Journal of Alloys and Compounds 765 (2018) 1243e1252

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Improvement in the mechanical properties of eutectic Sn58Bi alloy by

0.5 and 1 wt% Zn addition before and after thermal aging
Shiqi Zhou a, b, *, Omid Mokhtari a, Muhammad Ghufran Rafique c,
Vasanth C. Shunmugasamy c, Bilal Mansoor c, Hiroshi Nishikawa a
a
Joining and Welding Research Institute, Osaka University, 11-1 Mihogaoka, Ibaraki, Osaka 567-0047, Japan
b
Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan
c
Mechanical Engineering Program, Texas A&M University at Qatar, Doha, Qatar

a r t i c l e i n f o a b s t r a c t

Article history: A comparative analysis of the microstructure and the mechanical properties of the eutectic Sn58Bi,
Received 22 January 2018 0.5 wt% and 1 wt% zinc (Zn)-functionalized Sn58Bi alloys was conducted before and after solid-state
Received in revised form thermal aging. Cross-sectional microstructure observation and tensile tests were performed on bulk
21 May 2018
solder alloys. The fracture surfaces were observed after the tensile tests. In addition, the mechanical
Accepted 11 June 2018
Available online 15 June 2018
properties of individual Sn and Bi phases were obtained using nanoindentation tests. The results indi-
cated that finer microstructures were obtained in the Zn-added samples compared to the eutectic Sn58Bi
before and after aging since the SneBi phase boundary segregation of Zn occurred during aging, and the
Keywords:
Sn58Bi
movement of the diffusion entities (Sn and Bi atoms) through the boundaries was obstructed. The fine
Zinc microstructure was responsible for the ultimate tensile strength improvement obtained in the Zn-added
Phase boundary samples. Meanwhile, a significant hardness decrease of the Sn phase in the Sn58Bi1Zn alloy was believed
Tensile test to be a possible reason for the superior elongation of the Zn-added samples.
Nanoindentation © 2018 Elsevier B.V. All rights reserved.
Solid solute softening

1. Introduction temperature-sensitive components, such as LEDs, by avoiding

In recent decades, a great demand for lead-free solders has been
observed in the electronics industry because of the toxicity of lead
(Pb) in eutectic SnePb solder [1e3]. To date, many lead-free solder
alloys, such as tinesilverecopper (SnAgCu), tinecopper (SnCu) and
tinezinc (SnZn), have been developed and selected as potential
replacements of the eutectic SnePb solder [1].
Among these candidates, low-temperature solder alloys have
lately drawn a great amount of attention from researchers. First,
thinner components with high-density I/Os and smaller solder
bumps are required in most electronic devices [4]; hence, thermal
warpage has become a real issue, and the primary solution for this
is using a low-temperature solder alloy with a lower bonding
temperature. Second, low-temperature soldering allows the fabri-
cation of inexpensive assembly materials, such as printed circuit
boards, without high-assembly temperature resistance and
* Corresponding author. Department of Smart Green Processing, Joining and
Welding Research Institute, Osaka University, 11-1 Mihogaoka, Osaka 567-0047,
Japan.
E-mail address: zhoushiqi@jwri.osaka-u.ac.jp (S. Zhou).
thermal damage. It also reduces the energy cost of fabrication
processes [5].
The eutectic Sne58 wt% Bi (Sn58Bi) solder alloy with a low
melting temperature of 139
C, a good tensile strength [6e8], and
wettability [9] has become a promising candidate solder alloy in the
low-temperature category. However, Sn58Bi has some disadvan-
tages, such as microstructure coarsening during thermal aging and
intrinsic brittleness of the Bi phase [10,11]. Note that the coarsened
Bi phase easily forms during thermal aging because a thermally
activated diffusion during thermal aging can lead to Ostwald
ripening of the Bi particles, which grow their size while consuming
the smaller ones [5]. Consequently, the coarsening microstructure
deteriorates the mechanical properties [10]. Moreover, the Sn phase
with the Bi solid solution has been reported responsible for
degrading the ductility of the eutectic Sn58Bi solder alloy, because
the Bi solubility in Sn is approximately 3 wt% at room temperature
[12], in which solid solute strengthens the Sn phase [11,12].
Many efforts have been made to address these issues. Yang et al.
[10] showed that 0.5 and 1 wt% Ni addition into the eutectic Sn58Bi
solder could not only refine the microstructure but also increase
ductility. However, the ductility increment drastically varied with

