Journal of ELECTRONIC MATERIALS, Vol. 42, No.

12, 2013

DOI: 10.1007/s11664-013-2748-z
2013 TMS

Thermal Conductivity Variation with Temperature for Lead-Free

Ternary Eutectic Solders
Z,1 ESRA O
ZTU
Z,1
RK,2 U
MIT BAYRAM,3 SEZEN AKSO
NAMIK AKSO
1
4

SELC
UK KERVAN, AHMET ULGEN, and NECMETTIN MARASLI5,6
1.Department of Physics, Faculty of Arts and Sciences, Nevsehir University, 50300 Nevsehir,
Turkey. 2.Department of Physics, Faculty of Arts and Sciences, Kocaeli University, 41380 Izmit,
Kocaeli, Turkey. 3.Department of Physics, Faculty of Sciences, Erciyes University, 38039
Kayseri, Turkey. 4.Department of Chemistry, Faculty of Sciences, Erciyes University, 38039
Kayseri, Turkey. 5.Department of Metallurgical and Materials Engineering, Faculty of Chemical and Metallurgical Engineering, Yldz Technical University, 34210 Davutpasa, Istanbul,
Turkey. 6.e-mail: nmarasli@yildiz.edu.tr

The variations of the thermal conductivity with temperature for the lead-free
ternary eutectic solders Bi-42.73 wt.%Sn-1.03 wt.%Ag (Bi-Sn-Ag), Sn-3.5
wt.%Ag-0.9 wt.%Cu (Sn-Ag-Cu), Sn-6 wt.%Sb-5 wt.%Ag (Sn-Sb-Ag), Sn-42.8
wt.%Bi-0.04 wt.%Cu (Sn-Bi-Cu), and In-48.4 wt.%Sn-2.31 wt.%Ag (In-Sn-Ag)
were measured using a linear heat flow apparatus. It was observed that the
thermal conductivities of solid phases for the Bi-Sn-Ag, Sn-Ag-Cu, Sn-Sb-Ag,
Sn-Bi-Cu, and In-Sn-Ag solders decrease linearly with increasing temperature. The thermal conductivities of the Bi-Sn-Ag, Sn-Ag-Cu, Sn-Sb-Ag, Sn-BiCu, and In-Sn-Ag solders at their melting temperature were obtained
as 17.89 1.6 W/K-m, 49.89 4.5 W/K-m, 41.96 3.8 W/K-m, 20.03 1.8
W/K-m, and 70.21 6.3 W/K-m, respectively. The thermal temperature
coefficients for the Bi-Sn-Ag, Sn-Ag-Cu, Sn-Sb-Ag, Sn-Bi-Cu, and In-Sn-Ag
solders were also determined to be 2.894 9 103 K1, 0.907 9 103 K1,
1.246 9 103 K1, 2.638 9 103 K1, and 1.250 9 103 K1, respectively,
from plots of thermal conductivity versus temperature.
Key words: Metals, thermal conductivity, thermal temperature coefficient,
lead-free solders

INTRODUCTION
The thermal conductivity (K) is one of the main
fundamental properties of materials, along with the
density, melting point, entropy, enthalpy, resistance, and crystal structure parameters. Although
values of K have been obtained for pure metallic
materials both theoretically and experimentally,
there is insufficient information and data available
about the thermal conductivity of metallic alloys. As
for pure materials, the values of K for alloys change
with temperature, but they also change with the
alloy composition.

(Received November 27, 2012; accepted August 17, 2013;

published online September 25, 2013)

Heat in solids is conducted by various carriers:

electrons, lattice waves (or phonons), magnetic
excitations, and, in some cases, electromagnetic
radiation. The total thermal conductivity is additively composed of the contributions from each carrier type.1
Many attempts have been made to determine the
thermal conductivity values of solid and liquid
phases of various materials by using different
methods. One of the common techniques for measuring the thermal conductivity of solids is the
longitudinal heat flow method. In this method, the
experimental arrangement is designed such that
the heat flow is only in the axial direction of a rod
specimen. Under steady-state conditions and
assuming no radial heat loss or gain, the thermal
conductivity is determined by the following expression
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from the one-dimensional FourierBiot heat conduction

