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Title: Influence of ZnO nanoparticles addition on thermal analysis, microstructure evolution and tensile
behavior of Sn-5.0 wt% Sb-0.5 wt% Cu Lead-free solder alloy
Article Type: Original Article
Keywords: Keywords: Sn-5Sb; solder; composite; lead free; yield stress; ultimate tensile stress
Corresponding Author: Dr. Eid A Eid, Ph. D.
Corresponding Author's Institution: Basic Science Department, Higher Technological Institute, 44629
10th of Ramadan City Egypt
First Author: Eid A Eid, Ph. D.
Order of Authors: Eid A Eid, Ph. D.; Aly Fouda
Abstract: AbstractSn-5wt%Sb-0.5wt%Cu (plain SSC505) and Sn-5wt%Sb-0.5wt%Cu-0.5wt% ZnO (SSCZnO) composite solder alloys have been studied. The variation in thermal behavior, microstructure and
tensile characteristics associated with mixing of 0.5wt% ZnO nano-metric particles to plain SSC505
so
using differential scanning calorimetry (DSC) after addition of ZnO. X-ray diffraction (XRD) analysis
-Sn, SbSn and Cu6Sn5 intermetallic compounds (IMCs) beside some of ZnO
planes in SSC-ZnO composite solder. Field emission scanning electronic microscope (EF-SEM)
investigation of SSC-ZnO composite solder revealed a homogenous uniform distribution, size
-Sn grains. Addition of ZnO nano-metric particles into the plain SSC505
addition, adding ZnO nano-metric particles were found to be effective for reducing ductility by 43% of
-Sn grains within SSC305-ZnO composite solder.

Cover Letter

Dear Editor
Im pleased to present our work titled
"Influence of ZnO nano-particles addition on thermal analysis,
microstructure evolution and tensile behavior of Sn-5.0 wt% Sb-0.5 wt%
Cu Lead-free solder alloy"
The effect of adding ZnO nano-particles to Sn-5wt%Sb-0.5wt%Cu
(plain SSC505) were studied. The variation in thermal behavior,
microstructure and tensile characteristics associated with mixing of
0.5wt% ZnO nano-metric particles to plain SSC505 solder were
investigated. X-ray diffraction analysis of SSC-ZnO confirms the
existence of SbSn, Cu6Sn5 IMCs and ZnO. The microstructure
observations revealed finer IMCs due to active surface area of ZnO
nanoparticles that supports the strong adsorption effect. Improvement in
the tensile parameters was achieved because of presence of ZnO
nanopowders as reinforcement agent. The nano-sized particles are
dispersed uniformly and homogeneously distributed in Sn matrix which
provide high barrier by impeding grain boundary sliding and dislocation
movement.
The work is valuable to be published in Materials and Design.
We here confirm that:
1. The article is original.
2. The article has been written by the stated authors who are ALL aware
of its content and approve its submission.
3. The article has not been published previously.
4. The article is not under consideration for publication elsewhere.
5. No conflict of interest exists, or if such conflict exists, the exact nature

of the conflict must be declared.

6. If accepted, the article will not be published elsewhere in the same
form, in any language, without the written consent of the publisher.

Please accept my best regards

Dr. E. A. Eid
Dr. Aly Nabeih Fouda

Highlights (for review)

Highlights;
1- Melting point of SSC505-ZnO composite solder is slightly increased by 0.89 0C
compared with the plain SSC505 solder.
2- XRD and EDX analysis reflect the presence of SbSn, Cu6Sn5 IMCs
3- EF-SEM images of SSC-ZnO composite solder revealed homogenous uniform
distribution of -Sn grains and fine IMC particles.
4- A detectable improvement in the Young modulus, ultimate tensile strength and
yield strength were observed after addition of 0.5wt% ZnO nano-metric particles.