https://doi.org/10.1016/j.jallcom.2018.06.121
0925-8388/© 2018 Elsevier B.V. All rights reserved.
1244 S. Zhou et al. / Journal of Alloys and Compounds 765 (2018) 1243e1252
the increase of the aging time. Li et al. [13] reported that a 0.05 wt%
nanoscale Cu6Sn5 particle addition refines the eutectic Sn58Bi alloy
microstructure and increase the elongation, but decrease the ulti-
mate tensile strength (UTS). Li and Chan [14] reported that the
addition of 76 nm-sized silver nanoparticles effectively refined the
Sn58Bi solder microstructure and improved the hardness. Yang
et al. [15] showed that the introduction of a 0.07 wt% nanosized
graphite significantly increased the eutectic Sn58Bi elongation, but
simultaneously decreased the UTS. To date, some of the most
promising results have been obtained by doping Ag or In into the
eutectic Sn58Bi alloy. McCormack et al. found that the addition of a
small amount of Ag improved the Sn55Bi alloy elongation thrice
[16]. Meanwhile, the elongation increment of the In-added Sn58Bi
solder alloys was thoroughly studied by some researchers [5,11,17].
However, the UTS showed decreases in their results. Furthermore,
the expensiveness of the Ag and In must be considered in terms of
the mass production. In addition to the mechanical properties
study of a solder bulk, the reaction between Cu substrate and
Sn58Bi solder alloy has also been studied by many researchers. Li
et al. did a comprehensive study on the interfacial reaction kinetics
between Cu substrate and the Sn58Bi solder with a series of
elemental additions. They found that a barrier Cu5Zn8 IMC layer
forms between Cu substrate and the solder, thus resulting in a
better reliability [18].
Zn is one of the most accessible low-cost elements fabricated
with some of the solder alloys to yield a refined microstructure
and superior mechanical properties. El-Daly et al. reported that
SAC207 with 1.5 wt% Zn addition results in a refined microstruc-
ture, a higher UTS, and elastic modulus [19]. Hamada et al. studied
the increased flow stress and the inhibited intermetallic com-
pounds growth by adding a different amount of Zn into the low-Ag
SAC alloys. They found that the decline of flow stress during aging
can be suppressed [20]. McCormack and Jin proposed that the
quaternary Sn-3.5Ag-lZn-0.5Cu has better mechanical properties
than the binary Sn-3.5Ag alloy since it has a uniform fine disper-
sion of precipitates and a small effective grain size [21]. In addi-
tion, the effects of the interfacial reaction between Zn added SAC
solders and Cu substrate were thoroughly studied by some re-
searchers [22e25]. In terms of the eutectic Sn58Bi solder alloy, the
mechanical properties of ‘substrate/solder/substrate’ type solder
joint have been previously studied. Mokhtari et al. [26] reported
that, by adding Zn into the eutectic Sn58Bi solder, Cu5Zn8 IMC
layer formed on the solder/Cu interface during reflow instead of
Cu6Sn5 and Cu3Sn, thereby suppresing the SneCu IMC layer
growth. Ma and Wu found that both the Bi coarsening and the Sn-
Cu IMCs growth were suppressed by 0.7 mass% Zn addition in
Sn58Bi solder [27]. They also investigated how the mechanical
properties of Sn58Bi-0.7Zn solder joint are affected by coupled
stressing and solid-state aging [28]. However, the microstructure
and the mechanical properties of Sn58Bi solder bulk and how they
change during thermal aging with minor Zn addition are seldom
investigated.
This study investigates the microstructure and the mechanical
properties of 0.5 and 1 wt% Zn-added Sn58Bi alloys both before and
after solid-state thermal aging. Additionally, nanoindentation tests
were conducted on individual Sn and Bi phases in 1 wt% Zn added
Sn58Bi alloys. Nanoindentation can help in obtaining properties in
different phases of an alloy. The existing literature [10,13,29e31] on
nanoindentation show that Sn-based solders have been tested us-
ing loads in the range of mN and mechanical properties have been
reported for the bulk solder. However, we believe that nano-
indentation on individual phases will give insight on the correla-
tion between the mechanical properties and microstructure of the
solder and this experiment is attempted in the current study.
2. Experimental
The eutectic Sne58 wt% Bi solder (Sn58Bi) used in this study
was a commercially available solder rod. Accordingly, 0.5 and 1 wt%