equation:2,3
K

Q DX
;
A DT

(1)

where K is the thermal conductivity of the solid, Q is

the rate of heat flow through or input power flow to
the specimen, A is the cross-sectional area of the
specimen, DX X2  X1 is the distance between the
points of measurement of the temperatures T1 and
T2, and DT T2  T1 is the temperature difference
between points X2 and X1.
To determine the thermal conductivity from
Eq. 1, it is necessary to measure the rate of heat
flow into and/or out of the rod, the cross-sectional
area, the temperatures at at least two points along
the rod, and the distance between the points of
temperature measurement. Measurements of thermal conductivity at higher temperatures have been
made for different kinds of materials.416
Solders are the basis of many engineering materials.17 This has led to extensive theoretical and
experimental study of the relationships among their
microstructure, physical properties, and solidification processing parameters.1821 Solder is preferred
to have eutectic composition. The eutectic phase
diagrams of Bi-Sn-Ag, Sn-Ag-Cu, Sn-Sb-Ag, Sn-BiCu, and In-Sn-Ag solders have been evaluated.22
The intensive interest in these solders is attributed
to their low cost and unique material properties

including their high superplastic properties, low

melting temperature, wettability, and good thermal
and electrical conductivities.21,2326 The thermal
conductivity of Bi-Sn-Ag, Sn-Ag-Cu, Sn-Sb-Ag,
Sn-Bi-Cu, and In-Sn-Ag solders is well known at
room temperature, but few studies have been carried
out on the temperature dependence of the thermal
and electrical conductivities of these alloys.2731
Recently, we embarked on research pertaining to
the measurement of the temperature dependence of
the thermal conductivity of multicomponent metallic
alloys. Therefore, attention is given to the thermal
and electrical conductivities at high temperature,
which are required as input data for heat transfer
and solidification simulations. Thus, the purpose of
the present work is to measure the temperature
dependence of the thermal conductivity for some
Bi-Sn-Ag, Sn-Ag-Cu, Sn-Sb-Ag, Sn-Bi-Cu, and
In-Sn-Ag solders.
EXPERIMENTAL PROCEDURES
Experimental Apparatus
A linear heat flow apparatus was designed to
routinely measure thermal conductivity variation
with temperature for solid materials.32 The linear
heat flow apparatus consists of a hot stage, a cold
stage, and a sample holder as shown in Fig. 1;
details of the linear heat flow apparatus are given in
Ref. 32.

60 mm
Hot copper plate

12 mm

45 mm
8 mm
Cold copper plate

10 mm

8 mm
10 mm

3 mm

Measurements thermocouples

3 mm
4 mm
10 mm

Positions of measurements thermocouples into specimen

Fig. 1. Schematic illustration of the copper plates and thermocouple positions in the specimen.

Thermal Conductivity Variation with Temperature for Lead-Free Ternary Eutectic Solders