Manuscript
Click here to view linked References

Influence of ZnO nanoparticles addition on thermal analysis,

microstructure evolution and tensile behavior of
Sn-5.0 wt% Sb-0.5 wt% Cu
Lead-free solder alloy
E. A. Eid a, A. N. Fouda b

(a) Basic Science Department, Higher Technological Institute, 44629 10th of Ramadan City Egypt
(b) Physics department, Faculty of Science, Suez-Canal University, 41522 Ismailia, Egypt

Abstract
Sn-5wt%Sb-0.5wt%Cu (plain SSC505) and Sn-5wt%Sb-0.5wt%Cu-0.5wt% ZnO
(SSC-ZnO) composite solder alloys have been studied. The variation in thermal behavior,
microstructure and tensile characteristics associated with mixing of 0.5wt% ZnO nanometric particles to plain SSC505 solder were investigated. A slight increment in the
melting temperature [Tm= 0.89 oC] was recorded using differential scanning calorimetry
(DSC) after addition of ZnO. X-ray diffraction (XRD) analysis confirmed the existence
of -Sn, SbSn and Cu6Sn5 intermetallic compounds (IMCs) beside some of ZnO planes in
SSC-ZnO composite solder. Field emission scanning electronic microscope (EF-SEM)
investigation of SSC-ZnO composite solder revealed a homogenous uniform distribution,
size refinement of IMCs and -Sn grains. Addition of ZnO nano-metric particles into the
plain SSC505 enhanced the yield stress YS by ~12% and improved the ultimate tensile
strength UTS by ~13%. In addition, adding ZnO nano-metric particles were found to be
effective for reducing ductility by 43% of the plain solder due to the refinement of -Sn
grains within SSC305-ZnO composite solder.

Keywords: Sn-5Sb; solder; composite; lead free; yield stress; ultimate tensile stress

1. Introduction
Sn based alloys is promising for advance electronics components connections as a
lead-free composite solder. The substitution of toxic lead element (Pb) in the electronics
industry is one of the key issues in the current drive towards green ecology. [1] Recently,
high-temperature solders have been widely used in various types of applications like
assembling optoelectronic components, automobile circuit boards, circuit modules for
step soldering, etc. [2]. Eutectic composition of goldtin (Au-20wt% Sn) is the best
solder alloy for most applications in optoelectronic packaging, because of its high creep
resistance, wettability and good reliability. Although, goldtin solders have brittle phases,
more expensive, and has a melting point of 278 C which is unacceptable for some
bonding applications [3, 4]. Certainly, high soldering temperatures could damage the
properties of optical fibers and sensitive optoelectronics such as lasers, light emitting
devices, photodetectors, or waveguide devices [5, 2]. To solve this problem, great efforts
have been made to develop a new generation of solders with a low melting point,
reasonable cost, high dimension stability and supporting solder joints performance With
increasing miniaturization and more input/output terminals [6].
In high temperature applications, Sn5wt% Sb solder is one of great potential
alternative material to push out the AuSn solders and toxic Pb-rich solder alloys [7].
Sn5wt%Sb solder has stable microstructure, good mechanical properties, highly creep
and corrosion resistance and good solderability (contact angle of about 43o) [7, 8]. To
enhance the performance of Tin-Antimony solders, a third or more materials incorporated
as secondary phase with Sn-based matrix is one of the conventional approaches [9, 10].
Micro/nano size metallic, intermetallic, or oxide particles are the most widely used in the
reinforcement of composite materials. Consequently, great numbers of researches focus
their study on the effect of adding reinforcement compound to lead free solder alloys
[11].
literature survey indicate that no attempt has been made to reinforce the binary
Sn-5wt%Sb solder or Sn-5wt% Sb-0.5wt% Cu solders by ZnO nanoparticle. Meanwhile,
a nano-size oxide, intermetallic, or ceramic particles are used to reinforce the composite
solders of Sn-Ag and Sn-Ag-Cu (SAC). Babaghorbani et al. [12] added a different

