Superplasticity in the Pb-Sn-Zn and

Pb-Sn-Cd ternary eutectic alloys

M. D. C. Molesand

G. J. Davies

MATERIALS

The compositions and structures of the Pb-Sn-Cd and

Pb-Sn-Zn ternary eutecticslS are givenin Table 1.
The Pb-Sn-Zn
ternary eutectic temperature is 450 K
(177C) and the Pb-Sn-Cd ternary eutectic temperature is
433 K (l60C). The alloys were prepared by air-melting
commercial-purity base metals. After allowing time for the
liquid alloys to homogenize they were cast into graphite
boats 450 mm- long with a 12 mm square cross-section.
These bars were zone-refined for 14 passes at a rate of
38 mm/h following the method of Yue and Clark16 and
examined metallographically to ensure eutectic composition.
Composition analyses of a typical Pb-Sn-Zn
bar by
spectrophotometric techniques, microprobe analysis, or Xray fluorescence analysis were in broad agreement with the
results of Cooksey and Hellawell.ls

Superplastic behaviour has been examined in the

Pb-Sn-Zn and Pb-Sn-Cd ternary eutectic alloys.
Both alloys exhibited log at/log t and m/log t
relations similar to those of comparative binary
eutectic alloys. Activation-energy
values and
metallographic observations indicated that the
deformation mechanism was consistent with grainboundary sliding. It was also concluded that the
multiplicity of types of interphase boundary does not
play a significant part in determining superplastic
behaviour.
Paper No. MS 533. Manuscript received 23 February 1976; in
final form 30 April 1976. M. D. C. Moles, BA, PhD, was and
G. J. Davies, BE, MA, PhD, MIM, is in the Department of
Metallurgy
and Materials
Science at the University
of
Cambridge, where the work was carried out. Dr Moles is now in
the
Department
of
Mechanical
Engineering,
McMaster
University, Hamilton, Ontario, Canada.

EXPERIMENTAL
Tensile testing

Structural superplasticity is an unusual metallurgical

phenomenon wherein metals exhibit a high strain-rate
sensitivity which generally leads to high ductility, with
elongations sometimes greater than 1000% engineering strain.
During superplastic deformation the strain-rate sensitivity
index, m, usually lies in the range 03 < m < 08. The main
metallurgical requirement is a thermally-stable, very fine
equiaxed grain size. Polyphase materials have generally been
investigated because of their high thermal stability at
deformation temperatures. Structural superplasticity has
been the subject of reviewsl-3 which have fully described the
conditions necessary for superplastic flow as well as listing
fully the many materials for which superplasticity has been
reported. Generally superplastic deformation has been
shown to obey equations of the form2
at =K r.Lbexp

Metal Science

September

Table I
Compositions
eutectic alloys

and

structures

of

the

ternary

(1)

(Q;;/KT)

where at is the applied true stress, t the true strain rate, Qi

the activation energy at constant true strain rate, L the grain
size, and K and b are constants with b lying in the range
07-12.
Many investigations have been carried out on binary
alloys which exhibit superplasticity at room temperature,
particularly the Pb-Sn eutectic alloy.4-l4 Reports of
superplasticity in ternary eutectic alloys are rare, however,
limited data being available only for the Pb- Bi-Sn
eutectic.12 In the present work the effect of the presence of a
third phase on superplastic. behaviour was examined by
carrying out tests on the ternary eutectics Pb-Sn-Zn and
Pb-Sn-Cd.
314

A eutectic Pb-Sn-Zn bar was rolled to 95 mm square, the

corners ground off and surfaces smoothed, then swaged in
four stages down to 381 mm final diameter. Tensile
specimens with gauge-lengths of 127, 254, or 508 mm
were made by gluing sections of the swaged rods into thickwalled brass end-collets with Araldite. Specimens were cured
for 4 h at 343 K in a hot-air oven, and allowed to age for
several days before testing. This treatment permitted a small
amount of grain growth and grain stabilization to occur.
Specimens of each of these three gauge-lengths were pulled
to fracture at various constant cross-head velocities in air at
room temperature (295 K) using an Instron Model TM
testing machine. Strain-rate sensitivities were determined
using the change-in-strain-rate method of Backofen et al.17
Flat strip tensile specimens were made from eutectic bars
of Pb-Sn-Zn and Pb-Sn-Cd which were ground smooth,
then rolled to strip O75 mm thick in "'"12 passes. Parallel-