Zn (99.99%) wires were alloyed with the eutectic Sn58Bi to produce
alloyed solders, hereafter called Sn58Bi0.5Zn and Sn58Bi1Zn,
respectively. Corresponding metallic Sn58Bi solder rods and Zn
wires were melted in-house at 700
C for 5 h. During the alloying
process, manual stirring was performed to the molten solders every
30 min to ensure a homogenous alloy. The compositions of the al-
loys were measured using inductively coupled plasma optical
emission spectroscopy (ICP-OES) after the alloying procedure. The
precise Zn composition was found to be 0.35 wt% Zn for
Sn58Bi0.5Zn alloy and 0.67 wt% for Sn58Bi1Zn alloy, as shown in
Table 1. It is believed that a fraction of the added Zn was oxidized
during the alloying. After the alloying, the alloys were subsequently
remelted at 250
C for 1 h before casting. A bar-shaped steel mold
was then used for casting. After which, some of the solder bulks
were prepared for a cross-sectional microstructure observation. For
the tensile testing experiment, a number of these bulks were
machined into a dumbbell shape, as shown in Fig. 1.
In thermal aging studies, some of these solder bulks were sub-
sequently immersed in an oil bath at 80
C temperature for 504 and
1008 h. The specimens for the microstructure observations and the
tensile tests were prepared after aging.
The morphological study of the microstructure and the fracture
surface, following the tensile tests, was performed using a field-
emission scanning electron microscope (FESEM, Hitachi SU-70)
equipped with an energy-dispersive X-ray spectrometer (EDX).
The phase identification was analyzed using elemental-mapping,
elemental-line, elemental-point, and line analysis on a JEOL JXA-
8530F field-emission electron probe microanalyzer (EPMA).
A Shimadzu Autograph AG-X machine was used to conduct the
tensile tests at room temperature under a strain rate of 0.0005/s.
The strain-stress curves of each alloy were generated and the me-
chanical properties (e.g., UTS and elongation) were then calculated.
Nanoindentation tests were conducted at room temperature
using a Hysitron, TI Premier nanoindentation system to evaluate
the mechanical properties of individual Sn and Bi phases at the
nanoscale within the as-cast alloy. Berkovich indenter with 100 nm
tip radius and 142.3
total included angle was used to perform the
indents. The well-known Oliver-Pharr method was used by
applying a load function with a peak load of 300 mN and a loading
Table 1
The chemical composition of the solder alloys.
Alloys Composition (wt%)
Sn Bi Zn
Sn58Bi0.5Zn Bal. 57.89 0.35
Sn58Bi1Zn Bal. 57.78 0.67
Fig. 1. Schematic illustration of the tensile test specimen.
 S. Zhou et al. / Journal of Alloys and Compounds 765 (2018) 1243e1252
time of 15 s was employed for the tests [32]. The indenter was then
held at the peak load for 20 s before it was completely withdrawn
from the specimen with 5 s unloading time. The peak load applied
to the specimen was kept small to ensure that each indent was
within a single phase. The data was used to generate
forceedisplacement curves and calculate the mechanical proper-
ties, such as reduced modulus (Er), and hardness (H) corresponding
to each indent. The nanoindentation results presented are average
values obtained over at least 15 indents on each phase.
3. Result and discussion
3.1. Microstructure of the solder alloys before aging
Fig. 2 presents the FE-SEM cross-sectional microstructure of the
as-cast alloys. Fig. 2a shows the microstructure of the as-cast
eutectic Sn58Bi. The beSn and Bi phases were represented by the
dark and light regions in this image, respectively [5]. The eutectic
structure indicated in Fig. 2a depicts an interlocked lamellar
structure [5]. In addition, the beSn dendrite phases with Bi pre-
cipitation within it and a large-size Bi phase were also identified in
Fig. 2a.
The microstructure of the newly synthesized Sn58Bi0.5Zn and
Sn58Bi1Zn alloys was observed in detail, as shown in Fig. 2b and c.
The lamellar eutectic structure and the beSn dendrite phase were
observed within both 0.5 and 1 wt% Zn added samples. The black
color platelet-shaped phase indicated in the matrix was recognized
as a Zn-rich (Zn flake) phase, which has been mostly reported in
SneZn solders by other researchers [33,34].
The precise composition and distribution of each element were
analyzed using elemental-mapping and point analysis using an