addition of SnO2 nanopowders to Sn-3.5Ag lead-free solder alloy. Taso et al. [4] mixed a
different addition of TiO2 nano-size particles to Sn3.5Ag0.25Cu solder. Their results
showed profound effects on the thermal characteristics of solder solidification and
reduction of the grain size. Nai et al. reported that the mechanical properties of the carbon
nano-tubes/composite solders improved significantly [11]. However, some efforts have
been made to reinforce Sn-3.5Ag solder with nanopowders of ZrO2, SiC, Cu, Co, Ni, Ag,
and intermetallic particulates (Cu6Sn5, Ni3Sn4) using different

processing methods

[6,12,13,14,15]. Their results exhibit effective influence on the mechanical behavior

measurements indicated significant increases in yield strength, ultimate tensile strength,
and microhardness due to hinder the dislocation motion. However, the ductility decreased
with increasing amounts of nanoparticles additions. Moreover, the secondary phase must
be sufficiently fine, bond well, stable, have a higher flow resistance than the alloy matrix,
un-deformable and resist the fracture of solder joint.
The literature survey revealed that no studies have been reported so far on leadfree SSC505 solder joints containing nano-metric ZnO particles. So, the present work is
devoted for investigating the effect of addition of nano-metric ZnO particles on thermal,
microstructure and tensile properties of Sn5wt% Sb0.5 wt% Cu (SSC505) lead free
solder for trying to improve its microstructure and tensile properties.
2. Experimental
Zinc oxide (ZnO) nanopowders were selected as a reinforcement oxide because of
its capability to form physical bond with metallic matrix. Additionally, the main
advantages of nano-sized ZnO particles are: (i) it has density of (5.67 g/cm3) which is
nearly close to density of Sn-5wt%Sb (7.530 g/cm3) (ii) high hardness when compared to
Sn-5.0Sb matrix (iii) chemical stability and (iv) low cost when compared to other
nanoparticles such as TiO2, Y2O3, SiC and ZrO2. [19]
A lead-free solder, Sn-5.0 wt% Sb-0.5 wt% Cu (plain SSC505) solder alloy, was
prepared by melting together Sn, Sb and Cu ingots of 99.99 % purity. SSC-ZnO
composite solder was prepared by mechanical mixing of 0.5 wt% nano-metric ZnO
particles into plain SSC505 solder with subsequent remelting in a vacuum furnace at 300
o

C for 2 hr to obtain a homogeneous composition. A stainless steel mold was used for

casting, then left to cool slowly to room temperature. The two solder alloys in the form of
rods were cold drawn into a wire of 0.8 mm diameter. A part of each alloy was rolled into
a sheet of 0.5 mm thick for microstructure investigations. Specimens with a gauge length
of 50 mm were pulled for tensile testing. Prior to the tensile testing, all specimens were
heat-treated at a temperature of 150 oC for 2 h. Then, they cooled slowly to room
temperature in order to stabilize the microstructure and remove the residual defects which
produced during the cold drawn process. The densities ) of plain and composite solders
were determined using Archimedes principle. Polished samples taken from various
sections of the solidified rods were weighted in air and when immersed in distilled water
using an electronic balance (A&D HM-202) with an accuracy of 0.0001 g.
For metallographic observations, as-solidified specimens were prepared initially
by mounting in cold epoxy. They were finely polished using 3m and 1m alumina
powder which suspended in distilled water as a lubricant. Final polishing to near mirrorlike surface was achieved using 0.3m diamond paste. The as-polished samples were
chemically etched in a solution of 80% glycerin, 10% nitric acid and 10% acetic acid for
a few seconds.
The etched surfaces of the solder samples were observed in an optical microscope.
The surface morphology of the samples was characterized by using field emission
scanning electron microscopy (FESEM) SU8000 series equipped with energy dispersive
X-ray analysis EDX. X-ray diffractometry (Philips diffractometer (40 kV) with Cu K1
radiation ( = 0.15406 nm) was used for XRD measurements. XRD patterns were
recorded in the 2 range of 20o90 (step size 0.02 per 1 second).
The melting temperature and fusion heating of solders were analyzed using a
differential scanning calorimetry (DSC) Shimadzu DSC-50. DSC measurements were
carried out at heating rate of 5 oC/min and high purity nitrogen gas pass through heating
chamber to avoid oxidation of samples. Tensile testing was performed by straining each
specimen to fracture under a strain rate of 4.710-3 s-1 and testing temperature of 27 oC.