1976

(A) Pb-Sn-Zn

Pb

Composition, :wt.-%
Volume fraction, %
Structure of phases
Eutectic structure

311
655
34
25
71
4
fcc
bct
hcp
Sn-Zn lamellar eutectic with
irregular fibres of Pb

(B) Pb-Sn-Cd

Pb

Sn

Composition, wt.-%
Volume fraction, %
Structure of phases
Eutectic structure

32
24
fcc
Lamellar Snstructure

50
18
58
18
bct
hcp
Pb-Cd- Pb-Sn

Sn

Zn

Cd

Moles and Davies

sided tensile specimens were punched out parallel to the

rolling direction and rough edges trimmed smooth.
Specimens were electropolished, for 20 s at 50 V in a chilled
90 acetic: 10 perchloric acid solution and then annealed in
boiling water for 20 min..The strip specimens had a gaugelength of 20-22 mm, a width of 645 mm and a thickness of
O 70-0 80 mm. These strip specimens were tested in a water
bath at 298K (25C), 318K (45C), and 343K (70C).
Initial constant cross-head velocity tests showed that a"
significant amount of flow occurred in the grips.
Consequently simple correction procedures for the
evaluation of true stress and true strain were developed.
These assumed a constant rate of flow in the grips and
involved the evaluation of a factor which related the crosshead displacement to the gauge-length extension. Change in
strain-rate tests were performed on strip specimens of each
material with at least six specimens of each material being
tested at any given temperature. Cross-head velocity changes
were l11ade .in t~e sequence l,I2,I,'2,3,'2,
3, ...
where 1 < 2 <.3 or vice versa to reduce any effects
arising from .the direction of the change in cross-head
velocity. Cross-head velocities were generally kept within the
ratio 16 : 1. Tests were performed only when the specimen
load appeared to have reached a 'steady state'. Tests were
stopped when necking was observed. In no case was the
ratio width max: width min greater than 11 : 1 and m values
were determined over a range of strain up to 200%. For a
given true strain rate m was effectively independent of strain
over this range.

Superplasticity in Pb-Sn-Zn

700
600

127

11

508

o 254

06
- 05

/ '"-----'"...:,

Q 400

~//
.'

<.9300

z
o

Q 200

....
' ...
",

004

"-

",,,,,,,,,,,,,

31 5

eutectics

gauge length (mm)

~
o 500
Z
~

and Pb-Sn-Cd

0 0

' ....

11

100

,-

01

10-4

02

10-2

10-3

INITIAL

03

" ....
', ....
' ....

5-1

STRAIN-RATE,

Variation of elongation to fracture and strain rate

sensitivity index for cylindrical Pb-Sn-Zn specimens of
various gauge-lengths tested at 295 K.

..

100
298K

C\I

2: 10

cr

.....

"",.

...,...
......."...

N~

..

Microscopy

Optical metallographic specimens were cold-mounted and

etched in 3% Nital6 after conventional metallographic
preparation. Grain sizes were measured on a Quantimet 720
image analysing computer using a linear-intercept technique.
The Quantimet was set to measure the number of intercepts
falling into 13 categories under standard analysis conditions.
A histogram was built up and the mean free metallographic
path, or grain size L, was calculated from this.18 This
operation was repeated ten times on different areas of each
specimen and a mean and standard deviation for L were
calculated. These were converted directly to microns by
measuring a projected 10 Jlm grid.
With the etchant Pb-, Cd-, and Zn-rich grains could not be
readily distinguished. Thus the mean free metallographic
path, L, as measured was the grain size of joint Pb-Zn and
Pb-Cd phase mixtures. The final grain sizes were
293 015 Jlm for the Pb-Sn-Zn
eutectic alloy and
283 009 Jlm and 370 023 Jlm, respectively, for two
different preparations of the Pb-Sn-Cd eutectic alloy.
Surfaces specimens before and after deformation and
fracture surfaces were also investigated using scanning
electron microscopy.
MECHANICAL
Lead-tin-zinc

log t for Pb-Sn-Zn

eutectic

3 Dependence of log at on log Et for Pb-Sn-Zn

tested at 298, 318, and 343 K.

eutectic

2 Variation of log at with

tested at 298 K.