EPMA, as shown in Fig. 3. Fig. 3aec shows the mapping image of the
distribution of element Sn, Bi in eutectic Sn58Bi, and Sn, Bi, and Zn
in the Sn58Bi0.5Zn and Sn58Bi1Zn alloys, respectively. The dark
area in the eutectic structure was the Sn phase. The Sn distribution
was dominantly detected within the dark area, while Bi distributed
not only in the light area but also in the dark area. This result
indicated that Sn almost had no solid solution in the Bi phase, while
Bi dissolved in the Sn phase as a solid solution [12]. In contrast, Zn
was detected in both the Sn and Bi phases based on the mapping
and electrical-point result in Table 2.
Notably, Fig. 3b and c show that a large amount of Zn segregated
in the SneBi phase boundaries. The crystal structure difference
between the body-centered tetragonal beSn and the rhombohedral
Bi was the reason why the phase boundaries between them were
very likely to be non-coherent phase boundaries with high surface
energy and a large number of defects [35]. Therefore, the Zn ele-
ments may tend to segregate within these boundaries to reduce the
Gibbs free energy in the whole system [35]. Another reason is the
Fig. 2. FE-SEM images of the cross-sectional microstructure of as-cast solder bulks with the beSn and Bi phases represented by the dark and light regions. (a) Eutectic Sn58Bi. (b)
Sn58Bi0.5Zn. (c) Sn58Bi1Zn.
1245
limited solubility of Zn in both the Sn and Bi phases. In this study,
0.51 and 0.46 wt% Zn were detected in the Sn phase within 0.5 and
1 wt% Zn added samples, respectively. According to the literature
[20,36], the overall maximum solubility of Zn in Sn is 0.34 wt%.
Also, the Zn solubility in Bi was detected as 0.389 and 0.648 wt% for
0.5 and 1 wt% Zn added samples, respectively. The actual cooling
rate might be faster than the Zn precipitation rate. Thus we
assumed Zn to be supersaturated in the Sn phase because the alloys
we used herein were air-cooled within a steel mold to room tem-
perature after alloying. Comparing the actual Zn solubility in the Sn
and Bi phases with the amount of Zn added into the Sn58Bi alloy,
the extra Zn was assumed to exist in the form of segregated Zn on
the SneBi phase boundary and the Zn flakes.
The microstructures of the Zn-added Sn58Bi alloys were much
finer than those of the eutectic Sn58Bi. As previously reported [37],
during solidification, the impurities act as extra heterogeneous
nucleation sites within the eutectic Sn58Bi system, which signifi-
cantly refine the system microstructure. In addition, as shown in
Figs. 2 and 3, the pre-existing solid state Zn flakes acted as extra
heterogeneous nucleation sites during the solidification process
after remelting, which results in the refined microstructure in the
as-cast Zn-added Sn58Bi alloys.
3.2. Effects of thermal aging on the microstructure
Fig. 4 shows the cross-sectional microstructure changes of the
three alloys after being thermally aged for 504 and 1008 h,
respectively. The eutectic structure in the eutectic Sn58Bi alloy
coarsened as the thermal aging time increased. Several coarsened
Bi phases were also observed in Fig. 4a and d. This coarsened
microstructure as expected adversely affected the alloy mechanical
properties [10]. In contrast, the eutectic structure in the Zn-added
samples remained much finer and more homogeneous than the
eutectic Sn58Bi. Moreover, no sign of a coarsened Bi phase was
observed after aging. The eutectic spacing of these alloys was
measured using Image-pro Plus software to quantify the magnitude
of this microstructural change during thermal aging, as shown in
Fig. 5. The eutectic spacings of 0.5 and 1 wt% Zn-added samples
were much smaller than that of the eutectic Sn58Bi (2.06 and
2.34 mm, respectively versus 4.39 mm) before thermal aging. After
504 h thermal aging, slight changes in eutectic spacings were
observed in these three alloys. The eutectic spacing in the eutectic
Sn58Bi increased to 5 mm, while for Zn-added samples the increase
resulted in similar spacings of approximately 4.6 mm. However,
compared to the 508 h aging, by the time of 1008 h thermal aging,
the eutectic spacing for the eutectic Sn58Bi increased to 7.12 mm,
while the spacing for the Zn-added samples remained visually
unchanged, i.e. approximately 4.6 mm.
During thermal aging, the eutectic spacing for the eutectic
1246 S. Zhou et al. / Journal of Alloys and Compounds 765 (2018) 1243e1252

