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Article history:
Received 25 May 2011
Received in revised form 27 August 2011
Accepted 27 September 2011
Available online 5 October 2011
Keywords:
Lead-free solder
SnSb alloy
Tensile properties
Stress exponent
a b s t r a c t
Tensile deformation behavior of Sn5Sb, Sn5Sb1.5Bi, and Sn5Sb1.5Cu alloys was investigated at
temperatures ranging from 298 to 400 K, and strain rates ranging from 5 104 to 1 102 s1 . Addition
of Bi and Cu into the binary alloy resulted in an increase in both ultimate tensile strength (UTS) and ductility. The improved strength of the Bi-containing alloy can be attributed to the microstructural renement,
uniform distribution of the SnSb intermetallic particles, and solid-solution hardening effect of bismuth
in the -Sn matrix. The enhanced strength of the Cu-containing alloy was ascribed to the presence of the
Cu6 Sn5 intermetallic particles and structural renement. The ductility of both ternary alloys was, however, improved by the structural renement, caused by the addition of alloying elements. The results of
tensile tests indicate that the strength of all three alloys increase with increasing strain rate and decrease
with testing temperature. The variation of ductility with strain rate showed a descending trend, while it
exhibited a minimum at medium testing temperatures. Based on the obtained stress exponents and activation energies, it is proposed that the dominant deformation mechanism in Sn5Sb is dislocation climb
over the whole temperature range investigated. For the ternary alloys, however, grain boundary diffusion
and dislocation climb are the deformation mechanisms at high and low temperatures, respectively.
2011 Elsevier B.V. All rights reserved.
1. Introduction
Tinlead solders have long been used in the microelectronic
packaging industry. The widespread use of these solders is primarily due to their low cost, good wettability and satisfactory strength
properties for lifetime performance [1,2]. Despite the long-term
utilization of SnPb alloys, recent concerns about lead toxicity have
resulted in serious restrictions on their use. Therefore, there has
been a great deal of research work to develop alternative lead-free
solders [35]. Accordingly, many lead-free Sn-based alloy systems
with different alloying elements such as; Ag, In, Cu, Zn, Bi, Ni and Sb
have been developed and their microstructures, mechanical properties, creep resistance, and wettability have been studied.
Among the developed lead-free solders, the near-peritectic
Sn5Sb alloy with a relatively high melting point of 518 K and a solder substrate contact angle of about 43 has been developed as one
of the potential alternate materials for replacing lead containing
solder alloys. The Sn5Sb alloy has the advantages of good creep
resistance [69] and superior mechanical properties, particularly
strength and ductility [10,11]. To further improve the mechanical
properties of the binary SnSb alloys, third alloying elements such
Corresponding author. Tel.: +98 21 8208 4137; fax: +98 21 8800 6076.
E-mail address: mahmudi@ut.ac.ir (R. Mahmudi).
0921-5093/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.msea.2011.09.103
as Ag, Cu, In, and Au have been employed. Most of these studies are
concerned mainly with the creep resistance rather than strength
of the developed materials. Recently, El-Daly et al. [12] studied the
effect of 0.7% Cu and 0.7% Ag on the tensile behavior of a Sn5Sb
alloy. They showed that both Ag and Cu rened the microstructure and formed new intermetallic compounds. Addition of Cu was
found to be more effective than Ag in increasing the yield stress and
ultimate tensile strength (UTS) of the base material. The strength of
all tested alloys increased with increasing strain rate and decreasing testing temperature. Similar trends in strength have also been
reported when Ag and Au have been added to the Sn5Sb base alloy
[13].
The present paper examines the inuence of adding Bi and Cu
on the tensile properties of a wrought Sn5Sb solder alloy. It is well
established that Sn5Sb is a composition that can provide a wide
range of desirable soldering and mechanical properties. Addition
of alloying elements is usually aimed at improving some of these
properties without impairing the other ones. The amount of added
Bi and Cu was limited to 1.5 wt.% in order to increase the strength
and ductility without damaging the wettability and other soldering
characteristics. The tensile deformation and fracture behavior of
Sn5Sb1.5Bi and Sn5Sb1.5Cu solder specimens at various strain
rates in the range 5 104 1 102 s1 , over the wide temperature
range of 298400 K are compared with those of the Sn5Sb base
solder material.