To obtain a linear temperature gradient in the

specimen, the distance between the hot stage and
cold stage was typically kept at 102 m. The hot and
cold stages were placed at a separation of 102 m on
an insulating plate, and the insulating plate was
then fixed vertically. The hot stage was placed at the
top of the insulating plate while the cold stage was
placed at the bottom of the insulating plate to prevent convective effects on the heat conduction in the
specimen and to obtain a constant linear temperature gradient in the specimen, as shown in Fig. 1.
Specimen Preparation and Processing
Solder is a low-melting eutectic alloy. Eutectic tinlead (Sn-Pb) has a melting point of 456 K. The
ability to form a metallic bond with Cu at such a low
temperature is the key reason why Sn-Pb solder
joints have been used worldwide for so long. On the
other hand, the typical temperature of solder joint
applications is either near room temperature or the
device working temperature around 373 K.
A thin-walled graphite crucible (1.2 9 102 m
outer diameter, 0.8 9 102 m inner diameter, 5.0 9
102 m length) was made by drilling out a graphite
rod of 1.2 9 102 m diameter and 0.25 mm length.
A hole of 1.2 9 103 m diameter was drilled at the
bottom of crucible for an alumina tube for the
thermocouples, as shown in Fig. 1.
The Bi-Sn-Ag, Sn-Ag-Cu, Sn-Sb-Ag, Sn-Bi-Cu,
and In-Sn-Ag solders were separately melted in a
vacuum furnace by using Ag, Bi, Cu, In, Sn, and Sb
metals. The purity of the metals used was 99.99%.
After stirring, the molten alloy was poured into a
graphite crucible, held in a specially constructed
casting furnace at approximately 50 K above the
melting point of the alloy. The molten metal was
then directionally solidified from bottom to top to
ensure that the crucible was completely filled.
The solidified specimen was removed from the
graphite crucible and cut into lengths of typically
3.0 9 102 m. The 3.0 9 102 m length of specimen
was placed into the linear heat flow apparatus. Both
ends of the specimen were inserted into holes in the
hot and cold stages. Thus, a space of 1.0 9 102 m
between the hot and cold stages was adjusted to
obtain a linear temperature gradient in the specimen and to prevent radial heat loss from the rod.
The temperatures at different parts of the specimen
were measured with three mineral-insulated, metalsheathed, 0.25 9 103-m-diameter type K thermocouples, fixed within the specimen with spacing of
2.0 9 103 m to 3.0 9 103 m using silicone elastomer glue as shown in Fig. 1. Before inserting the
thermocouples into the specimen, a photograph of
the thermocouple positions was taken to measure
the distance between them (DX) using an optical
microscope. All thermocouples were then inserted
together into an insulating alumina tube, and the
ends of the thermocouples were then connected to
the measurement unit, which consisted of a data
logger and computer.

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The specimen was heated from one side by using

the hot stage in steps of 20 K up to 10 K below the
melting temperature of the material while the other
side of the specimen was kept cool by using the cold
stage to obtain a linear temperature gradient. As
mentioned above, the temperature of the hot stage
was controlled to accuracy of 0.01 K using a Eurotherm type 2604 controller while the temperature of
the cold stage was kept constant to accuracy of
0.01 K using a PolyScience digital model 9102
heating/refrigerating circulating bath. The specimen
was kept at steady-state condition for at least 2 h for
each temperature.
To determine the thermal conductivity from
Eq. 1, it is necessary to measure the rate of heat
flow into the rod, the cross-sectional area, the temperatures at at least two points along the rod, and
the distance between the points of temperature
measurement. The radius of the rod specimen was
measured by using an optical microscope to determine the cross-sectional area (pr2 ). The temperatures of the stationary thermocouples were recorded
using a Pico TC-08 data logger during the heating
process, and the difference between the temperatures of two thermocouples, DT, was taken from the
data logger records. The distance between two
thermocouples was measured from the photograph
of the thermocouple positions. The heat flow rate
into the specimen (Q) for each steady-state condition was determined by measuring the input power
applied to the experimental system (heater) without the specimen (QWOS) and with the specimen
(QWS ).32
After all the desired temperature measurements
had been completed during the heating process, the
cooling procedure was started in the same steps
down to room temperature to see if there was any
hysteresis.
The sample was then removed from the linear
heat flow apparatus, and the longitudinal section of
the specimen was examined for porosity, cracks, and
casting defects to exclude error in the measurements that would be caused by these effects.
Variations of the thermal conductivity with temperature for the Bi-Sn-Ag, Sn-Ag-Cu, Sn-Sb-Ag,
Sn-Bi-Cu, and In-Sn-Ag alloys were determined
from Eq. 1 using the corresponding measured values of A, Q = QWS  QWOS, DT, and DX (Table I).
Experimental Error Analysis for the Thermal
Conductivity Measurement
The estimated experimental error in the measurement of K is the sum of the fractional uncertainties of the measurements of heat flow rate,
temperature difference, cross-sectional area of
specimen, and thermocouple positions, which can be
expressed as
    

   
DKs  DQ DT   DA DX 
    

 
 K   Q   DT   A   X :
s

(2)

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Table I. Typical experimental data to determine the heat flow rate into a Sn-6 wt.%Sb-5 wt.%Ag rod at
different temperatures
Temperature (K)
313
353
393
433
473
513

IWOS (A)

VWOS (V)

QWOS (W)

IWS (A)

VWS (V)

QWS (W)

Q = QWS 2 QWOS (W)