3. Results and Discussion:

3.1 Thermal analysis
For the soldering process, the melting temperature of solders is a crucial
parameter, because it is main factor in deciding the process temperature. The melting
point of the prepared plain and composite solders was accurately determined by DSC
thermograms. Fig. 1(a-b) shows the endothermic peak as a function of temperature of the
prepared solders during the heating rate of 5 oC/min. The melting temperature of the plain
and composite solders is 237.38 and 238.27 oC respectively. This result is agree with
other previous studies on SAC composite solders [4, 20, 21]. The slightly increase in
melting point of the SAC355 composite solder can be attributed to the effect of the nanosized ZnO particles on the rate of solidification. Such particles may serve as retardation
sites for the solidification process of the IMCs [22].
Additionally, The endothermic peak of DSC curve in Fig. 1 is initiated at solidus
temperature Ts and ended at liquidus temperature TL that are estimated by using intersection
point between the horizontal tangent of baseline and the tangent line for each side of
endothermic peak. The features of endothermic peak of synthesized solder alloys are
summarized in Table 1. For plain SSC505 and composite solders, there is a significant
difference between solidus temperatures Ts = 2.11oC) and a negligible difference
between liquidus temperatures TL = 0.13 oC). For any alloy to be worthwhile as a solder
for electronics industry, it must possess certain specific quantities like melting range or pasty
range which is an essential parameter to estimates the time required for finishing the soldering
process. The pasty range of plain and composite solder alloys are 23.88 and 21.90 C
respectively. The results reflect that, the solidus and liquidus temperature of the synthesized
solder alloys are lower than Sn-5wt% Sb binary solder alloy. On the other hand, Sn-5wt% Sb
has the smallest pasty range of 10.0 C and a higher melting temperature of 246 oC that
provides a useful compromise between them. [9, 23]
The calculated values of fusion heat of both solder alloys are tabulated in table 1. The
heat of fusion of plain is higher than composite solder alloy [HSSC505 HSSC-ZnO = 36.56 J/g).
Indeed, The heat of fusion H) plays an important role in packaging technology. Therefore,
SSC-ZnO composite solder alloy is considered as a promising solder for saving energy

and/or the consumed energy for its melting process is lower than Sn-5wt% Sb HSn-5Sb = 140.5 J/g)
by 37% [9].
3.2 Microstructure evolution
3.2.1 XRD analysis
Representative x-ray diffraction of plain solder and composite solders are shown in Fig.
2a-b. The diffraction pattern exhibits sharp peaks, which are attributed to the crystalline
nature of the two samples. The qualitative analysis of the peaks reflects the existence of
the body center tetragonal -Sn-rich phase. The diffraction planes (101), (110), (021), and
(202) at angles of (2 29.3o, 41.9o, 42.3o and 60.5 o) respectively, confirm the existence
of cubic SbSn IMC. Regarding to Fig. 2b, it consists of the same phases which exist in
the plain solder (Fig. 2a). On the other hand, the emergence of (101) and (002) peaks at
angles 32.7 o and 34.3 o of ZnO is an evident of ZnO nanoparticles dispersion within -Sn
matrix. Moreover the disappearance of some ZnO peaks can be attributed to interfere of
its peaks with the peaks of -Sn phases. However, a slow speed scan (0.02 deg/s)
conducted on the plain and composite solders revealed several peaks at angles of (2=
30.36, 42.88o, 53.65, 57.58, 62.33 and 79.71) that corresponding to Cu6Sn5 IMC. The
small peaks of Cu6Sn5 IMC assigned to the low volume fraction of the copper in the
solder matrix. Fig. 3, shows a comparison between diffraction peaks (200) and (101) of
-Sn for plain and composite solders. One can observe that, the diffraction lines are
slightly shifted towards lower angles, indicating a refinement of -Sn grain size with
addition of ZnO nano-metric particles [24, 25].
It is well known that, the broadening of XRD peaks of an alloy is caused not only by the
small grain size but also by the lattice micro-deformations of the alloy [15]. The
crystallite size d and an approximate upper limit of the lattice strain can be evaluated by
XRD peaks analysis according to the Williamson-Hall formula [25]:

cos

K
2 sin
d

(1)

where is the peak width at half the maximum intensity (FWHM) in radian of the main
peak, is the Bragg angle, K is the Scherrer constant (0.9), is average of lattice strain ,
and is the X-ray wavelength (Cu = 0.154056 nm).

When cos was plotted against sin using main peaks of -Sn, a straight line is
obtained with the slope of 2 and the intercept as (0.9/d). Results of linear fitting of
extracting data summarized in table 2. The crystallite size of Sn-based supersaturated
solid solution was measured to be 116 and 99 nm for the plain and composite solders,
respectively. From table 2, one observed that the average of lattice strain of -Sn phase
for SSC-ZnO composite solder was higher than plain solder. The lattice strains observed
in the solid-solution phases during solidification are caused not only by defect formation
but also by another factor; this strain was originally introduced during sample
preparation, particularly in crushing of the sample [26]. The peaks in the X-ray
diffraction (XRD) patterns for composite solder broadened. This broadening was
supposed to be due to lattice strain. Moreover lattice strain is introduced upon phase
transition from coarsen -Sn phase to refinement phase. The anisotropic strain in the
diffraction peaks has the same orientation as the Burgers dislocation vectors [24]. That
indicating the strain is accompanied by density dislocations, which is closely related to
defect formation.
3. 2. 2 Metallographic Analysis
Results of microstructural characteristics of the plain and composite solders are discussed
in terms of: (i) grain morphology, size, and homogenous distribution, (ii) the presence,
distribution and morphology of the second phase particles, and (iii) percentage of
porosity, cracks and voids. Fig. 4, shows two optical images (OM) with same powers of
magnification for the as-cast plain and composite solders that solidified at cooling rate of
2 oC/min. Results revealed the plain solder composed of larger non-equiaxed grains, nonuniform solidification microstructure; the large dark islands are rich-Sn grains with grain
size in the range of 100-140 m. The bright region between Sn grains actually consists of
mixture of lamellar phases of Sn matrix phase (dark phase) and the circular bright dot
phase termed as SnSb IMC. Moreover, the finer rich-Sn grains within composite solder
reveal near-equiaxed grains with average grain size in the range of

90-50 m

approximately homogenous distribution and narrower dendrites are shown in Fig. 4b.
The decrement of average grain size of -Sn phase with addition of 0.5 wt% Zinc nanometric particles can be attributed to its pinning action on grain boundaries and by the

