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The State Key Lab of Refractories and Metallurgy, Wuhan University of Science and Technology, Wuhan 430081, China
State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, China
a r t i c l e
i n f o
Article history:
Received 24 July 2015
Revised 27 September 2015
Accepted in revised form 9 January 2016
Available online 11 January 2016
Keywords:
CuW composites
Interfacial bond
Microstructural evolution
Properties improvement
a b s t r a c t
The effects of interfacial bond and homogeneous microstructure on the physical properties of CuW composites
have been investigated. To acquire strong interfacial bond and homogeneous microstructure, different modied
W powders have been designed, which W powders were coated with different Cu contents using electroless plating
method. The results showed that by increasing the Cu content of the coating, the microstructure of CuW composites becomes homogeneous, and the physical properties, including thermal, electrical and mechanical properties,
improved greatly. When 20Cu@W composite powders were used to fabricate CuW composites, the physical properties reached the optimal values: The thermal conductivity was 239 W/(mK) which was close to the theoretical
vaule of 240 W/(mK), the electrical conductivity was 50.6%IACS, coefcient of thermal expansion was the minimum value of 7.3 106/K, the bending strength and Vickers hardness were 976.7 MPa and 224.8 HV, respectively.
These optimal values were much higher than those of mixed CuW composites. The properties enhancement of
CuW composites is attributed to the strong interfacial bond between Cu and W and homogeneous microstructure.
This enhancement effect was strengthened by increasing the coating's Cu content, resulting in the continuous
improvement of the physical properties.
2016 Elsevier B.V. All rights reserved.
1. Introduction
Due to their low coefcient of thermal expansion, high thermal and
electrical conductivity, coppertungsten (CuW) composites have been
widely used in many applications such as heat sinks, electrodes and
vacuum interrupter [13]. Also, CuW composites can be used as kinetic
projectiles, armor penetrators, warhead materials and so on [4,5].
However, the fabrication of CuW composites proves to be difcult
because Cu and W are completely immiscible in both solid and liquid
phases. Therefore, the most effective way to fabricate CuW composites
is powder metallurgy. Conventionally, there are several alternative
methods to fabricate CuW composites, such as liquid-phase sintering,
inltration and activated sintering. Bhalla et al. [6] have fabricated full
density CuW composite by liquid-phase sintering using explosive
method, and Yang et al. [7] have prepared CuW composites by inltration. Although liquid-phase sintering at high temperature and inltration
could fabricate CuW composites with full densication, the sintering
temperatures of both methods are higher than the melting point of Cu
(Tm = 1358 K) leading to Cu exudation, so it is difcult to acquire the
Corresponding author.
E-mail address: luogq@whut.edu.cn (G. Luo).
http://dx.doi.org/10.1016/j.surfcoat.2016.01.014
0257-8972/ 2016 Elsevier B.V. All rights reserved.
et al. [13] pointed out that coating W powders with Ni alloy could obtain
a more homogeneous microstructure of CuW composites. Some
researchers [14,15] have also reported the method of plating Cu on
some metals and ceramics by electroless plating method, and found
that the properties of composites could improve a lot. Though
some researches have been reported to fabricate CuW composites
with electroless plating method to obtain full densication and
high properties, relatively less attention has been paid to the interfacial
bond between Cu and W and the mechanism of physical properties
enhancement. And it is not clear how the W powders with different
modications can transform to the differences in interfacial bond and
microstructure affecting the physical properties. Therefore, in order to
clarify the dependence of physical properties on interfacial bond and
microstructure of CuW composites, W powders have been modied
using electroless plating method to get Cu@W composite powders
with different Cu content in the coating in this work. The effect of W
powders with different modications on interfacial bond between Cu
and W has been investigated. The emphasis has also been placed on
microstructure evolution and properties enhancement of CuW
composites as the coating's Cu content increases.
used to obtain the average grain sizes of the Cu coating grains through
Scherrer equation. The exact Cu contents of Cu@W composite powders
were measured by inductively coupled plasma (ICP, Optima 4300DV,
USA). The morphologies of Cu@W composite powders and microstructure of CuW composites were observed using eld emission scanning
electron microscope (FE-SEM, Quanta-250, USA). The density of CuW
composites was measured based on the Archimedes principle. The
thermal conductivity of CuW composites can be calculated based
on the equation K = Cp, where K, , and Cp represent thermal
conductivity, thermal diffusivity, bulk density and specic heat of the
sample, respectively. The thermal diffusivity was measured using
laser ash apparatus (Netzsch, LFA 457, German) in Ar atmosphere at
room temperature. The coefcient of thermal expansion was measured
(DIL 402C, NETZSCH, Germany) in Ar atmosphere from room temperature to 350 C. The bending strength (U.S. MT810 Ceramic test system)
was measured with three-point bending method with 20 mm
6.25 mm 5.25 mm bars at a crosshead speed of 0.5 mm/min. Vickers
hardness (430 SVD) was measured on polished sections by Vickers
indentation with 1 kg load and holding 15 s. The reported bending
strength and Vickers hardness were the average value of three
measurements.