0.77
1.39
1.95
2.35
2.88
3.28

7.59
13.04
19.34
23.50
29.62
33.35

5.87
18.12
37.71
55.23
85.32
109.46

0.95
1.57
2.29
2.68
3.25
3.61

9.0
14.65
19.90
26.80
32.15
36.25

8.55
23.00
45.20
65.00
99.00
124.50

2.68
4.89
7.49
9.78
13.68
15.04

IWOS current passing through the heater without the specimen, VWOS potential drop at the ends of the heater without the specimen, QWOS
input power applied to the heater without the specimen, Q heat flow rate through the specimen, IWS current passing through the heater
with the specimen, VWS potential drop at the ends of the heater with the specimen, QWS input power applied to the heater with the
specimen.

Typical data for measurements of heat flow rates

are given in Table II. The estimated experimental
error in the measurement of K in the present work
is about 9%.32
Determination of the Thermal Temperature
Coefficient
For a given composition, the dependence of the
thermal conductivity of the solid phase on temperature is linear, and the thermal temperature coefficient, aTTC, is expressed as33,34
aTTC

K  K0
1 DK
;

K0 T  T0 K0 DT

(3)

where K is the thermal conductivity at temperature

T, K0 is the thermal conductivity at room temperature, T0 = 300 K, and aTTC is the thermal temperature coefficient. This means that the thermal
temperature coefficient, aTTC, can be obtained from
a plot of thermal conductivity versus temperature.
RESULTS AND DISCUSSION
Dependence of Thermal Conductivity
on Temperature for Lead-Free Ternary Solders
The eutectic melting temperatures of the Bi-SnAg, Sn-Ag-Cu, Sn-Sb-Ag, Sn-Bi-Cu, and In-Sn-Ag
ternary systems are about 411.4 K, 490.2 K,
507.8 K, 411.8 K, and 386 K, respectively.22 In the
present work, the variations of the thermal conductivity with temperature for the Bi-Sn-Ag, Sn-AgCu, Sn-Sb-Ag, Sn-Bi-Cu, and In-Sn-Ag solders were
measured by using the linear heat flow apparatus.
Experimental results are given in Table II and
plotted in Figs. 26. As can be seen from Figs. 26,
the values of K decrease with increasing temperature. Because of phononphonon collisions at high
temperatures, the thermal conductivity decreases
with increasing temperature. This indicates that
the mean free path of atomic displacements is
shorter at higher temperatures. Also, the mean
free path is proportional to the thermal conductivity,

so the thermal conductivity of materials should

decrease at high temperatures.
Comparison of the values of K for Bi-Sn-Ag,
Sn-Ag-Cu, Sn-Sb-Ag, Sn-Bi-Cu, and In-Sn-Ag as
measured in the present work with the values of K
for Sn, Ag, Bi, Cu, In, and Sb as measured in previous works2732 is also given in Figs. 26.
According to the phase diagrams of the Sn-Ag,
Sn-Bi, and Bi-Ag binary systems, the solid solubility
of Ag in Sn and Bi solids is negligible at the eutectic
melting temperatures of 494 K and 544 K, the solid
solubility of Bi in Sn and Ag solids is 20 wt.% and
2 wt.% at the eutectic melting temperatures of 412 K
and 535 K, and the solid solubility of Sn in Ag and Bi
solids is 20 wt.% and negligible at the eutectic melting temperatures of 494 K and 467 K, respectively.39
Typical optical images of microstructures for
the Bi-Sn-Ag, Sn-Ag-Cu, Sn-Sb-Ag, Sn-Bi-Cu, and
In-Sn-Ag alloys are shown in Fig. 7. From the
micrograph of Bi-Sn-Ag shown in Fig. 7a, it can be
seen that the alloy consists of solid Sn solution (dark
color) and solid Bi (white color) phases below its
eutectic melting temperature. The volume fraction
of solid Bi phase in the Bi-Sn-Ag alloy is higher than
other solid phases below its eutectic melting temperature. Thus, the plot of thermal conductivity
variation with temperature for the Bi-Sn-Ag alloy
determined in the present work lies between the
lines of the thermal conductivity variations with
temperature for Sn33 and Bi33 and is close to the line
of thermal conductivity variation with temperature
for Bi,33 as shown in Fig. 2.
The solid solubility of Ag in Sn and In solids is
negligible at the eutectic melting temperatures of
494 K and 417 K, the solid solubility of In in Sn and
Ag solids is 27.0 wt.% and 22.1 wt.% at the eutectic
melting temperatures of 393 K and 417 K, and the
solid solubility of Sn in Ag and In solids is 20 wt.%
and 44.8 wt.% at the eutectic melting temperatures
of 494 K and 393 K, respectively.39 As can be seen
from Fig. 7b, the In-Sn-Ag alloy consists of solid Sn
solution (dark color) and solid In solution (white
color) phases below its eutectic melting tempera-