Fig. 3. EMPA mapping images of the microstructure of solder bulks before aging. (a) Eutectic Sn58Bi. (b) Sn58Bi0.5Zn. (c) Sn58Bi1Zn.

Table 2 Sn58Bi0.5Zn and Table 3 for Sn58Bi1Zn and the elemental-line

The change of the element composition in Sn and Bi phases within Sn58Bi0.5Zn results in Fig. 7. Tables 2 and 3 present the three points within
alloy during aging.
each individual Sn and Bi phases tested for both as-cast and ther-
Phase Element Composition of each phase in Sn58Bi0.5Zn mal aged 0.5 and 1 wt% Zn added samples. The result showed that
(wt%) the amount of the Zn solid solution within both Sn and Bi phases
As-cast 504 h 1008 h decreased during thermal aging. Especially in the Bi phase, the
Sn Sn 95.10 95.18 94.48 atomic percentage of Zn dropped to a very low level (below 0.05 wt
Bi 4.39 4.56 5.29 %) compared to the as-cast 0.389 and 0.648 wt% in 0.5 and 1 wt%
Zn 0.51 0.26 0.23 Zn-added samples. Fig. 7c also shows that in the as-cast Sn58Bi1Zn
Bi Sn 0.67 0.27 0.31 alloy, the phase boundary segregation of Zn was not obvious. In
Bi 98.94 99.69 99.65
Zn 0.39 0.04 0.04
contrast, as shown in Fig. 7d, the Zn count level on the phase
boundaries in a 1008 h aged Sn58Bi1Zn alloy was much higher than
that in the as-cast one, indicating an obvious Zn segregation (Fig. 7a
and b are the corresponding SEM images to Fig. 7c and d). As
Sn58Bi increased [38] because of the accelerated diffusion rate
previously mentioned, the SneBi phase boundaries were very alike
between the Sn and Bi phases and the tendency to achieve chemical
non-coherent grain boundaries, which provides an energy differ-
equilibrium under a high temperature. Especially after 1008 h ag-
ence between the lattice inside the phase and the phase bound-
ing, the eutectic spacing reached its highest value, 7.12 mm, which
aries. Moreover, the Zn atoms may tend to diffuse out of the
was approximately one-third higher than that of the as-cast one. In
individual supersaturated phase and predictably toward the phase
contrast, Zn-added samples also experienced an eutectic spacing
boundaries to minimize the overall free energy in the matrix
increase between 0 and 504 h aging. However, the value remained
because Zn was considered a supersaturated solid solution in Sn
almost unchanged after 1008 h aging, which was significantly
and Bi phases [35]. In addition, the Zn segregation on the SneBi
lower than that of the 1008 h aged eutectic Sn58Bi, as shown in
phase boundaries was considered homogeneous throughout the
Fig. 5.
entire matrix because the eutectic Sn58Bi alloy was mainly
Fig. 6 illustrates the EPMA mappings of how the Zn distribution
composed of a homogeneous SneBi eutectic structure.
changed during thermal aging. The elemental count level of the Zn
Based on the earlier discussion, the segregation of a large pro-
segregation on the SneBi phase boundaries was observed to in-
portion of Zn atoms on the SneBi phase boundaries were believed
crease during thermal aging. This phenomenon was also demon-
to act as an obstacle on the SneBi phase boundary diffusion paths
strated by the EPMA elemental-point result in Table 2 for
and, therefore, slowed down the diffusion rate of the Sn and Bi
 S. Zhou et al. / Journal of Alloys and Compounds 765 (2018) 1243e1252
Fig. 4. FE-SEM images of the cross-sectional microstructure of solder bulks after thermal aging. (a) and (d) eutectic Sn58Bi aged for 504 and 1008 h. (b) and (e) Sn58Bi0.5Zn aged for
504 and 1008 h. (c) and (f) Sn58Bi1Zn aged for 504 and 1008 h.
Fig. 5. Average eutectic spacing within eutectic Sn58Bi, Sn58Bi0.5Zn and Sn58Bi1Zn
solder bulks, before and after 504 and 1008 h thermal aging.