2. Experimental procedure
3. Results and discussion
2.1. Synthesis of Cu-coated W composite powders
3.1. Preparation of Cu@W composite powders
In this work, W powders with average size of 10 m were provided
by Xiamen Golden Egret Special Loy Co. Ltd. in China. Before electroless
plating process, the W powders were washed with HCl (37 wt.%) and
NaOH (30 wt.%) for 30 min, respectively, and then washed using deionized water. After that, electroless plating process was carried out. The
compositions of plating solution and reaction conditions are shown in
Table 1. The pH value in the bath was measured using an online pH
monitoring instrument, and was maintained by constantly adding
NaOH solution using a peristaltic pump. The temperature during electroless plating process was controlled using a constant temperature water
bath. After electroless plating process, Cu-coated W (Cu@W for short)
composite powders were washed using deionized water for more than
3 times and dried by vacuum freezing dried machine. The Cu contents
of the coatings in Cu@W composite powders were controlled by varying
the cupric sulfate contents in plating bath. 5Cu@W, 10Cu@W, 15Cu@W
and 20Cu@W composite powders represent that the coatings' Cu
contents are 5 wt.%, 10 wt.%, 15 wt.% and 20 wt.% Cu, respectively. The
Cu@W composite powders and some pure Cu powders (sphere, average
particle size is ~10 m, provided by Alfa company) were mixed by ball
milling with speed of 150 rpm for 3 h to get 20 wt.% CuW mixtures,
which were then cold pressed into green compacts. Additionally, pure
W powders and Cu powders were also mixed together to prepare
20 wt.% CuW compact for comparison. Finally, compacts were sintered
at 950 C100 MPa2 h by hot-press sintering.
2.2. Properties measurement and microstructure characterization
The phases of Cu@W composite powders and average grain sizes of
Cu coating were analyzed using X-ray diffraction (XRD, Ultima III,
Japan). The scanning range of 3095 and scanning speed of 4/min
were used to analyze the main phases of the composite powders. A
slow scanning speed of 0.24/min with the same scanning range was
Table 1
Bath compositions and reaction conditions for electroless plating.
Chemical
Function
Concentration
CuSO45H2O
KNaC4O6H44H2O
(C5H4N)2
HCHO
Source Cu
Complexing agent
Stabilizing agent
Reducing agent
20 g/L
50 g/L
5.0 mL/L
25 mL/L
10
Fig. 1. Characterizations of Cu@W composite powders: SEM of (a) raw W powders and (b) 20Cu@W; (c) XRD of Cu@W.
Fig. 2. The thickness of Cu layer and Cu grain size (a), and ICP (b) of Cu@W composite powders.
structure could form in the CuW composites which is benecial for the
electron conduction. What's more, the enhanced interfacial bond also
improves the electron conduction efciency at the interface of Cu and W.
It is worth noting that the maximum value of thermal conductivity is
close to the theoretical value with the mode proposed by German et al.
[16] as follows:
Q comp
Q W Q Cu 4R4R2 R2
R Q Cu 12R Q W
:
3
3
RQ W 1 R Q Cu
2
2
2
11
R 0:0113 1:58 VCu 1:83 VCu 3=2 1:06 VCu 3 , VCu is the Cu
volume fraction; Qcomp is the thermal conductivity of composites, QW
and QCu are the thermal conductivity of W and Cu, respectively. According
to the mode, the theoretical thermal conductivity of 20 wt.% CuW
composites is 240 W/(mK), and the maximum value of 239 W/(mK)
is very close to that when CuW composites are prepared with 20Cu@
W composite powders. It suggests that the ideal Cu network structure
has been obtained in this work to improve the thermal properties of
CuW composites.
The essence of CTE of metals is the vibration of the crystal lattice,
and there are many factors inuencing it, such as relative density,
components, homogeneity. When CuW composites are prepared
12
Fig. 6. Microstructures of CuW composites prepared with: (a): mixed W and Cu powders; (b): 20Cu@W composite powders.
13
Fig. 7. Fracture morphologies of CuW composites prepared with: (a): mixed W and Cu powders; (b): 20Cu@W composite powders.
and Cu pools, which also increases the electron scattering and lowers
the thermal and electrical conductivity as well as the mechanical properties of CuW composites. After W powders are coated with Cu, W and
Cu grains distribute homogeneously resulting in the formation of the
ideal Cu network structure in the CuW composites. What's more
important, there is excellent interface between Cu and W, as shown in
Fig. 8. It can be seen that W grains have good contact with Cu without
obvious defects at the interface, and W and Cu are bonded tightly
together which is benecial for the electron transportation and stress
transfer. What's more, the expansion of Cu grains could be effectively
restrained by W grains resulting in low coefcient of thermal expansion.
4. Conclusions
This work has provided a comprehensive study about the effect
of interfacial bond and homogeneous microstructure on the physical
properties of CuW composites. The detailed conclusions are as follows.
(1) W powders were uniformly coated with highly puried Cu by
electroless plating method. The coating's Cu content could be
adjusted accurately from 5 wt.% to 20 wt.% and the thickness of
Cu layer increased from 1.4 m to 3.6 m. The deposited Cu
acted as a catalytic agent resulting in increasing the thickness
and grain size of the deposited Cu layer.
(2) With the coating's Cu content increasing, the microstructure
of CuW composites become homogeneous, the thermal and
electrical conductivity, as well as mechanical properties increased
greatly, and the CTE decreased. When 20Cu@W composite powders were used to prepare Cu-coated powder CuW composites,
the physical properties reached the optimal values, which the
thermal and electrical conductivity improved to the maximum
values of 239 W/(mK) and 50.6%IACS, respectively, and CTE was
the minimum value of 7.3 106/K, the bending strength and
Vickers hardness reached the highest values of 976.7 MPa and
224.8 HV, respectively.
(3) The coating's Cu content on the W powders achieved homogeneous microstructure of CuW composites and had a positive
effect on improving physical properties. The ideal Cu network
structure formation and strong interfacial bond between W and
Cu improved the efciency of electron transportation and stress
transfer resulting in the high thermal, electrical and mechanical
properties.
Acknowledgment
This work has been supported by the National Natural Science
Foundation of China (51572208) and the 111 Project (B13035).
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Fig. 8. TEM of the interfacial structure between Cu and W: (a) low magnication; (b) high
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