0.1
0.1
0.11
0.11
0.21

1.04
1.61
2.18
2.73
3.16

0.02
0.1
0.1
0.1
0.2

59.41
57.57
57.42
56.66
55.64
53.58
52.42
51.96
50.52

2.59
4.17
5.86
7.56
9.23

0.1
0.1
0.1
0.2
0.2

DT (K)

0.03
0.04
0.1
0.1
0.1
0.2
0.2
0.2
0.3

DT (K)
1.42
1.89
2.72
3.69
4.98
6.71
8.22
9.44
10.88

0.1
0.1
0.1
0.2
0.2

Q (W)

5.3
5.1
5.1
5.1
5.0
4.8
4.7
4.6
4.5

1.20
1.82
2.43
2.95
3.29

K (W/K-m)

Sn-42.8 wt.%Bi-0.04 wt.%Cu

Q (W)

0.1
0.1
0.1
0.1
0.2
0.3
0.3
0.4
0.4

55.01
54.91
53.55
52.16
51.50
49.36
48.16
46.02
45.65
42.26

5.0
5.0
4.8
4.7
4.6
4.4
4.3
4.1
4.1
3.8

K (W/K-m)

1.41
1.83
2.62
3.50
4.64
6.02
7.22
8.21
9.20

Q (W)

Sn-3.5 wt.%Ag-0.9 wt.%Cu

K thermal conductivity of specimen (W/K-m), DT temperature difference along specimen (K), Q heat flow rate into specimen (W).

2.4
2.3
2.2
2.1
1.9

27.66
26.00
24.83
23.31
21.26

313
333
353
373
393
413
433
453
473
493

K (W/K-m)

2.48
3.86
5.31
6.82
8.38

DT (K)

Temperature (K)

2.2
2.2
2.2
2.1
2.0

25.03
24.97
24.58
23.92
22.54

313
333
353
373
393
413
433
453
473
493

K (W/K-m)

Temperature (K)

Bi-42.73 wt.%Sn-1.03 wt.%Ag

6.9
6.7
6.7
6.4

3.40
5.19
7.08
9.06

0.1
0.1
0.2
0.2

DT (K)

2.91
3.92
5.45
7.07
8.68
10.35
12.12
15.47
17.90
20.00

0.1
0.1
0.1
0.1
0.2
0.3
0.3
0.4
0.4
0.5

DT (K)

Sn-6 wt.%Sb-5 wt.%Ag

77.66
75.31
74.72
71.29

K (W/K-m)

0.2
0.3
0.4
0.5

2.68
3.60
4.89
6.17
7.49
8.56
9.78
11.92
13.68
14.15

0.1
0.2
0.2
0.3
0.4
0.4
0.5
0.6
0.7
0.7

Q (W)

4.42
6.55
8.86
10.81

Q (W)

In-48.4 wt.%Sn-2.31 wt.%Ag

Table II. Experimental data for measurements of the thermal conductivity variation with temperature for lead-free ternary eutectic solders

Thermal Conductivity Variation with Temperature for Lead-Free Ternary Eutectic Solders
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500

Thermal Conductivity (W/Km)

Thermal Conductivity (W/Km)

500

400
Bi- 42.73 wt. % Sn-1.03 wt. %Ag
Pure Bi
Pure Ag
Pure Sn

300

200

100

400
Sn- 42.8 wt. % Bi-0.04 wt. %Cu

300

Pure Bi
Pure Cu

200

Pure Sn

100

0
280

320

360

400

280

440

320

Temperature (K)

Fig. 2. Thermal conductivity versus temperature for Ag, Bi, Sn, and
Bi-Sn-Ag.