atoms crossing the phase boundaries. Consequently, the eutectic
spacing was nearly unchanged for both the 0.5 and 1 wt% Zn-added
samples after aging for 504 h.
3.3. Mechanical properties and deformation behavior
Fig. 8 illustrates the tensile test results of the eutectic Sn58Bi
and Zn-added samples, with the strainestress curves in Fig. 8a and
the mechanical properties, i.e., UTS and elongation. Before aging,
the elongations of the 0.5 and 1 wt% Zn added samples and that of
the eutectic Sn58Bi were 41.3%, 45.0%, and 37.5%, respectively, as
shown in Fig. 8b. The elongations of all the alloys decreased as the
thermal aging time increased. The elongation of the Sn58Bi1Zn
alloy remained the highest throughout the aging period, whereas
that of the eutectic Sn58Bi was the lowest. Fig. 8c depicts the UTS.
Both 0.5 and 1 wt% Zn-added samples showed a higher UTS
compared to that of the eutectic Sn58Bi both before and after aging.
Moreover, the UTS for the eutectic Sn58Bi remained almost
1247
unchanged after thermal aging, whereas that for both 0.5 and 1 wt%
Zn-samples noticeably increased.
Fig. 9 shows the fracture surfaces of all the samples that were
tested before and after thermal aging. It is obvious that the fracture
morphologies for the samples tested after different thermal aging
times were different. Before aging, all the three fracture surfaces
were dominated with a bulge structure, indicating the ductile
fracture mode [39] and the relatively small eutectic spacing. After
504 h thermal aging, a number of cleavage fractured phases and a
bulge structure were observed in the eutectic Sn58Bi, as shown in
Fig. 9d. According to the previous studies, the cleavage phases were
fractured brittle Bi phases [40], and the bulge structure indicated
the ductile Sn phase. The fracture of the Zn-added samples was
finer than that of the eutectic Sn58Bi in Fig. 9e and f. After 1008 h
thermal aging, as shown in Fig. 9g, the cleavage and the bulge
structure in the eutectic Sn58Bi became much easier to distinguish,
indicating that the eutectic structure became significantly coars-
ened at this aging stage.
As previously reported by others, finer the microstructure,
higher the UTS and elongation a tensile sample can produce [10,41].
Compared with the eutectic Sn58Bi before and after aging, the
superior elongation properties were obtained in the Zn-added
samples because the Zn-added samples contained a fine micro-
structure with a small eutectic spacing before and after aging,
whereas the eutectic spacing of Sn58Bi noticeably increased after
504 h thermal aging (Fig. 5). On the other hand, the increase of UTS
of the Zn-added Sn58Bi during thermal aging could be potentially
attributed to the pinning effect of the Zn segregation on the phase
boundaries, thereby impeding the phase boundaries from sliding
during the tensile tests.
Attributing the promising increase of mechanical properties, i.e.,
elongation and UTS to the microstructure refinement of the Zn-
added Sn58Bi alloys induced by the phase boundary segregation
of Zn was reasonable. However, the effects of the Zn solid solution
on the mechanical properties of the individual Sn and Bi phases
must also be taken into account. Thus, nanoindentation testing was
conducted to investigate how the mechanical properties of each
single phase (i.e., Sn and Bi phases) in Zn-added Sn58Bi change. In
addition, a possible explanation of how the two influencing factors
(i.e., microstructure and single phases' mechanical properties) co-
affect the tensile test results is discussed in the next section.
1248 S. Zhou et al. / Journal of Alloys and Compounds 765 (2018) 1243e1252