100
C\I

.
z

~10

tr

318 K

06
0'5

TEST RESULTS
eutectic

The variation of elongation to fracture with initial strain rate

in the Pb-Sn-Zn eutectic is shown in Fig. 1 for cylindrical
specimens of 127,254, and 508 mm gauge-lengths. Also
included in this figure is the variation of the strain-rate
sensitivity index measured on 254 mm gauge-length
specimens (cf. Fig. 4). Fig. 2 shows the relationship between
log at and log t for Pb-Sn-Zn strip specimens tested at
298 K. Similar results were obtained at the other test
temperatures and Fig. 3 shows the best-fit curves for this
alloy calculated from data similar to those of Fig. 2 using
polynomial regression analysis. Each curve was derived
using between 60 and 100 data points. The corresponding

04

298K

03
02
01

4 Variation of strain rate sensitivity index, m, with log t for

Pb-Sn-Zn eutectic tested at 298, 318, and 343 K.

Metal Science

September 1976

316

Moles and Davies

Superplasticity

in Pb-Sn-Zn

and Pb-Sn-Cd

Table II
Activation energies for superplastic flow in the
Pb-Sn-Zn ternary eutectic

Et,

QE, kJ/mol

3 x 10-3
197

10-3
257

3 X 10-4
273

a,N/mm2
Qa,kJ/mol

59
687

98
624

127
561

S-1

10-4
252

3 X 10-4
257

m/log t curves (also derived using between 60 and 100 data

points) obtained using the change-in-strain-rate procedure
are shown in Fig. 4. Using the curves of Fig. 3 the activation
energies at constant strain rate" Q i;, and constant stress, Q a,
for superplastic flow in Pb-Sn-Zn were determined. These
activation energies are given in Table II and are related by
the equation 19
1
Qa = - . Qi: . . . . . . . . . . . . . . . . . . . (2)

Lead-tin-cadmium

eutectic

The curves for the variation of log 0t with log Et and m with
log t, obtained by multiple regression for the Pb-Sn-Cd
eutectic alloy tested at 298, 318, and 343 K, are shown in
Figs. 5 'and 6, respectively. These results were all obtained
using strip specimens. The values of the activation energies
for flow obtained from Fig. 5 are giyen in Table III.
METALLOGRAPHIC

OBSERVATIONS

Examination of the microstructures of both the Pb-Sn-Zn

and the Pb-Sn-Cd
alloys before and after deformation
showed that there were no significant changes. Table IV lists
some typical results for Pb-Sn-Cd.
In some cases a limited amount of grain growth was
observed ('" 3-45 /lm) at the highest temperature and after
100
C\I

298K

.
z

2 10

343K

eutectics

Table III
Activation energies for superplastic flow in the
Pb-Sn-Cd ternary eutectic

Q, kJ/mol

3 x 10-3
215

10-3
260

3 X 10-4
271

a,N/mm2
Qa, kJ/mol

29
507

98
582

118
548

Et,

S-1

3 x 10-5
276

10-4
253

Table IV Grain-size measurements on Pb-Sn-Cd eutectic

specimens tested under various deformation conditions

Undeformed grain size 283

Test temp.,
K

Cross-head
velocity,

009 flm
Strain,
%

Ilm

290
393
3580
746
620
433
4790

254
254
275
297
292
273
305

Grain size,

mmlmin

343
343
343
343
343
298
298

50
5
5
05
005
05
05

003
007
008
014
006
008
011

long testing times. Static grain-growth studies showed that

these two materials were essentially stable for long time
periods (up to 500 h) at these deformation temperatures,
which is in agreement with similar observations for the Pb-Sn
binary eutectic alloys.20,21 Fig. 7 shows the surface of a
Pb-Sn-Zn specimen given an elongation of 20% under
conditions of superplastic deformation. The offset of fiducial
markings originally parallel to the tensile direction are
consistent with grain-boundary sliding having occurred. This
figure also shows that fiducial markings across the grain
centres have remained straight. This indicates that up to this
stage the bulk of the deformation has occurred in the grainboundary regions.
At higher strains, grain displacements occurred with
components normal to the specimen surface and it was no

318K

5 Dependence of log at on log Et for Pb-Sn-Cd

tested at 298,318, and 343 K.

eutectic

06
05
04

E
03
02
01
10-4

10-3

10-2

Et 75-1
6 Variation of strain rate sensitivity index, m, with log t for
Pb-Sn-Cd eutectic tested at 298, 318, and 343 K.

