)
When the liquid is in equilibrium with pure W (I),

AFw - -AFWf (5)

where AFw f is free energy of fueion of W, which may be given as (assuming

ACp=O)

dFWf = AhWf (I- T/T),,) (6)

where T is the melting point of W and & is the difference in the specific
heats between liquid and solid of W. ComputBtion of the liquidus based on this
equilibrium produced two liquidus segments one each at Cu and W ends of the
phase diagram with a discontinuity in the middle(Fig.1).

L,+(W)

woo-
10BL.87’C H.P
1000 - mJl ’ I 1 1 I I I I ,
0 10 20 30 40 50 60 70 60 90 10
cu ATOMIC PERCENT TUNGSTEN
W

Calculated Phase diagram for Cu-W system without the constraint

of total pressure of I-atm.
 PHASE D~AGR~S OF Ob44, Ag-W and Au-W BINARY SYSTEMS 179

Liquid-LiquidEquilibrium:
At lower temperatures. the free energy of fusion of W is large and
therefore free energy of solid tungsten representedby B in Pig.2. io below A,
tbe partial molar free energy of W for coexistenceof two liquid phaeen of
comporitiona x and x . Thus, coexistenceof pure W with Cu rich liquid
represents a lower frei energy state in the intermediate compoaition8 than
coexistenceof two liquid phases.
As temperature increases, B moves up in relationto A. When B reaches A,
two liquid phases and pure solid W coexirt producinga monotectic reaction.
Above this temperature, B is above A and two liquid phatses coexirt. The
thermodynamic condition for such a situation is that the tangents at
compositions x and x of the two liquids are one and the 6ame. In other
words, the pariial molaj free energies of the componentsare equal at xl and
x2'
i.e. = RT In (l-xl) + (tl-L2) x12+ 2L2 x;
c”FCU

= RT In (l-x21 + (L1-L2) xt + 2L2 xi

which can be written as
RT In (l-xl/l-d:)- x: [(Ll-L2)+ 2 L2 x$ - x: [(L1-L2)+ 2 L2 x1 (7)
and mw =RTlnx 1 +L 1 (l-xl)2+ 2L2 [l-x2)2x1
= RT ln x2 + LL U-x2)2 * 2L2 x2(1-x2)2
which can be written as
RT In x1 / x2 - U-x2)2 [Ll + 2L2 x,1 - (l-x1)2 I Ll + 2L2 Xl 1 @I
Equations (7) and (8) can be solved for x and x the two boundaries of
miscibility gap. The miscibilitygap thu8 pkced2is rhown in Pig.1. The
intersection of the miscibilitygap boundarieswith the liquidurn
defines the
positfon of the three phase monotactic reaction. The existence of the
miacibifity gap is a consequenceof large interactionparameter values as
suggestedby Hiedema (2).

: W
COMPOSITION COMPOSITION ’
Fie,2: Free energy diagram far Cu-W system Fig. 3: Free energy diagram for Cu-W system
just below the monotectic temperature, just above the boiling point of Cu.
180 M. VIJAYAKUMAR, A.M. SRIRAMAMURTHY and S.V. NAGENDER NAIDU

Equilibria with vaoour phase:

Cu boils at 256O’C. Therefore another constraint to be uaed for celculating

phase equilibria bounded by vapour phaae ia that the l um of partial vapour
preaaurea of Cu and W la equal to one atomaphere i.e.

PCu + PW = 1 (9 1
where p end pw are the partial vapour preaaurea of Cu and W under
equiAibr%. Therefore the phase diagram shown in Fig.1 is invalid above
2560 C.

At a temperature just above the boiling point of Cu, the eituetion existing
with respect to thermodynamic equilibrium ia depicted in the free energy
diagram, Fig.). The tangent at the liquid composition x corresponding to a
total vapour pressure of one atmosphere , cut6 the free energy axeaGat Cu end W
enda below the free energy values of Cu vapour at 1 atmosphere, P and that
of solid W, F respectively. The pertial preaaure of CU end ‘# at the
composition x ma 1 be written aa

RT In (pcu/pocu) = kpe”,, + RT ln (1-x)

RT In (pW / pow) -EeXW + RT lnx.

where and p are the aaturag d and

vapour
~ ~f;eaaurea over pure liquid Cu and
liquid P6j”reapectYvely, and r 6re l xceaa partiel molar free
energies of Cu end W in liquid &! X. These Bquetion can be rewritten ea

pcu=scu(1-x) exp ( ET: / RT))

PW
= p& x exp ( nexw / RT)

The vapour pressure over pure liquid6 may be represented as

dlnp/ d(l/T) = - ASG / R

which may be integrated to give

o - exp I - (AR’ / R)(l/T - UTR.p,l (11)

P
where AHG is the lnthalpy of evaporation end T ia the boiling point of pure
liquid, eaouming that the enthalpy is temperatur @ inverfent i.e. ACp-0.

The exceaa partial molar free energies of Cu end W are given by

Gwex = Ll (l-x12 + 2L2x(l-x).2

2 3 (12)
zcuex = (L1-L2)X + 2L2 x
Subatitution of these excess partiel molar free lnergie6 and vepour
preaaurea on pure liquids from equation (11) end (12) in the eqUatiOna (10)
partiel prersure of Cu and W et x.