second phases resulting in limited grain growth [18]. In Fig. 4b, the -Sn phase is not
only composed of pure Sn crystals but rather contain several of tiny intermetallic particles
that scattered throughout Sn matrix. Furthermore, with higher magnification of field
emission scanning electronic microscope (FE-SEM), the precipitated particles like as
platelets or scallop morphology of the Cu6Sn5 IMC are observed in both solders (see Fig 5a-b).
The precipitation of IMCs within -Sn matrix is confirmed by utilizing energy
dispersion X-ray (EDX) analysis, the eutectic areas were found to contain Zn, O, Cu, Sb
and Sn elements in composite solder. Thus, it can be concluded that the network eutectic
areas are Cu6Sn5 and SbSn besides the ZnO particles as shown in Figs. 6a-c. Stichometric
analysis of EDX data implies the existence of Sn, Sb and Cu atoms and termed IMCs
according to the atomic ratio of each element in compound [see table 3]. An identified
reduction in size of SbSn, Cu6Sn5 IMCs was confirmed by FE-SEM images (see Fig.5ab). This was assigned to ZnO nanoparticles which incorporated into the solder matrix.
According to the adsorption theory, increasing the adsorption of elements could decrease
the surface energy and/or decrease the growth of IMCs size [14]. For the composite
solder, the micro-size of SbSn and Cu6Sn5 IMCs are larger than the size of the ZnO nanometric particles. Therefore, the incorporation of active surface ZnO nano-metric particles
refines the size of IMCs. Previously, similar behavior has been reported [20, 22].
The Curve of EDX analyses of a selected area (+) in Fig. 6b shows that, the
Cu6Sn5 IMC contain 7.01 at.% of Sb element [see table 3]. The existence of antimony
atoms inside the Cu6Sn5 grain confirms that tin-antimony intermetallic compound might
be the nucleating agent acting as a heterogeneous nucleation of Cu6Sn5 grains. The
proposed mechanism for the effect of Sb on IMC formation can be summarized as
follows; because Sb has higher affinity to the constituent element of Sn in SnCuSb
ternary system, it will reduce the activity of Sn at the Sn-Cu interface by forming SnSb
compound, resulting in a decreased driving force for CuSn IMC formation [27]. SnSb
particles may be initially formed and finely dispersed in the molten solder, and then some
of them precipitate and become the heterogeneous nucleation sites of Cu6Sn5 IMC.
According to the theory of heterogeneous nucleation, the Cu6Sn5 phase prefers to
nucleate on the SnSb surface in order to reduce the thermodynamic barrier [28]. The
increase in nucleation probability of Cu6Sn5 grains consequently lends to the refinement

of the grains. As a result, the small and uniform grains obtained in the composite solder
slow down the ripening rate, and the refinement effect is achieved
3.3 Density measurement
The results of density measurements were conducted on the solidified plain and
composite solders. In Table 4, all the density values were very close which is predicted
because of the slight difference in density between Sn and ZnO. The porosity
measurement was theoretically calculated [12, 24]. The value of porosity implied that the
higher percentage of pores exists in the case of SSC-ZnO composite solder.
3.4 Strengthening effect
Fig. 7 shows the typical tensile stressstrain curves of plain and composite solders
stretched with constant strain rate of 7.410-3 s-1 and performed 27oC. The stressstrain
obtained curves exhibited plateau shaped with steady stable flow stress of the two solder
alloys. It was found to be strongly dependent on alloy composition of the tested material.
Furthermore, steady state flow of composite solder was higher than plain solder by ~12%.
This observation can be explained as; during plastic deformation the solder alloy suffers
from simultaneous work hardening and dynamic recovery [17]. They have contrary
influences on the mechanical deformation of the alloy. Hence the steady stable stresses
seem to be represented equal combination effects for those. Additionally, existences of
the ZnO nanoparticles must increase dislocation densities because of their restrict effect
for the motion of dislocation, besides the dispersion hardening mechanism of the IMCs.
Therefore the dislocations have much less freedom that can't pass through climb and
cross slip planes that lead to increase the flow stresses [20].
The average values of Young modulus E, ultimate tensile strength UTS, yield
stress YS, fracture stress f and ductility of the synthesized solder alloys were tabulated
in Table 5. Addition of 0.5 wt% ZnO nanopowders was found to have a significant effect
on the tensile parameters. Detectable increments in E by 52%, UTS by 11% and in YS by
13% were recorded. However, the ductility of SSC-ZnO composite solder was less than
plain solder by 43%. Improvement in the tensile parameters was achieved because of
presence of ZnO nanopowders as reinforcement agent. The nano-sized particles are

dispersed uniformly and homogeneously distributed in Sn matrix which provide high