Metal Science

September 1976

7 Scanning electron micrograph of surface of Pb-Sn-Zn

specimen elongated 20% at 343 K, ,..,10-3 s-1. x1700.
Tensile direction arrowed.

Moles and Davies

Superplasticity

in Pb-Sn-Zn

and Pb-Sn-Cd

eutectics

317

lack of correlation between maximum m and maximum

elongation. This lack of correlation could be attributed to a
number of causes, namely:
(i) An increase in the local strain rate during neck
formation which would increase m if deformation
was
occurring below peak m and thus tend to stabilize further
deformation. This seems unlikely, however, since the strain
rates for maximum elongation were more than an order of
magnitude smaller than those at which peak m was observed.
(ii) Inhomogeneities in specimens under test could cause
premature failure. Metallographic evidence does not support
this hypothesis
since it showed that the zone-refining
procedure gave rise to very uniform microstructures.
(iii) If a backstress existed which had to be overcome
before deformation was initiated, the measured value of m
would not be the true value.24 Estimated values of the
backstress are small23,25 so it is unlikely to significantly alter
m, although it would shift peak m to somewhat lower strain
rates.

8 Surface of Fig. 7 specimen, elongation to ",400%. x800.

Tensile direction arrowed.
.

longer possible to identify the fiducial marks. The surfaces of

specimens
deformed
to high strains had a granular
appearance (Fig. 8) with the size of the granules approximately equal to the grain size. Comparison of the grain sizes
parallel and perpendicular
to the tensile direction after
deformation
showed that within experimental error the
microstructure remained equiaxed during deformation. Some
representative results are given in Table V.

FRACTOGRAPHY
All specimens necked down until only a few grains thick
before fracturing. Fracture initiated at the specimen edges
and propagated intergranularly. No cavitation was observed
on metallographic
examination
of internal sections of
specimens
deformed
at low strain rates other than
immediately adjacent to the fracture surface. Some surface
cavitation occurred at all strain rates (cf. Fig. 7). Fracture
surfaces of specimens deformed
at high strain rates
(10-3 S-I) showed substantial evidence of cavitation.
DISCUSSION
The present results (Fig. 1) show that for one of these alloys
the maximum elongation does not correlate directly with
. maximum m, in contrast to previously reported results for
some other superplastic systems.4, 8, 22 It should be noted,
however, that Dunlop and Taplin23 have observed a similar

Table V Grain sizes of Pb-Sn-Cd

eutectic
after superplastic deformation (E'" "0-3 S-1)
Undeformed grain size 370 023 /lm