Equation (9) in conjunction with equation (101, (11) and (12) can k
aolved for x.

The corresponding composition of the wepqur cm be found, 866Uing that

both the v6poura lxiat in monortomic state, using the equation xW - pW.

The relevant thermodynesic drte ured for crlculetionr bre ohown in the
Table6 Al and AZ. The computrtlonrl methodology ia given in the Annexure. The
pheae boundaries computed from lbove lquationr are shown in 119.4. It my be
obaerved that in the lnaeta 1 and 2, the L/L + G boundaries cut the liquid6
producing three pheae reaction between solid, liquid and vepour pheeer 8t Cu
end w rich ends.
The three pheae reaction near Cu end is

G+(W) d L et 2561.6oC.

i.e. about 1.6’C above the boiling point of Cu. The liquid phaoe her a
composition of 0.73 et 8 W. The three-phaee reaction near the W rich end ir

L * (w)+c
 PHASE DIAGRAMS OF Cu-W. Ag-W and Au-W BINARY SYSTEMS 181

WEIGHT PERCENT TUNGSTEN

0 20 40 f&l +0 II

5555-c
6.P.
5600 - G

3b22-C H.P.

i-
a
g
fY&
3200
-P
2sca
INSET-1
25616-C
G+(W)

a
II L+(W)
k 1600 -
llllb WC np.

800 -
([u)+(W) (W) -
- Ku1

a ID 20 30 60 50 60 70 80 90 100

cu W
ATOMIC PERCENT TUNGSTEN
Ceiculared phct~c diagram for Cu-W system at a total pressure
0I J-atm.

-I
IINSET_I

3bZ2

Y
2
2 3b17
ff
“r
g
3b12
00 02 9.b 06 0.9 1.0 99 1 99.9 99.9 w
at % v

at 3lli.f% i.e. about 7.3oC below the melting point of W. The L/L+G boundary
at thi6 end shift6 towrrds W 6ide 66 temperature rises and meet6 lOOI W axis
6t the boiling point of (WI. The G/G +L boundary also shifts toward w axis
more rlowly in the beginning and very rapidly approachs 1OOb W axis at higher
temperatures.

Solid-vapour equilibrium:

In the temperature region between the 6bove two three phase reactions, (WI is
in equilibrium with vapour.

Referring to Fig.), the tangent to liquid pha6e free energy curve

corresponding to the total pressure of one atmosphere rotate6 in the
anticlockwise direcion a6 temperature rise6, whereas the free energy point
corre6ponding to one atmosphere presoure of Cu vapour. F d6Cr66666 rapidly
while free energy point corresponding to solid W, F rc Pe6 gently. Soon a
6ituation d6VelOp6 when the tangent to liquidus repre%nting a total pressure
of one atmosphere pa66es through F Iwhich represents the three phase
equilibrium at Cu rich region. Beyond this temperature 6olid (Wt will be in
182 M. VIJAYAKUMAR, A.M. SRIRAMAWRTHY and S.V. NAGENDER NAID!J

equilibrium with Cu vapour. The straight line representing free energy of this
equilibrium will be well below the liquid free energy curve. However, close to
the melting point of W, this line approaches liquid free energy at W rich end
as P approaches that of the pure liquidus , and a situation arisea when the
straitht line representing the (W) vapour equilibrium just touches the free
onergy curve for liquid. This reprerents the three phase equilibrium at W rich
end.

Since the vapour pressure over solid (W) i5 insignificant in this temperature
region, the vapour phase will be of pure Cu. Thus the G / G + (W) boundary
will be along the pure Cu axis. Therefore no calculation of phase boundaries
was necessary in this temprature region.

-The Ag-W System

As in the case of Cu-W, no experimentally determined phase diagram data
exiata. Further, existing literature indicate8 that there is no mutual
lolubility. however, Wiedema (2) has given th?linteraction parameter!1 which
are very highly positive; viz. Hl = 156 kJ mole and W2 - 161 kJ mole .

The calcuations of phase boundaries based on the procedures deocribed above

produced a phase diagram shown in Fig.5. The thermodynamic data used for the
calculations are tabulated in Tables Al and AZ. The aolubilitiea in the pure
liquidus were found to be insignificant. Therefore the poritions of the three
phase equilibria were not calculated. Insignificant solubilities ahown in
Fig.5 are consistant with the existing litersture (3).

Au-W Svste!n

A phase diagram for Au-W was recently caltulated by Okamoto(41 using the
interaction parameters reported by hiedema (2) for the liquid solutiona.

AU boils at 2Q60°C, i.e. below the melting point of W. Therefore it is

possible that the liquid-vapour equilibrium at one atmosphere interferea with
the solid-liauid eauilibrium, which was not considered by Okamoto (4).