M.J. Esfandyarpour, R. Mahmudi / Materials Science and Engineering A 530 (2011) 402410
2. Experimental procedure
Sn-5Sb-1.5Cu
Sn
SnSb
Cu6Sn5
Sn-5Sb-1.5Bi
CPS
403
Sn-5Sb
20
30
40
50
22 , Degree
Degree
60
70
obtained over the whole gage length, from which the true stress
at the peak load was calculated as the ow stress needed for the
calculation of the stress exponent (n). Fractography was performed
on the fractured surfaces in order to study the effect of Bi and
Fig. 2. SEM micrographs of: (a) Sn5Sb, (b) Sn5Sb1.5Bi, (c) Sn5Sb1.5Cu, and EDX analyses of (d) SnSb, (e) -Sn, and (f) Cu6 Sn5 particles in the respective alloys.
404
M.J. Esfandyarpour, R. Mahmudi / Materials Science and Engineering A 530 (2011) 402410
70
T = 298 K
50
A:
=1X10-2 s -1
40
B:
=5X10 s
30
-3
-1
-3
-1
-4
-1
C:
=1X10 s
D:
=5X10 s
20
55
45
1: Sn-5Sb-1.5Bi
2: Sn-5Sb-1.5Cu
3: Sn-5Sb
35
10
0
0
B C
50
100
150
(a)
25
200
250
0.005
170
70
T = 298 K
(b)
60
0.01
Strain Rate, s
Strain, %
50
A:
=1X10-2 s -1
40
B:
=5X10 s
30
C:
=1X10 s
D:
=5X10 s
-3
-1
-3
-1
-4
-1
20
120
95
1
2
70
10
A
0
0
50
100
150
(b)
45
200
250
0.015
-1
1: Sn-5Sb-1.5Bi
2: Sn-5Sb-1.5Cu
3: Sn-5Sb
145
Sn-5Sb-1.5Bi
Elongation ,%
Stress, MPa
65
UTS, MPa
Stress, MPa
60
75
(a)
Sn-5Sb
0.005
0.01
Strain Rate, s
0.015
-1
Strain, %
Fig. 4. Effect of strain rate on mechanical properties at 298 K: (a) tensile strength,
and (b) elongation.
Stress, MPa
70
(c)
60
Sn-5Sb-1.5Cu
50
A:
=1X10-2 s -1
40
B:
=5X10 s
C:
=1X10 s
30
D:
-3
-1
-3
-1
-4
-1
=5X10 s
20
10
0
0
50
100
150
200
250
Strain, %
Fig. 3. Stressstrain curves of: (a) Sn5Sb, (b) Sn5Sn1.5Bi, and (c) Sn5Sb1.5Cu
alloys, obtained at 320 K and different strain rates.
M.J. Esfandyarpour, R. Mahmudi / Materials Science and Engineering A 530 (2011) 402410
50
80
(a)
Sn-5Sb
10
298KK
1:1:
298
320Kk
2:2:
320
340Kk
3:3:
340
370 K
4:4:
370
K
5: 400 K
UTS, MPa
Stress, MPa
20
60
0
0
50
100
150
200
250
20
280
300
Strain, %
1:Sn-5Sb-1.5Bi
2:Sn-5Sb-1.5Cu
3:Sn-5Sb
320
. =
120
(b)
Sn-5Sb-1.5Bi
1: 298 K
Elongation, %
Stress, MPa
40
2
1: 298 K
30
2: 320 k
2: 320 K
3: 340 k
3: 340 K
20
4: 370 K
10
360
4: 370 K
5: 400 K
5: 400 K
50
100
150
200
250
300
Strain, %
50
Stress, MPa
30
20
80
40
1:Sn-5Sb-1.5Bi
2:Sn-5Sb-1.5Cu
3:Sn-5Sb
320
360
Temperature, K
400
440
1: 298 K
2: 320 K
3: 4:
340
370KK
3: 340 k
4: 5:
370
400KK
5: 400 K
0
0
0
280
1: 298 K
2: 320 k
10
(b)
(c)
Sn-5Sb-1.5Cu
40
440
1 10-2
0
0
400
Temperature, K
50
1
-2
3
40
5: 400 K
(a)
= 1 10
40
30
405
50
100
150
200
250
300
Strain, %
Fig. 5. Stressstrain curves of: (a) Sn5Sb, (b) Sn5Sn1.5Bi, and (c) Sn5Sb1.5Cu
alloys, obtained at a strain rate of 5 103 s1 and different temperatures.