barrier by impeding grain boundary sliding and dislocation movement.
The reinforcement nanoparticles play two different roles. They may strengthen the
alloy matrix and enhance the formation of large dislocation pile-ups at grain boundaries.
Simultaneously, the higher friction of nanoparticles generates microcracks nucleation at
the interface between Sn matrix and IMCs which speed up the failure process. [29, 30]
So, ductility decreased because of a large amount of microporosity throughout grain
boundaries and crack nucleation sites in the form of hard and brittle ZnO nanopowders.
[20, 24, 31]
Eventually, the influence of the nano-metric size particles can be summarized in:
(i) pinning grain boundaries and thus impeding sliding of the grain boundaries, (ii) the
increase of dislocation densities and obstacles to restrict the motion of dislocation and
(iii) the dispersion hardening mechanism of the IMCs and ZnO nanopowders. [30, 32]

4. Conclusion
ZnO nanoparticles dissolve and react with the molten SSC505 solder at 600 oC during the
fabrication of SSC-ZnO composite solder. Thermal behavior, microstructure and
mechanical characteristics were discussed. The melting point of SSC505 solder is slightly
increased after the addition of ZnO nanoparticles. X-ray diffraction analysis of SSC-ZnO
confirms the existence of SbSn, Cu6Sn5 IMCs and ZnO. The microstructure observations
revealed finer IMCs due to active surface area of ZnO nanoparticles that supports the
strong adsorption effect. According to the tensile measurements, an improvement in UTS
and YS were established. However, the ductility of SSC-ZnO composite solder was
decreased. The variation in tensile properties is attributed to ZnO pinning effect which
obstructed dislocations and migration of grain boundaries.

10

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12

Figure caption
Fig. 1. DSC curves of (a) SSC505 and (b) SSC-ZnO composite solder alloys.
Fig. 2. XRD profiles of (a) SSC505 solder and (b) SSC-ZnO composite solder alloys
Fig. 3. Comparison between diffraction peaks of (200) and (101) of -Sn for plain and
composite solders.
Fig.4. Optical images showing the grains of (a) SSC505 solder and (b) SSC-ZnO
composite solder alloys
Fig. 5. FE-SEM micrographs showing the grains of (a) SSC505 solder and (b) SSC-ZnO
composite solder alloys
Fig. 6. High-magnification FE-SEM micrographs with corresponding EDX of
intermetallic compound of (a) SbSn (b) Cu6Sn5 (c) eutectic region in SSC-ZnO
composite solder
Fig. 7. StressStrain curves showing the effect of adding 0.5 wt% ZnO nanoparticles to
SSC505 plain solder alloy

13

Highlights;
1- Melting point of SSC505-ZnO composite solder is slightly increased by 0.89 0C
compared with the plain SSC505 solder.
2- XRD and EDX analysis reflect the presence of SbSn, Cu6Sn5 IMCs
3- EF-SEM images of SSC-ZnO composite solder revealed homogenous uniform
distribution of -Sn grains and fine IMC particles.
4- A detectable improvement in the Young modulus, ultimate tensile strength and
yield strength were observed after addition of 0.5wt% ZnO nano-metric particles.

14

Table

Table1. Comparison of melting temperatures(T m), solidus temperature (T s),

liquidus temperature (T L), pasty range T) and heat of fusion ( H) for various
solder alloys
H

Reference

9.0

(kJ/kg)
141

El-Dally[9]

223.45 247.33

23.88

125.52

This study

225.56 247.46

21.90

88.96

This study

Material

Tm oC

Ts oC

TL oC

Sn-5Sb

246

240

249

SSC505

237.38

SSC-ZnO

238.27

T= T L -T S
o

Table 2. The average crystallite size (d) and lattice strain () for plain SSC505 solder,
SSC-ZnO composite solder and SbSn, Cu6Sn5 IMCs
-Sn (Matrix)
SSC505
2

(R = 0.042)
d(nm)

