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A

MASS

SPECTROMETRIC

C. B.

STUDY
OF THE
A&In
AND Cu-Sn*

ALCOCK?,

R.

SRIDHAR:

and

BINARY

R.

C.

LIQUID

ALLOYS,

SVEDBERGg

A study of the thermodynamics of the liquid alloy systems silver-indium and copper-tin has been made
The systems were chosen to afford a comwith the combination of Knudsen cell and mass spectrometer.
parison with literature data. The results show a good agreement with activity measurements using
EMF techniques for Ag-In, and with calorimetric heats of mixing for Cu-Sn.
ETUDE

AU

SPECTROMETRE

DE

MASSE
Ag-In

DES

ET

ALLIAGES

LIQUIDES

BINAIRES

Cu-Sn

Une etude de la thermodynamique


des systemes dalliages liquides argent-indium
et cuivre-etain
a
et& effect&e a laide de la methode de la cellule de Knudsen combinee a la spectrometrie de masse. Les
systemes Studies ont et& choisis de facon 8, pouvoir etre compares aux don&es de la litterature.
Les
result&s sont en bon accord avec les mesures dactivites utilisant les techniques de mesures des forces
electromotrices pour Ag-In, et avec les mesures de chaleur calorifique de melange pour Cu-Sn.
EINE

MASSENSPEKTROMETRISCHE

UNTERSUCHUNG

LEGIERUNGEN

Ag-In

DER

UND

FLUSSIGEN

BINAREN

Cu-Sn

Eine Untersuchung
der Thermodynamik
der fliissigen Legierungssysteme
Silber-Indium
und
Kupfer-Zinn
wurde mit Hilfe einer MeBanordnung
aus Knudsen-Zelle
und Massenspektrometer
durchgeftihrt.
Es wurden gerade diese Systeme untersucht, urn Vergleiche mit Daten aus der Literatur
zu ermoglichen.
Die Ergebnisse zeigen gute Ubereinstimmung
mit Aktivitiitsmessungen
an Ag-In
mit der E.M.K..Methode
und mit kalorimetrischen Messungen der Mischungswarme im Cu-Sn-System.

INTRODUCTION

knowledge

Studies of the thermodynamics

of binary

systems by the simple Knudsen-weight


are limited

to those systems

a much larger vapour


other.

pressure

Experimental

in which,
Knudsen

by sampling

the scope

the vapour

efllciency

apparatus

raise problems

of sample

and the thermal

emitted

collection

concerned

The

use of

a mass

to obviate

spectrometer
the separation

above

an alloy

the mass spectrometer


to criticism

where I,+/I,+

offer

the

coefficient

and

position,

of the simple

found in the equilibrium

system.

The application

In

It

of the partial

VOL.

17, JULY

1969

is known

at a given com-

calculated

can again be

thus

= Xi)

also

is

It follows that if the activity

of a component

X,=X,

= -

follows

considerations

x, =X1

from

X,d

standard

that the partial

lng-lng
1

thermodynamic

molar heats may be

thus

X,=X,

AR,=-R

* Received August 31, 1968; revised November 22, 1968.


t Department of Metallurgy, Imperial College, London.
$ Chemical
Engineering
Division,
Argonne
National
Laboratory, Argonne.
4 Westinghouse Astronuclear Laboratory, Pittsburgh.
METALLURGICA,

is the ion current ratio and X,/X,

Yl(Xl = Xl)
yr(X,

of

to alloy studies has been subject

in that the determination

ln;c--lng
[

say Xi then the value at X,

calculated

pressure of a component
from the measured ion
current of the mass spectrometer required accurate

ACTA

X,d

x=1
1

fluxes, which are needed from the polyatomic

species which are sometimes


vapour

does

most of these problems,

X,=X,

lnl5= -

by Gibbs-

thus

with the

isothermal

species of

then the activi-

could be calculated

the mole fraction ratio.

it also makes possible


atomic

Duhem integration

a cool condensing

has been

who showed that if

of a binary alloy system was measured

ties of each component

cell.

opportunity

of this difficulty

across the whole range of composition

for each component,

effects of placing

of instrumental

the ratio of the ion currents of the atomic

has been wider.