cooling from the liquid state, and thus it can act as a nucleation
site for SnSb and -Sn with the respective melting points of 350
and 232 C [15]. The EDX analysis of the rod-shape particles, given
in Fig. 2f, indicates that they have a composition of 64.6 wt.% Sn
and 35.4 wt.% Cu. This corresponds closely to the stoichiometric
composition of the Cu6 Sn5 intermetallic phase, already detected
by the XRD analysis. Concerning the chemical composition of the
second phase particles, it should be noted that the quantitative EDX
results slightly overestimates the Sn percentage in all cases. This
can be a result of a large interaction volume of electron beam with
the Sn matrix, which leads to the emission of X-ray from material
beneath the particles.
406
M.J. Esfandyarpour, R. Mahmudi / Materials Science and Engineering A 530 (2011) 402410
renement, uniform distribution of the SnSb intermetallic particles, and solid-solution hardening effect of bismuth in the -Sn
matrix [1922]. The addition of Cu to the base alloy also improves
the strength, mainly due to the presence of the addition of Cu6 Sn5
intermetallic particles. However, it is evident that the strengthening effect of Cu is not as strong as that of Bi.
Fig. 4b shows the variation of total elongation with the applied
strain rate for the investigated solder alloys at room temperature. It
can be observed that elongation to failure decreases continuously
with increasing strain rate. This consistent behavior is in contrast
to those reported for a cast Sn9Zn base alloy containing Ag and
Cu [18], in which total elongation had shown a pronounced uctuation with strain rate. It seems that in the present wrought alloys a
more uniform and rened microstructure excludes the possibility
of microstructural inhomogeneities, which can result in inconsistent elongation values, usually observed in the cast structures.
The observed strain rate dependency of ductility can be interpreted based on the interaction of dislocations with intermetallics
and other barriers. These barriers can effectively obstruct the fast
mobile dislocations at low strain rates. At high strain rates, however, the obstacles cannot lock the moving dislocations any more
because of the faster dislocation. This means that at low strain rates
dislocation generation is less favored, and thus, thermally activated
processes such as dynamic recovery and recrystallization have sufcient time to act to extend the total elongation. Similar to the
strength data, shown in Fig. 4a, the Sn5Sb1.5Bi alloy displays
the highest elongation, followed by Sn5Sb1.5Cu and Sn5Sb
over the whole range of strain rates studied. The elongation values of 153, 138 and 113%, found respectively for the Sn5Sb1.5Bi,
Sn5Sb1.5Cu and Sn5Sb alloys at the strain rate of 5 104 s1 ,
are indicative of the excellent ductility of the tested alloys at room
temperature. The superior ductility of the ternary alloys relative to
the base binary material is attributed to the structural renements
caused by the addition of Bi and Cu.
3.3. Effect of temperature on mechanical properties
In order to determine the temperature dependence of deformation behavior of the tested solder alloys, their tensile properties
were investigated at temperatures in the range of 298400 K. Typical stressstrain curves of the alloys obtained at a strain rate of
5 103 s1 are shown in Fig. 5ac. It is evident that the overall strength of the alloys shows a consistent declining trend with
increasing temperature. This is in contrast to the variation of
total elongation, which exhibits a more complicated pattern. For
a more complete view on the overall temperature dependence of
the mechanical properties, the UTS and elongation to failure values were determined for Sn5Sb, Sn5Sb1.5Bi and Sn5Sb1.5Cu
alloys, and plotted against testing temperature at a constant strain
rate of 1 102 s1 in Fig. 6. It is clear from Fig. 6a that tensile
strength of all three solders dramatically decreases with increasing
temperature. This is a consequence of the activation of softening
processes, which are encouraged at high temperatures. In such a
case, the rate of decrease in the dislocation density (annihilation)
increases, leading to continuously falling of stress level. This implies
that at high temperature substructure strengthening becomes inactive and subgrain boundaries are no longer dislocation barriers. It
is to be noted that the room-temperature strengthening effects of
Cu and Bi also persist at high temperatures. Fig. 6b shows the effect
of temperature on the elongation of the three investigated solder
alloys. It is evident that the ductility of all materials passes through
a minimum at about 340 K, after which it increases with temperature. Furthermore, the Bi- and Cu-containing alloys possess higher
ductility than the base alloy at all tested temperatures in such a
way that at 400 K the elongation of these alloys are 1.6 and 1.2
times higher than that of the base alloy, respectively.