Fig. 6. EMPA mapping images of the microstructure of solder bulks after aging, showing the clear Zn segregation on the Sn-Bi phase boundary. (a) and (b) Sn58Bi0.5Zn after 504 and
1008 h aging, respectively. (c) and (d) Sn58Bi1Zn after 504 and 1008 h aging, respectively.

Table 3 the indenter modulus (Ei ), reduced modulus (Er ), Poisson's ratio of
The change of the element composition in Sn and Bi phases within Sn58Bi1Zn alloy tested materials (v), and the diamond indenter (vi ). For each
during aging.
parameter in this case, vi ¼ 0.07; Ei ¼ 1140 for the diamond
Phase Element Composition of each phase in Sn58Bi1Zn indenter; and v ¼ 0.35 for the Sn-based alloys [12]. Accordingly, Er
(wt%) for each indent was calculated based on the Oliver-Pharr method.
As-cast 504 h 1008 h Fig. 11c and d shows the elastic modulus (E) and the hardness
Sn Sn 94.97 95.15 94.01 (H) change between the Sn and Bi phases within the eutectic
Bi 4.57 4.51 5.67 Sn58Bi and Sn58Bi1Zn alloys, respectively. Notably, the elastic
Zn 0.46 0.34 0.32 modulus and the hardness of both the Sn and Bi phases in
Bi Sn 0.32 0.34 0.23
Sn58Bi1Zn, were lower than those in the eutectic Sn58Bi, especially
Bi 99.03 99.64 99.77
Zn 0.65 0.02 0.00
the significant hardness decrease for the Sn phase.
Based on the elemental-point results in Table 2, in the Sn phase
composition within the eutectic Sn58Bi system, Sn phase was the
solvent with approximately 4.5 wt% Bi solid solution. A little
3.4. Nanoindentation tests
amount of the Bi solid solution in the phase slightly increases the
elastic modulus and dramatically increases the hardness because Bi
Fig. 10 presents a comparison of the loadedisplacement curves
can effectively hinder the dislocation movement within the Sn bulk
(Peh curves) of the individual phases tested under the same con-
lattice [12]. Moreover, the Bi solid solution in Sn phase can reduce
ditions, which were explained in the experimental section. Fig. 10a
the Sn phase ductility because of the intrinsic brittleness of the Bi,
shows the Peh curves of the Sn and Bi phases from the as-cast
thereby increasing the brittleness of the eutectic Sn58Bi solder
Sn58Bi alloy. For comparison, Fig. 10b displays the Peh curves of
alloy [11]. Thus, for the case of the reduced hardness and the
the Sn and Bi phases from the as-cast Sn58Bi1Zn alloy. The Peh
slightly reduced elastic modulus observed in Sn58Bi1Zn alloy and
curves in Fig. 10 were representatives of the entire data set for
combining the fact that the Zn was also a solid solution in both the
each sample. The displacement of the Sn and Bi phases in
Sn and Bi phases, the Zn solid solution was very likely responsible
Sn58Bi1Zn were noticeably higher than those of the eutectic
for this phenomenon.
Sn58Bi.
Many studies reported that the solid solution not only can
Fig. 11a and b shows the two scanning probe images of the post-
harden a material but also soften one [43e47]. In other words, the
indent areas in our tested samples. The white arrows in the figure
solid solute softening (SSS) reduces the material's ability to resist
indicate the indent positions in each sample, where points 1e4 and
indentation (hardness) [44]. The SSS in metals with a body-
points 5e8 represent the indent positions within the Sn and Bi
centered cubic (BCC) crystal structure with various solid solutes
phases, respectively.
was mostly studied in these reports. For the SSS specifically
The initial unloading part of P-h curve represents elastic re-
attributed to the Zn solid solution, Soldatov at el. [43] found that a
covery and slope of this part is used to calculate reduced modulus.
small amount of Zn decreases the yield stress of pure beSn at low
The elastic modulus is calculated based on reduced modulus as
temperatures (1.6e150 K) because impurity atoms act as the cen-
[42]:
ters of nucleation of paired kinks and lead to a potential relief of a
Peierls crystal. Wu and Lee [46] found that 15 at% Zn-added Ag
1 1  v2i 1  v2 significantly increases the UTS and elongation probably because of
¼ þ (1)
Er Ei E the ease of destroying the short-range order for the leading dislo-
cation. In this study, we believe that aside from the refined
where, the elastic modulus (E) of the tested specimen is related to
 S. Zhou et al. / Journal of Alloys and Compounds 765 (2018) 1243e1252 1249

Fig. 7. EPMA elemental-line results obtained with a testing distance of 3 mm crossing two SneBi phase boundaries in each Sn58Bi1Zn solder bulk and the corresponding SEM
images. (a) and (c) In an as-cast sample. (b) and (d) In a 1008 h aged sample.

Fig. 8. (a) Tensile stain-stress curves of eutectic Sn58Bi and Zn added Sn58Bi solder slabs before aging. (b) Elongations of eutectic Sn58Bi and Zn added Sn58Bi before and after
aging. (c) UTSs of eutectic Sn58Bi and Zn added Sn58Bi before and after aging.

microstructure, the SSS of the Zn solid solution was also responsible nanoindentation test results because the irreversible plastic
for the elongation improvement of the Zn-added Sn58Bi alloys. deformation easily happened in the Sn phase in the Sn58Bi1Zn
The hardness, which is directly related to the ability of a material alloy. Because the indents of the nanoindentation tests were within
to resist plastic deformation showed a decrease in our the individual phases, i.e., the Sn and Bi phases, the mechanical
1250 S. Zhou et al. / Journal of Alloys and Compounds 765 (2018) 1243e1252

Fig. 9. FE-SEM images of tensile fracture surfaces. (a), (d) and (g) eutectic Sn58Bi aged for 0, 504 and 1008 h. (b), (e) and (h) Sn58Bi0.5Zn aged for 0, 504 and 1008 h. (c), (f) and (i)
Sn58Bi1Zn aged for 0, 504 and 1008 h.