surface near the orifice of the supposedly


Knudsen

from

resolution

each component

been devised

an alloy at high temperature,

of the simple

Such techniques

have

information
cross sections.

found by Belton and Fruehan,o)

has

(> 1000: 1) than the

techniques

cell containing

An elegant

loss technique

where one element

of ancillary

factors and ionization

metallic

x,=1

In
839

order

to

test

the

Xsd

accuracies

which

may

be

ACTA

840

achieved in this application

METALLURGICA,

of the mass spectrometer,

a study has been made of the alloys Ag-In


both to provide
compare

data of theoretical

and Cu-Sn

interest,

the results with literature

and to

data for the same

systems.

For the Ag-In

chemical

studies which are in fair agreement

system there are two electrofor the

activities(2*3) and for the Cu-Sn system there are data


for the heats of mixingt4) but not for activities.
theoretical
electron

need is for an accurate


theory

dynamics

in its application

measurements

time-of-flight
tached

mass

made

heated

in length.
hole

which

through
ion

is 6 mm

thermo-

source.

Knudsen
The

The

was at-

furnace.

tungsten
through

and then

before

from

the

The

and 180 mm

escapes

shutter

is placed

steel vacuum
radiation
Vacuum

Bendix

passes

entering
orifice

in the centre

chamber,

shields

of

tungsten

the

of the

Knudsen

cells

and

Knudsen

without

alumina

lids

The

held

cell orifices

ion

current

only

satisfy

in position

of a standard

and

vacuum.
and

with

tungsten

wire.

mm

diameter.

since it is only

which

are required.

the

Knudsen

condition

This
of

being

must
less

mean free path within

couple attached

by means

f2C.

by means

to the cell lid.

The

cell

of a thermo-

The system has been

The ionization

water-cooled

shutter

ion currents

energy

between

always

to zero on being

for the electron

11 and 20 V.

beam was

At the higher value,

to the background

from hydrocarbons

samples of high purity metals in each Knudsen


The total alloy weights were l-2 g.
subsequently

analysed

chemically

change in composition

cell.

The alloys were

and no significant

from the original mixture was

found.
In the Bendix
element,

were

machine two channels, one for each


used

measurements.
reported

during

The

ion

are therefore

the instrumental

the

vapour

current

ratios

independent

pressure
which

are

of variations

in

factors.
RESULTS

In Figs. 1 and 2 the measured ion current ratios for


and Ag-In

calculation

are shown

of activity

for Ag-In

spectively.
values

for Cu-Sn

and

in Figs. 3 and 4 re-

The curves for calculation


are within

for the

which are obtained

at 1573K

are shown

heats have not been included


the

of alloy

The results

coefficients

from these measurements


1300K

as a function

and temperature.

of the partial

but the accuracies

error

limits

*300

of

cals and

1700

cals in the middle and dilute range of composi-

tion

respectively.

temperature

At

to 1% of its value.
of

mixing

fixed

the ion intensity


and

composition

and

ratio was reproducible

The integral free energies, heats

entropies

of mixing

Figs. 5 and 6. A table of activities


for Cu-Sn

to aid any subsequent

are shown

in

in both systems is

and 1300K

calculations

for Ag-In

with the results.

to be 70.5 kcal

This is in close
The vapour
agreement
with literature
data.)
pressure could be measured down to lo-lo atm before
the signal-background

at 1573K.

the background

for a given element would build up presumably

Previous

work on the Ag-In

due

force

lithium-potassium
fraction of indium

of indium

The temperature

was 400-700C
only 680-730C

on liquid

Terpilowski

alloys

et al. used

bromide
containing
0.1 mole
monobromide.@)
Niwa and co-

workers used sodium-potassium


small amount

system is confined to

measurements

using molten salt electrolytes.

lyte.(s)

ratio became unity.

a series of measurements,

DISCUSSION

Silver-i&urn
electromotive

studies from 200 to 2000C.