M.J. Esfandyarpour, R. Mahmudi / Materials Science and Engineering A 530 (2011) 402410
13.0
ln ( T/E),K/MPa- s
Table 1
Creep characteristics of the tested alloys.
(a)
T = 298 K
11.0
Sn5Sb
Sn5Sb1.5Bi
Sn5Sb1.5Cu
10.0
Sn-5Sb,
n = 6.1
Sn-5Sb-1.5Cu, n = 4.5
Sn-5Sb-1.5Bi, n = 6.5
8.0
14.0
14.5
15.0
ln (
15.5
16.0
E)
13.0
ln ( T/E),K/MPa- s
Low temp.
High temp.
298 K
320 K
340 K
370 K
400 K
55
73
67
55
45
44
7.1
7.8
6.2
6.6
7.3
5.8
6.1
6.5
4.5
5.1
4.2
3.9
4.4
3.7
3.4
(b)
T = 340 K
12.0
11.0
10.0
Sn-5Sb,
n = 7.1
Sn-5Sb-1.5Cu, n = 6.2
Sn-5Sb-1.5Bi, n = 7.8
9.0
8.0
13.5
14.0
14.5
ln (
15.0
15.5
E)
13.0
(c)
T = 400 K
ln ( T/E),K/MPa- s
Q (kJ mol1 )
Material
12.0
9.0
407
12.0
11.0
10.0
Sn-5Sb,
n = 3.4
Sn-5Sb-1.5Cu, n = 3.7
Sn-5Sb-1.5Bi, n = 4.4
9.0
8.0
12.5
13.0
13.5
ln (
14.0
T
n
=A
Q
exp
(1)
RT
where T is the temperature, E is the elastic modulus, A is a material parameter, n is the stress exponent, Q is the creep activation
energy, and R is the universal gas constant. Since A is a constant, it
14.5
15
E)
14
ln (
T/E), K/MPa- s
Fig. 8. Relationship between true strain rate and true stress at different testing
temperatures: (a) 298, (b) 340 and (c) 400 K.
13 45 kJmol -1
12
11
55 kJmol -1
44 kJmol -1
10
9
67 kJmol -1
73 kJmol -1
7
6
2.2
2.4
2.6
2.8
3.2
3.4
3.6
3.8
1000/T, K -1
Fig. 9. Relationship between the tensile stress and the reciprocal temperature for
three solder alloys.
408
M.J. Esfandyarpour, R. Mahmudi / Materials Science and Engineering A 530 (2011) 402410
Fig. 10. SEM fractograph of the solders deformed at 340 and 400 K and at the constant strain rate of 5 104 s1 .
(2)
According to Eq. (1), plotting the variation of the temperaturecompensated strain rate rates against normalized true tensile
strength on a double logarithmic scale, would yield a straight line
with the slope of stress exponent, n. This is depicted in Fig. 8
for the three lead-free solders at various temperatures. The stress
exponents were determined according to Eq. (1) by plotting the
temperature-compensated strain rate against normalized tensile
strength at different temperatures, as shown in Fig. 8ac. The
M.J. Esfandyarpour, R. Mahmudi / Materials Science and Engineering A 530 (2011) 402410
409
410
M.J. Esfandyarpour, R. Mahmudi / Materials Science and Engineering A 530 (2011) 402410
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