In- 48.4 wt. % Sn-2.31 wt. % Ag

Pure In
Pure Ag
Pure Sn

200

100

400
Sn- 6 wt. % Sb-5 wt. %Ag

300

Pure Sb
Pure Ag

200

Pure Sn

100

0
280

320

360

400

440

Temperature (K)

500

400

300

200

Sn- 3.5 wt. % Ag-0.9 wt. % Cu

Pure Cu
Pure Ag
Pure Sn

100

0
280

320

360

400

440

280

320

360

400

440

480

520

Temperature (K)

Fig. 3. Thermal conductivity versus temperature for Ag, In, Sn, and
In-Sn-Ag.

Thermal Conductivity (W/Km)

440

500

Thermal Conductivity (W/Km)

Thermal Conductivity (W/Km)

300

400

Fig. 5. Thermal conductivity versus temperature for Bi, Cu, Sn, and
Sn-Bi-Cu.

500

400

360

Temperature (K)

480

520

Temperature (K)
Fig. 4. Thermal conductivity versus temperature for Ag, Cu, Sn, and
Sn-Ag-Cu.

Fig. 6. Thermal conductivity versus temperature for Ag, Sb, Sn, and
Sn-Sb-Ag.

ture. The volume fraction of the solid In solution

phase is higher than the solid Sn solution phase
below the eutectic melting temperature in the InSn-Ag alloy. Thus, the line of thermal conductivity
variation with temperature for the In-Sn-Ag alloy
determined in the present work lies between the
lines of thermal conductivity variations with temperature for Sn33 and In33 and is close to the line of
thermal conductivity variation with temperature for
In,33 as shown in Fig. 3.
The solid solubility of Ag in Sn and Cu solids is
negligible and 22.1 wt.% at the eutectic melting
temperatures of 494 K and 1052 K, the solid solubility of Cu in Sn and Ag solids is negligible and
8.8 wt.% at the eutectic melting temperatures of
500 K and 1052 K, and the solid solubility of Sn in
Ag and Cu solids is 20 wt.% and 15.8 wt.% at the
eutectic melting temperatures of 494 K and 1069 K,

Thermal Conductivity Variation with Temperature for Lead-Free Ternary Eutectic Solders

(a)

3579

(b)
Sn rich solution
phase

Bi phase

Sn rich
solution phase
30 m

30 m

(c)

(d)

Sn rich
solution
phase

In rich solution
phase

Bi phase
Sn rich solution
phase

Ag3Sn
phase
Cu6Sn5
phase

30 m

(e)

30 m

Ag3Sn
phase
Sn3Sb2 phase
Sn rich solution
phase

30 m
Fig. 7. Typical optical images of microstructures for specimens of (a) Bi-42.73 wt.%Sn-1.03 wt.%Ag, (b) In-48.4 wt.%Sn-2.31 wt.%Ag,
(c) Sn-3.5 wt.%Ag-0.9 wt.%Cu, (d) Sn-42.8 wt.%Bi-0.04 wt.%Cu, and (e) Sn-6 wt.%Sb-5 wt.%Ag.

respectively.39 From the micrograph of Sn-Ag-Cu

shown in Fig. 7c, the alloy consists of solid Sn
solution and solid Ag3Sn and Cu6Sn5 phases below
the melting temperature of the Sn-Ag-Cu alloy. The
volume fraction of solid Sn solution phase is higher
than the other phases below the eutectic melting
temperature of the Sn-Ag-Cu alloy. Thus, the line of
thermal conductivity variation with temperature for
the Sn-Ag-Cu alloy determined in the present work
is just below the line of thermal conductivity variation with temperature for Sn,33 as shown in Fig. 4.