For initial calibration the vapour pressure of pure


tin was measured and the heat of vaporization was

During

The

given for 1573K


was controlled

temperature,

was measured

used for quantitative

found

the

difference amplifier system@) and could

at constant

temperature

this

rotating

closed.

composition

crucibles

ratios

than one tenth of the vapour

be held

with
0.1-0.5

is unimportant

the cell.
The furnace temperature

source.

the metallic

CuSn

with sorption

alumina

were about

The precise diameter

ion

reduced

of the major

breaking

separately

cells were

the

molybdenum.

of operation at
ion pumps, and under conditions
1500C a pressure of 10-T mm Hg can be maintained.
The

by

The

from

Knudsen cell so that the beam was pointing away from

by five

axis of the furnace make it possible to introduce


The furnace is pumped

shields.

arising

be obtained

of a stainless

and is surrounded

locks at the top and bottom

remove

cell to the centre of the ion source is 5 cm.

furnace

current

The alloys were made by melting together weighed

to which

vacuum

beam

distance

ion

always

always

with

in diameter

a water-cooled

could

the contribution

the

which is 30 mm diameter

The molecular

source

test of the free

heating element in the furnace is a cylindrical


mesh cylinder

the

to

became important.

spectrometer

a resistance

on the inner radiation

contribution

to

METHOD

were

17, 1969

to condensation

The

of liquid systems.c5)
EXPERIMENTAL

The

VOL.

iodide

mono-iodide

containing

as the electro-

range of the Polish

study

in the indium-rich
composition
but
at X1, = 0.3. Although the results

ALCOCK

STUDY

ei al.:

OF

l!HE

BINARY

LIQUID

Temperature

I-

AND

no0

1200

Ag-In

*C

1300

1400
2.0

ALLOYS,

I[

xcu
0.91

W=

R_;

:-

-1.0
0.20

-2.01

0.10

5;

0.05

r--

1
5.6

--

FIG. 1. Ratio of the ion currents in the copper-tin

0.70

7.2

system as & fun&ion of tempertlture.

.-*------

O:~~e----

@79_e/.---NJ

I
6.6

6.4

6-O

e.*-0-e

ye---

._*-

__AHv.2--C---

.---

,_.-d--e--_*__*_.@65A_*_,,.---r*
0.56
a
:=
4
-~

12

__-*c-c-_*_.-.---*----*

044
0.37

-.----*

___----C*-_.-I-**

FIG. 2. Ratio of the ion currents in the sib-indimn

system as a function of temper&we.

Cu-Sn

841

ACTA

842

METALLURGICA,

VOL.

17,

1969

XS
0

1
-06

I
-0.4

Fra. 3. Gibbs-Duhem

I
-0-2

I
0

I
0.2

plot for the calculation

of activity

I
0.6

I
0.4

coefficients in the copper-tin

I
0.8

system.

,O-

0,,2-

O*9-

XI
0. 6-

0,6-

1. O-

0.2

FIa. 4. Gibbs-Duhem

0.6

1.0

1.4

1.6

plot for the crtlculation of &ctivity coefficients of the silver-indium

system.

ALCOCK

et al.:

STUDY

OF

THE

BINARY

TABLE 1. Activities of copper and tin in Cu-Sn alloys


at 1573K and ctctivities of silver and indium
in Ag-In alloys at 1300K
XCU
0.90

0.80
0.70
0.60
0.50
0.40
0.30
0.20
0.10

BCU

CWl

X&Z

aAs

am

0.876
0.684
0.490
0.367
0.281
0.212
0.156
0.104
0.052

0.018
0.073
0.192
0.336
0.446
0.582
0.692
0.796
0.898

0.90
0.80
0.70
0.60
0.50
0.40
0.30
0.20
0.10

0.866
0.689
0.507
0.400
0.285
0.204
0.123
0.087
0.042

0.015
0.057
0.143
0.273
0.419
0.559
0.683
0.787
0.900

were used to calculate heats and entropies of mixing


after extrapolation to pure silver of the activities,
it is proposed here only to use the measured indium
activities for comparison. The Japanese study was
conducted in the temperature range 727-927C and,
again, the composition range which was covered was
X,, = 0.208 to X,, = 0.823. It is therefore proposed
to use only the partial thermod~amic
data for
indium for comparison with the present study.
Table 2 shows the partial heats and entropies from
all three studies which together cover the temperature
range from, at the lowest, 4OOC, to the highest
temperature in the present study, 1200C.
It can be seen immediately that the partial entropies which are obtained from this work and that of
Terpilowski are in very good agreement. Since the
partial heat of solution of indium in the common
composition range is zero within experimental error,
this shows that the indium activities obtained in one