SSC-ZnO
2

(R = 0.061)

d(nm)

116

10
R2

SbSn (IMC)

(nm)

99

55

SSC505
2

(R = 0.3337)

SSC-ZnO
2

(R = 0.6108)

d (nm) d(nm)

693

300

Cu 6 Sn 5 (IMC)

116

565

SSC505
2

(R = 0.4255)

SSC-ZnO
(R 2 = 0.7218)

d(nm) d (nm)
754

346

205

588

Table 3. Energy dispersive R-Ray (EDX) analysis

Composition
Phase
Sn

Zone

Sb

Cu

Zn

identification

O2

Wt%

At%

Wt%

At%

Wt%

At%

Wt%

At%

At%

Wt%

+ (See fig. 6a)

65.43

66.01

34.57

33.99

-------

-------

------

-------

-------

-------

SnSb

+ (See fig. 6b)

72.76

61.61

3.68

7.01

23.56

27.37

-------

-------

-------

-------

Cu6Sn5

+ (See fig. 6c)

83.59

40.53

8.75

6.61

2.06

2.98

3.51

4.94

3.60

13.08

Eutectic

Table 4. Results of density and porosity

Material

Density (g/cm3)a

Porosity (g/cm3)

Reference

Sn-5wt% Sb
SSC505
SSC-ZnO

7.5260.005
7.5530.006
7.5330.006

0.50
0.750.17
0.870.20

M. El-Bahay [23]
This study
This study

Table 5. Tensile Results at room temperature and strain rate of 4.7 x 10-3 s-1
Material
Sn-5wt% Sb*

E (GPa) UTS (MPa) YS (MPa) f (MPa)

f %

Reference

44.5

35.50

25.70

---

22

El-daly [9]

SSC505

43.4

77.48

64.68

42.59

17.0

This study

SSC-ZnO

60.3

86.35

73.10

72.80

9.7

This study

Figure

HEAT FLOW (mW)

SSC-ZnO

238.27 C
SSC505

237.38 C

100

200
300
400
TEMPERATURE (C)

500

Fig.1 Eid et.al

30

40

2 (degree)

60

70
SnSb(104)

SbSn(113)
Cu 6Sn 5

Sn(301)

Sn(112)

Sn(211)

Sn(220)

Sn(101)

Sn(200)

Sn(312)

Sn(321)

Cu 6Sn 5

Sn(420)
Sn(411)

Cu 6Sn 5
Sn(400)

SbSn(202)

50
Cu 6Sn 5

SbSn(003)
Cu 6Sn 5

SbSn(110)
Cu 6Sn 5

SbSn(010)
Cu 6Sn 5

INTENSITY (arb.units)

ZnO(101)
ZnO(002)

INTENSITY (arb.units)

b) SSC-ZnO

a)SSC505

80

Fig.2 Eid et al.

SSC-ZnO

Intensity (arb.unt)

SSC505

30.2 30.4 30.6 30.8

31

31.2 31.4 31.6 31.8

32

32.2 32.4 32.6

2 (degree)

Fig.3 Eid et al.

-Sn

-Sn

Fig.4, Eid et al.

Cu6Sn5
SbSn

Cu6Sn5
SbSn

Fig.5, Eid et al.

(a)

SbSn

Sn
Sn

+
Sn Sb

Sb

Sn Sb

Sn

10

Energy (keV)

Sn

(b)

Cu6Sn5

Sn
+

A
Cu

Sb Sn
Sn

4
5
6
Energy (keV)

Cu
Cu

10

Sn

(C)

+
Sn
Sb
Sn

O2
Cu

Zn
Cu

Sn

4
5
6
Energy (keV)

10

Fig.6a-c, Eid et al.

6

100
SSC-ZnO
SSC505

STRESS (MPa)

80
60
40
20
0
0.00

Room temperature

-4 -1
=4.710 s

0.05

0.10

0.15

0.20

STRAIN

Fig.7, Eid et al.