Fig. 10. Representative load-displacement curves of individual Sn and Bi phases within (a) eutectic Sn58Bi and (b) Sn58Bi1Zn before aging.

properties of the Sn and Bi phases were considered independently,
regardless of the other influence factors, such as eutectic structure
and the phase boundary. Moreover, based on the linear positive
correlation in equation (2) [10,48,49], theoretically, the hardness
reduction lead to the UTS decrease of the Sn phase in the Sn58Bi1Zn
alloy.
Hv z3sUTS
However, the UTS results from the tensile test in this study were
slightly higher in both the Sn58Bi0.5Zn and Sn58Bi1Zn compared
to the eutectic Sn58Bi in Fig. 8c. The microstructure refinement can
result in a simultaneous effective improvement in the alloy
strength but only slightly in the ductility because a finer structure
may contain smaller flaws, which need great stress to achieve
failure [41]. Hence, the effects of both the microstructure refine-
ment and the Zn segregation pinning were believed to overlap and
trump the effect of the hardness reduction, and were more domi-
(2) nant in terms of the UTS increase. On the other hand, the increase of
the elongation observed in the 0.5 and 1 wt% Zn-added Sn58Bi al-
loys was attributed to the possible solid solution softening effect of
 S. Zhou et al. / Journal of Alloys and Compounds 765 (2018) 1243e1252
Fig. 11. Post-indent surfaces as well as elastic modulus and hardness result. (a) and (b) Post-indent surfaces of eutectic Sn58Bi and Sn58Bi1Zn, respectively. (c) and (d) Elastic
modulus and hardness comparison of Sn and Bi phases within eutectic Sn58Bi and Sn58Bi1Zn alloys, respectively.
the Zn solid solution mainly in the Sn phase. In addition to the SSS
discussion, Chen at el. [11] reported an impressive elongation
improvement of 2.5 wt% In-added Sn58Bi alloy. They explained that
the In solid solution in the Sn phase interacted with the strength-
ening effect of the Bi solution, thereby softening the Sn phase. In
this study, considering the 0.51 and 0.46 wt% Zn solid solution in Sn
phase (Tables 2 and 3), this Zn solid solution might also has the
similar effect as the In solid solution counteract with the Bi solu-
tion, therefore softening the Sn phase.
The eutectic spacings of both 0.5 and 1 wt% Zn-added samples
remained almost unchanged when compared to that of the eutectic
Sn58Bi after 504 h thermal aging. This might be the reason why the
superior UTS of these Zn-added samples after aging were obtained,
as shown in Fig. 8. On the other hand, the effect of solid solution
softening reduced during the aging process because the Zn solid
solution content in both Sn and Bi phases reduced. As a result, the
elongation for both 0.5 and 1 wt% Zn-added samples decreased
probably because the solid solution softening was very sensitive to
the solute concentration [44].
4. Conclusions
The effects of the microstructure and the mechanical properties
induced by 0.5 and 1 wt% Zn addition in the eutectic Sn58Bi alloy
were studied. This work provided a new method and understand-
ing of how to refine the eutectic Sn58Bi alloy microstructure.
1251
Both 0.5 and 1 wt% Zn effectively refined the eutectic Sn58Bi
alloy microstructure. Before aging, Zn atoms acted as extra solidi-
fication sites. During aging, Zn atoms moved from the solid solution
within both the Sn and Bi phases to the SneBi phase boundaries as
a Zn segregation, which suppressed the microstructure from
coarsening.
A significant hardness decrease of the Sn phase was observed in
the Sn58Bi1Zn sample. And a potential SSS phenomenon of 1 wt%
Zn solid solution in the Sn phase was proposed.
The improved elongation and UTS were obtained both before
and after thermal aging. The microstructure refinement and the
potential SSS were responsible for these improvements. In addition,
the fracture surfaces showed mainly ductile fractures in the Zn-
added samples and brittle fractures in the eutectic Sn58Bi sam-
ples, especially after 1008 h thermal aging.
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