The solid solubility of Cu in Sn and Bi solids is

negligible at the eutectic melting temperatures of
500 K and 543.5 K, the solid solubility of Bi in Sn
and Cu solids is 20 wt.% and 100 wt.% at the
eutectic melting temperatures of 412 K and 543.5 K,
and the solid solubility of Sn in Cu and Bi solids is
15.8 wt.% and negligible at the eutectic melting
temperatures of 1069 K and 467 K, respectively.39
Below its melting temperature, the Sn-Bi-Cu alloy
consists of solid Sn solution and solid Bi phases, as
shown in Fig. 7d. The volume fraction of solid Bi

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3580

Table III. Some thermal properties of lead-free eutectic solders at their melting temperature

Solder
Sn-0.99 wt.%Cu28
Sn-7.9 wt.%Sb31
Sn-42 wt.%Sb31
Sn-5.1 wt.%Sb34
Sn-21 wt.%Bi27
Sn-25 wt.%In27
Sn-3.5 wt.%Ag-0.9 wt.%CuPW
Sn-4 wt.%Ag-2 wt.%In29
Sn-20 wt.%Ag-2 wt.%In36
Sn-40 wt.%Ag-2 wt.%In36
Sn-20 wt.%In-25 wt.%Ag37
Sn-20 wt.%In-10 wt.%Ag37
Sn-20 wt.%In-15 wt.%Ag38
Sn-6 wt.%Sb-5 wt.%AgPW
Sn-42.8 wt.%Bi-0.04 wt.%CuPW
In-48.4 wt.%Sn-2.31 wt.%AgPW
Bi-42.73 wt.%Sn-1.03 wt.%AgPW
Ag-38 wt.%Sn-2 wt.%In36
Ag-27 wt.%Sn-2 wt.%In36
Ag-20 wt.%In-8 wt.%Sn37
Ag-20 wt.%In-15 wt.%Sn37
Ag-20 wt.%In-35 wt.%Sn37

Temperature
(K)

Thermal
Conductivity, K (W/K-m)

Thermal
Temperature
Coefficient, aTTC (K21)

500.12
518.7
518.7
518.7
412.8
391.5
490.2
490.7
490.7
490.7
490.7
490.7
486.0
507.8
411.8
386.0
411.4
490.7
490.7
490.7
490.7
490.7

58.90
40.50
31.98
43.00
25.7
65.90
49.89 4.5
62.50
55.10
49.50
65.10
68.10
55.72
41.96 3.8
20.03 1.8
70.21 6.3
17.89 1.6
45.70
44.40
46.90
53.80
61.20

0.2928 9 103
0.460 9 103
0.907 9 103
0.280 9 103
0.620 9 103
0.750 9 103
0.805 9 103
0.867 9 103
0.940 9 103
1.246 9 103
2.638 9 103
1.250 9 103
2.894 9 103
0.750 9 103
0.560 9 103
1.114 9 103
0.756 9 103
0.712 9 103

PW, present work.

phase is close to the volume fraction of Sn solution

phase below the eutectic melting temperature of the
Sn-Bi-Cu alloy. Thus, the line of thermal conductivity variation with temperature for the Sn-Bi-Cu alloy
determined in the present work lies between the
lines of thermal conductivity variations with temperature for Sn33 and Bi33 and is close to the line of
thermal conductivity variation with temperature for
Bi,33 as shown in Fig. 5.
The solid solubility of Ag in Sn and Sb solids is
negligible at the eutectic melting temperatures of
494 K and 758 K, the solid solubility of Sb in Sn and
Ag solids is 8.1 wt.% and 9.6 wt.% at the eutectic
melting temperatures of 515 K and 758 K, and the
solid solubility of Sn in Ag and Sb solids is 20 wt.%
and 12.7 wt.% at the eutectic melting temperatures
of 494 K and 515 K, respectively.39 As can be seen
from Fig. 7e, the Sn-Sb-Ag alloy consists of solid Sn
solution and solid Ag3Sn and Sn3Sb2 phases below
its eutectic melting temperature. The volume fraction of solid Sn phase in the Sn-Sb-Ag alloy is higher
than solid Ag solution below its eutectic melting
temperature. Thus, the line of thermal conductivity
variation with temperature for the Sn-Sb-Ag alloy
determined in the present work is just below the
line of thermal conductivity variation with temperature for Sb,33 as shown in Fig. 6.
The values of K for the Bi-Sn-Ag, Sn-Ag-Cu,
Sn-Sb-Ag, Sn-Bi-Cu, and In-Sn-Ag solders at their
melting temperature were obtained as 17.89 1.6