Deformation
temp., K

298
318
343

Elongation,
%

636
390
361

Grain diameter,

specimens

/lm

Parallel to
tensile axis

Perpendicular
to tensile axis

391 006
392 006
388 010

387
369
380

005
006
006

Clearly the height/diameter

ratio is of importance since
increasing this ratio increased the elongation to failure proportionately, as was observed previously in binary Pb-Sn
eutectic alloys.8 There is a large scatter in the measured
values of elongation, particularly at lower strain rates; this,
together with the dependence on specimen dimensions,
indicates that elongation
is not necessarily
a reliable
parameter for the characterization of superplasticity:
The general form of the log at flog Et and m/log t curves
(Figs. 3-6) for the two ternary eutectics agrees with results
reported for binary systems.4-14 The log at/log Et curves are
essentially
straight over several orders of magnitude.
Nicholson26 has observed that curves of this nature are
generally
obtained
with isotropic
equiaxed-grained,
superplastic materials. Comparable data that exist for the
binary alloys relating at and Et, e.g. Pb-Sn,6,l1 Pb-Cd,27
show that insofar as detailed comparison is possible the
characteristics of superplasticity are largely unaltered by the
addition of a third phase, either in small (Zn) or large
proportions (Cd). For example, the flow stresses at 25C' at
strain rates of 167 x 10-3 S-I and 167 x 10-4 S-I for the
Pb-Sn eutectic* (after correction for grain-size differences)
are '37 and 137 MN/m2, respectively. For two ternary.
eutectics
the corresponding
values
are 384 and
144 MN/m2
The scatter in activation energies is large. A failing of this
type of analysis is that at both constant at and constant t
the values of m will vary. The activation-energy values are
given in Table VI together with comparable values obtained
with binary systems and for the constituent components.
These values show that Qi is normally lower than both the
activation energies for grain-boundary diffusion and volume
diffusion, whereas Q a is approximately
the same as that
reported
for grain-boundary
diffusion.
Recently,
Padmanabhan
and Padmanabhan35
and Mohamed
and
Langdon36 re-examined the relationships between the two
apparent activation energiesl9 (see eqn. (2 and concluded
that Qa is greater than35 or equal t036 the true activation
energy. Thus it follows from the tabular data that grain
boundary diffusion processes playa predominant role. It also
follows from the similarity between the activation-energy
values for the ternary and binary alloys that the mechanism of
superplastic deformation is essentially the same in both cases.
The high correlations
between both the mechanical
property data and the activation energies for the ternary and

* Values quoted are the averages from the data of Cline and
Alden6' and Baudelet and Suery.ll
Metal Science