WEIGHT PERCENT TUNGSTEN

0 2p 10 60 80 100
sss* u
5600 - G

G+L

3422Kw
3200 -

G+(W) (WI -
2coo - zra%IP

1600 - L+(W)
9hLHI lw.
800 -
- (Agl lAgI+
0. I 1 I 1 I
10 20 30 CO 50 60 70 60 90 MO
W
ATOMIC PERCENT TUNGSTEN

Fig. 5: Calculated phase diagram for Ag-W system at a total pressure

of I-arm.
 PHASE DIAGRAM OF Cu-W, Ag-W and Au-W BINARY SYSTEMS 183

WEIGHT PERCENT TUNGSTEN

a 70 co $0 80
r 1 I I I I
5600 - G ISIS7.

3370
Y I422T
3200 -
G+(W) _-_---0'
_-_=_ c_
2929Y - -,-
\ IS14 2929 TI

L+(W) (WI -

800 -

-(Au) (Au)+(W)
0 1 I 1 I I I I I 1
0 10 20 30 LO 50 60 70 80 90 100
Au
ATOMIC PERCENT TUNGSTEN
Fig.6: Calculated phase diagram for Au-W system at a total pressure

of I-arm.

Therefore Au-W diagram is recalculated using the methods described above for
solid-liquid and liquid-vapour equilibria end is shown in Fig.6. It is seen
that0 the L / L + G bogndary intersects the L / L + (WI boundary at 51 at-w,
2929 C and 968W, 3310 C where three phase e,quilibriawere produceed. Between
these temperatures the vapour phase is in direct equilibrium with solid (WI.
Thus, the constraint of one atmosphere of total pressure modifies the phase
diagram calculated by Okamotofl) to the one shown in Fig.6.

ACKNOWLEDGEWXNTS

The authors thank Director, DMBL for his interest and permission to
publish this work.

REFERENCES

1. H.Hanaen and K.Anderko. "Constitution of Binary Alloys', MC Graw Hill, New

York
(19581.
lays - Fundamentals
Z.A.R.Wiedema, P.F.de Chatel and F.R.de Boer, 'Cohesion in al.
of a semiempirical model', Physics, 1008, l-28 (1980).
3.H.Okamoto and T.B.Harralaki, 'The Au-W System', Bull. Alloy Phchoe Diagrams,
6(2), 136-137 (1985).
4.S.V.Nagender Naidu and P.Rama Rae’, The Silver- Tungsten System., J-Alloy
Phase Diagram, 20), 210 (1986).
S.H.Vijayakumar, A.M.Sriramamurthy and S.V.Nagender Naidu, ‘A note on the
calculation of phase diagrams in simple binary systems' - (to be published)
b.E.A.Brandes. 'Smithell Metals Reference Book', 6th edition, Butterworths
(1983).
184 M. VIJAYAKUMAR, A.M. SRIRAMAHURTHY and S.V. NAGENDER NAIDU

ANWEXtlRE - 1
--_

In the region where solid tungsten is in' equilibrium with the liquid solutior.,
we have the following equation controlling the equflibriumr
Af$+ RT in x - 11-x)2 IL1 + 2L2 x1

This equation is solved for x at different temperature@ .uring oucceesivc

approximation6 approach. Initial estimates of x for the iterations axe
obtained by solving the above equation analytically assuming that the
heteroatoms do not interact with each i.e. Ll - L2 - 0.

i.e. x = lxp f -AF:/RTl

The thermodynamic data used are presented in Table Al vhile the interaction
parameters are given in Table A2. The computatfonal whema used is described
elsewhere (5).
Table AI
ThermodynamicData (6)
w CU 4 AU

1 36Y5K 1358.05K l?iS.c&K 1337.9&K

J#IPK 2133K 2473K 3133K
+l*
AH r&G 13.0) 11.3 13.0 (k3 mol-'1
AH‘ 737 3Ui.8 257.P 362.6 lh3 md-t)

Annexure-2

Above the boiling point of Cu/Ag/Au, the vapour state also enters the
equilibrium. As explained in the text, the governing equatfons then are the
following t
P,; ’ Ppt = 1 WI)

pel = p;l (1-r) cxp ( d?;,= I RTI

(AX)
pw=p; x lxpf AFw
- =’ i RT)

p; - erp(-( Ati,GiR)({- T’ 1))

(AZQ
i, B.P

CX
I
bF, - RTIn x + (I-x)f[L, * 2 i.“i I I

t (An)
q, cx = RTInw+ x2k141..$*2L2’1 !
Solution to eq. (A-21) will give tk l COmpOlrit%On on the liquid side, while
composition on the gaacous side is x = pW_

&q. A tl can be rewritten 8s

(1-x) f (xtTl+x x(x,Tf = t fA231

bJtd g(x,n=p; erp ( Z$’ I RT)

fn the comput@on, my
#bitrary value of x ii rrmmcd as the initial
estimate. and F are then calculted used cq. (A24). (AZS) ia then
solved
FW
for x. This it&ion is continued till the difference between the
succe~ive values of x < 0.00051. This value of x io ~1s~ ured l e the initial
ratimate for the next tempemature.
Table AZ
Parameters (2)
InceractiDn

11 12
w -cu I 07 -21 -t
kJ mot_,
U'-Ag 1% k3 mol_,
w - A" 66 : kl mot