W/K-m, 49.89 4.5 W/K-m, 41.96 3.8 W/K-m, 20.03

1.8 W/K-m, and 70.21 6.3 W/K-m, respectively, by
extrapolating the thermal conductivity curves to
their melting temperature as shown in Figs. 26
and presented in Table III. A comparison of the
values of KS measured in the present work at the
melting temperature for Bi-Sn-Ag, Sn-Ag-Cu,
Sn-Sb-Ag, Sn-Bi-Cu, and In-Sn-Ag with the values
of KS for similar binary or ternary eutectic alloys
measured in previous works2732,3538 is also presented in Table III. As can be seen from Table III,
the results of this work are in good agreement with
those obtained in previous works for similar binary
or ternary alloys and slightly different from previous results.2732,3538
Determination of Thermal Temperature
Coefficients for Lead-Free Solders
The temperature coefficient is the relative change
of a physical property when the temperature is
changed by 1 K. The temperature coefficient may be
negative or positive. A negative temperature coefficient occurs when a physical property such as
thermal conductivity or electrical conductivity of a
material rises with increasing temperature, typically in a defined temperature range. For most
materials, conductivity will decrease with increasing temperature. A negative temperature coefficient
avoids excessive local heating and may infrequently

Thermal Conductivity Variation with Temperature for Lead-Free Ternary Eutectic Solders

cause fires. A positive temperature coefficient refers

to materials that experience an increase in thermal
resistance when their temperature is raised. Materials which have useful engineering applications
usually show a relatively rapid increase with temperature, i.e., a higher coefficient. The higher the
coefficient, the greater the increase in thermal
resistance for a given temperature increase.
As mentioned above, the thermal temperature
coefficient can be determined from a plot of the
thermal conductivity variation with temperature.
As can be seen from Figs. 26, the slopes of the
graphs of the thermal conductivity variation with
temperature for these lead-free solders are negative. The thermal temperature coefficients of Bi-SnAg, Sn-Ag-Cu, Sn-Sb-Ag, Sn-Bi-Cu, and In-Sn-Ag
were found to be 2.894 9 103 K1, 0.907 9 103
K1, 1.246 9 103 K1, 2.638 9 103 K1, and
1.250 9 104 K1, respectively, from Figs. 26, as
presented in Table III. A comparison of the values of
the thermal temperature coefficient determined in
the present work for the Bi-Sn-Ag, Sn-Ag-Cu,
Sn-Sb-Ag, Sn-Bi-Cu, and In-Sn-Ag alloys with values of the thermal temperature coefficient determined in previous works2732,3538 is also presented
in Table III. As can be seen from Table III, the
thermal temperature coefficients for the lead-free
solders depend on the composition of the solder, and
the values of the thermal temperature coefficient for
the Bi-Sn-Ag, Sn-Ag-Cu, Sn-Sb-Ag, Sn-Bi-Cu, and
In-Sn-Ag solders agree with the values of the thermal temperature coefficient for similar binary or
ternary eutectic solders.
CONCLUSIONS
The thermal conductivity of the lead-free ternary
solder alloys Bi-Sn-Ag, Sn-Ag-Cu, Sn-Sb-Ag, Sn-BiCu, and In-Sn-Ag at their melting temperature was
obtained as 17.89 1.6 W/K-m, 49.89 4.5 W/K-m,
41.96 3.8 W/K-m, 20.03 1.8 W/K-m, and 70.21
6.3 W/K-m, respectively, by using a linear heat
flow apparatus. The thermal temperature coefficients
for the Bi-Sn-Ag, Sn-Ag-Cu, Sn-Sb-Ag, Sn-Bi-Cu, and
In-Sn-Ag solders were also determined to be 2.894 9
103 K1, 0.907 9 103 K1, 1.246 9 103 K1,
2.638 9 103 K1, and 1.250 9 103 K1, respectively, from plots of thermal conductivity variation
with temperature.
ACKNOWLEDGEMENTS
This project was supported by the Erciyes University Scientific Research Project Unit under
Contract No. FBA-10-3297 and the Nevsehir University Scientific Research Project Unit under
Contract No. 2012/5. The authors would like to
thank the Erciyes University Scientific Research
Project Unit and Nevsehir University Scientific
Research Project Unit for their financial support.

3581

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