September 1976

318

Moles and Davies

Superplasticity

in Pb-Sn-Zn

Table VI

Comparative activation-energy

Superplastic
in Pb-Sn-Cd

flow

Qi

Superplastic
in Pb-Sn-Zn

flow

and Pb-Sn-Cd

eutectics

values, kJ/mol

REFERENCES

215-276

Qa

507-548

Qi

197-273

Qa

561-687

Superplastic flow
in Pb-Sn
eutectic6, 11,28

Qi

326

Qa

461-502

Superplastic
in Pb-Cd
eutectic29

251-335

1. R. H. JOHNSON: Met. Rev., 1970, 15, 115.

2. G. J. DAVIES, J. W. EDINGTON, C. P. CUTLER, and K. A.
PADMANABHAN: J. Mat. Sci., 1970,6, 1091.
3. J. W. EDINGTON, C. P. CUTLER, and K. N. MELTON: Progress !vIat.
Sci., 1976,21,61.
4. D. H. AVERY and w. A. BACKOFEN: Trans. ASM, 1965,58,551.
5. P. J. MARTIN and w. A. BACKOFEN: ibid., 1967,60,352.
6. H. E. CLINE and T. H. ALDEN: Trans. Met. Soc. AIME, 1967,
239,710.
7. s. W. ZEHR and w. A. BACKOFEN: Trans. ASM, 1968,61,300.
8. w. B. MORRISON: Trans. Met. Soc. AIME, 1968,242,2221.
9. D. E. NEWBURY and D. c. JOY: Scr. Metall., 1970,4,825.
10. s. P. RAWAL and G. S. MURTY: Trans. Japan Inst. Metals, 1972,
13,57.
11. B. BAUDELET and M. SUERY: J. Mat. Sci., 1972,7,512.
12. A. M. S. GUTHRIE, D. E. NEWBURY, and P. M. HAZZLEDINE: Scr.
Metall., 1972, 6, 841.
13. A. E. GECKINLI and c. R. BARRETT: ibid., 1974,8, 115.
14. R. HORIUCHI, A. B. EL-SEGAI, and M. OTSUKA: Physica Status
Solidi (aJ, 1974, 21(a), K89.
15. D. J. S. COOKSEY and A. HELLAWELL: J. Inst. Metals, 1967,95,
183.
16. A. S. YUE and J. B. CLARK: Trans. Met. Soc. AIME, 1961,221,
383.
17. w. A. BACKOfEN, I. R. TURNER, and D. H. AVERY: Trans. ASM,
1964,57,980.
.
18. E. E. UNDERWOOD:. 'Quantitative
Stereology',
p.243.
1970:
NewYork (Addison-Wesley).
19. K. A. PADMANABHAN and G. J. DAVIES: Physica Status Solidi
(aJ, 1973, 18,295.
20. T. Y. M. AL-NIAB and J. L. DUNCAN: Internat. J. Mech. Sci., 1970,
12,363.
21. A. GHOSH and J. L. DUNCAN: ibid., 1970, 12,499.
22. D. A. WOODFORD: Trans. ASM, 1969,62,291.
23. G. L. DUNLOP and D. M. R. TAPLIN: J. Mat. Sci., 1972, 7, 83.
24. A. KARIM: Scr. Metall., 1969,3,887.
25. B. BURTON: ibid., 1971,5,669.
26. R. B. NICHOLSON: 'Electron Microscopy and the Structure of
Materials', p. 689. 1972: Berkeley (Univ. California Press).
27. s. SRINIVASA RAO, O. SIVAKESAVAN, S. H. GHUDE, and R. v.
TAMHANKAR:
Trans. Indian Inst. Met., 1970, 23, (4), 44.
28. J. W. ALDRICH and D. H. AVERY: 'Ultra-Fine Grain Metals', (ed.
J.. J. Burke and V. Weiss), p.397. 1970: New York
(Syracuse Univ. Press).
29. P. CHAUDHARI and s. MADER: 'High-Speed Testing Vol. VII:
The Rheology
of Solids', (Applied Polymer Symposia
No. 12), p. 1. 1969: New York (Interscience).
30. J. P. STARK and w. R. UPTHEGROVE: Trans. ASM, 1966, 59,479
and 486.
31. B. OKKERSEE: Acta Met., 1954,2,551.
32. T. H. ALDEN: J. Australian Inst. Metals, 1969, 14,207.
33. W. LANGE and D. BERGNER: Physica Status Solidi, 1962, 2,
1410.
34. E. S.WAJDA: Acta Met., 1954,2, 184.
35. G. PADMANABHAN and K. A. PADMANABHAN: Phil. Mag., 1976,
33,371.
36. F. A. MOHAMED and T. G. LANGDON: Physica Status Solidi (aJ,
1976,33,375.
37. T. H. ALDEN: Acta Met., 1967, 15,469.
38. D. J. DINGLEY: 'Scanning Electron Microscopy
1970'. p. 329.
1970: Chicago (ITT Press).
.

flow

Grain-boundary
diffusion

lead3O,31
209-657
tin33
358-427

cadmium32
493
zinc34
607

Volume diffusion

lead31
tin33

cadmium32

1076
955

775

binary systems lead to the conclusion that the

crystallographic structure of the constituent phases plays a
minority part in determining the nature of superplasticity.
This, in turn, implies that bulk intragranular processes, e.g.
dislocation movement, are not of significant importance,
particularly in view of the fundamental differences in the slip
behaviour of the constituent phases. Offset observations
(Fig. 7) indicate that some grain-boundary displacements
have occurred. The absence of any surface evidence of
internal grain deformation at low strains (Fig. 7) and the
absence of either surface evidence (cf. Figs. 7 and 8) or
internal metallographic evidence (see Table V) of grain
elongation at all strains provides further support for the view
that the deformation is consistent with grain-boundary
sliding playing a central role. Similar results reported by
other workers using both static (e.g. Alden37) and dynamic
(e.g. Dingley38) observations have been used as evidence for
a significant contribution to deformation by grain-boundary
sliding (see also Edington et al. 3).
As a consequence of the increased number of phases there
will be an increased number of different types of interphase
boundaries. For. example in Pb-Sn-Cd (for phase volume
fractions see Table I) there will be Pb/Pb, Sn/Sn, Cd/Cd,
Sn/Pb, Pb/Cd, and Cd/Sn boundaries. As the deformation
characteristics of the Pb-Sn-Cd ternary alloy are similar to
those of the Pb-Sn binary it can also be concluded that the
multiplicity of interphase boundaries does not have a
significant effect on superplastic deformation. Certainly
previous work has suggested that interphase and intercrystalline boundaries are similar in their contribution to
rate-sensitive deformation.
ACKNOWLEDGEMENTS

The authors would like to thank Professor R. W. K.

Honeycombe for providing laboratory facilities and the
Science Research Council for financial support (M.D.C.M.).

Metal Science

September 1976

THE METALS SOCIETY

1976