ALLOYS,

Ag-In

AND

P
7.
m
::

At 1400K the ratio of vapour pressures is 1.6.

t
cu

f
3:
I.
0

843

In this system there are no comparable activity


measurements. This is because the vapour pressures
of the elements are quite close together,* and hence
a simple weight loss by Knudsen study is not possible;
the halides have comparable stabilities and SnO is
quite volatile thus precluding EMF studies.
There have been a number of measurements of the
heat of mixing which are summarized in the publication of Benz and Elliott.(4) The present results agree

5
:

Cu-Sn

ease from an electrochemical study at low temperatures, and from vapour pressure measurements at
high tem~ratures can lead to close agreement concerning thermodynamic data. The results of Niwa
et al. although qualitatively in agreement with the
present results, in fact lead to too high activities.
This could be the result of a significant eleotron
transport number in the electrolyte leading to low
electromotive forces and the observed effect.
Concerning the heat of mixing it can now be seen
that because of the asymmetry of the beat of mixing
curve, significant partial heats of solution of indium
would only be found between X,, = 0 and 0.3.
Hence it is only in the present study of the silver-rich
alloys that reliable information for the integral heat
of mixing can be obtained. The EMF studies by
virtue of their small temperature range cannot give
results for the integral heat of mixing.

Cu- Sn System (1573. K )

LIQUID

Sn

4-

c
FIG. 5. Integral thermodynamic results for the copper-tin system.

844

ACTA

METALLURGICA,

VOL.

17,

1969

In

Y
I.
%

1~

08
Ra.

TABLE 2. Comparison of the~od~amio

XIII

AHrn (Cal g. atom-)


Present
Ref. 3
study
Ref. 2

0.9
0.8

-125

8::
0.6
0.4

-175
-277
-383
-172

8.;
0:r

6. Integral thermodynamic results for the silver-indium system.

-76

1200
-

data for liquid Ag-In alloys


ASID (cal deg-1 g, atom-i)
Present
Ref. 2
Ref. 3
study

+2:

0.30
0.65

0%

0.21
0.39

--iI
-317
-705

ilO0
t50
+I25
+60

1.48
1.01
2.03
2.63

0.62
0.82
1.00
1.22

0.80
1.23
1.63
2.54

-1298
-2137
-

-1450
-350
-6000

3.34
-

2.25
1.60
-

3.6
6.96
3.7

.__

32

Liquid indium is the standard ststo.

with these in showing an asymmetry with the maximum heat of mixing at X,, = 0.8. The values
which are obtained from the present temperature
coefEcient calculations agree with published data to
within 200 cal g. atom-l over the entire composition
range and this is within the stated experimental
error.
ACKNOWLEDGMENTS

We wish to thank the Science Research Council for


the financial support of this project, and especially
&. J. Butler of this department, who designed and
constructed the vacuum furnace.

REFERENCES
1. G. R. BELTONand R. J. FRUEHAN,J. phys. Chem. 71,1403
(1967).
2. E. P. MYCIELSKA, J. TERPILOWSKIand K. STROZECBA,
Archwn. Hun. 7, 85 (1963).
3. T. NOZAEI, M. SHI~~OJIand K. NIWA, Trans. Jap. Inst.
MW
7.62 119661.
4. M. G. RENZ and J. F. ELLIOTT, Tram. Am. Inst. M&s.
Fng78 239,706 (1964).
5. N. H. MARCH, I&&
Metals. Pergrtmon (1968).
6. W. E. DENNIS, F. D. RICHARDSONand J. H. WESTCOTT,
J. a&en&Inatruna. 30, 463 (1963).
7. R. HULTQEEN, R. L. ORR, P. D. ANDERSONand K. K.
KELLEY,
Thermodynam& Properties of Met& and AEluya.
Wiley (1963).