Accepted Manuscript

Synthesis and thermal conductivity improvement of W-Cu

composites modified with WC interfacial layer

Chengcheng Zhang, Guoqiang Luo, Jian Zhang, Yang Dai, Qiang

Shen, Lianmeng Zhang

PII: S0264-1275(17)30447-1
DOI: doi: 10.1016/j.matdes.2017.04.090
Reference: JMADE 3012
To appear in: Materials & Design
Received date: 27 December 2016
Revised date: 19 April 2017
Accepted date: 26 April 2017

Please cite this article as: Chengcheng Zhang, Guoqiang Luo, Jian Zhang, Yang Dai,
Qiang Shen, Lianmeng Zhang , Synthesis and thermal conductivity improvement of W-Cu
composites modified with WC interfacial layer. The address for the corresponding author
was captured as affiliation for all authors. Please check if appropriate. Jmade(2017), doi:
10.1016/j.matdes.2017.04.090

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 ACCEPTED MANUSCRIPT

Synthesis and thermal conductivity improvement of W-Cu composites

modified with WC interfacial layer

Chengcheng Zhang1, Guoqiang Luo1, Jian Zhang1,*, Yang Dai1, Qiang Shen1,

Lianmeng Zhang1

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1 State Key Laboratory of Advanced Technology for Materials Synthesis and

Processing, Wuhan University of Technology, Wuhan 430070, PR China

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*Corresponding author.
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Tel: +86 027 87168606; Fax: +86 027 87879468.

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E-mail: isaiah178@hotmail.com.
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Abstract: In this study, the WC doped W-Cu composites with high excellent thermal

conductivity were fabricated by using coated composite powders combined with

vacuum hot-pressure sintering. As-received W powders were pre-modified with

organic additives via pyrolysis process (carburization process), and then Cu coated by

electroless plating. The WC formed in situ doped W-Cu composite was obtained. X-ray

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diffraction (XRD), scanning electron microscopy (SEM), and transmission electron

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microscopy (TEM) techniques were used to characterize the composite powders and

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sintered composites. The results show that the structure of coated composite powders

was W/C/Cu and the structure of sintered sample turned into W/WC/Cu. Both Cu
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matrix network and WC interfacial layer were obtained in the W-Cu composite.
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Compared with the W-20 wt.%Cu composite without WC modification, the WC doped

W-20 wt.%Cu composite have excellent thermal conductivity (287.5 W/(m·K)), low
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coefficient of thermal expansion (4.40 ppm/k) and relatively high Vickers hardness
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(230.5 HV). The excellent properties are mainly because of Cu network structure
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formed and its interfacial layer WC yielding improved bonding between the W and Cu
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matrix.
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Keywords: W-Cu composites; Powder metallurgy; WC interfacial layer;

Microstructure; Thermal conductivity

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1. Introduction

Cu matrix composites (CMCs) reinforced with reinforcement phases are widely

used as heat sinks [1, 2], electrical contact components [3], electric resistance welding

electrodes [4], etc. The tungsten-copper (W-Cu) composites composed of two

immiscible phases among CMCs are typical pseudo-alloys and the leading candidates

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of heat sinks owing to the combination of high thermal properties of copper with low

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thermal expansion coefficient, high strength and good ablation resistance of tungsten

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[5-7]. The ideal material for heat sinks in electronic industry should have a proper

coefficient of thermal expansion (CTE) to meet the requirements for packaging of

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semiconductors. Thus, normally the suitable mass fraction of Cu in W-Cu composites
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is less than 20 %. Meanwhile heat sinks are also required to have a high thermal

conductivity to dissipate heat generated in packages.

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High relative density and homogeneous microstructure of W-Cu composites make

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a great contribution to thermal properties [8-10]. The fabrication methods such as

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powder metallurgy, infiltration method and high-temperature liquid-phase sintering can

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be used to obtain W-Cu composites with high relative density, while composition
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segregation and specimen deformation happen easily [7, 11-15]. To solve these

problems, mechanical alloying (MA) method and activated sintering have been

developed rapidly in recent years [16-21]. However, during MA method, strong grain

refinement leads to an increase of interfaces between phases. The increasing grain

boundaries produce main barriers to high thermal conductivity of the composites [18].

In addition, composites made by MA method are vulnerable to impurities (such as Fe

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and O) that also affect thermal properties of the composite. Impurities introduced with

the methods of mechano-thermochemical processing (MTP) [18], thermo-mechanical

method (TMM) [22], wet-chemical methods [23], and spray drying [24], also decrease

the performance of W–Cu composites. Furthermore, the fact that residues of activator

(such as Zn and Ni) during activated sintering affect thermal conductivity is based on

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similar principle [19, 20].

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The W-Cu composites with a high-purity Cu network structure and homogeneous

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distribution of W particles are obtained by hot-pressure sintering using copper-coated

tungsten [25, 26]. Hence, the sintered composites with high relative density are of
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perfect thermal performance. When W particles are fully surrounded by Cu matrix, the
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interface between the two phases plays a key role in determining thermal conductivity.

It has been proved that an ideal interface should provide good adhesion and minimum
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thermal boundary resistance [27]. To modify the interface further, it is possible to

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optimize the properties by adding an appropriate interfacial layer to decrease interfacial

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thermal resistance and meet the demands for high thermal conductivities in thermal
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management applications [28, 29]. It is well known that alloying of Cu with a strong
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carbide-forming element promotes wetting and bonding of particles [30]. The wetting

angle of Cu on WC varies in the range 10-20° and the wetting angle of Cu on W varies

in the range 10-55° depending on the surface processing. Intrinsic wettability is similar,

but the contact angle values of Cu on W are sensitive to impurities, particularly oxygen

[31]. A better wettability is related to the effect of C on reducing the oxygen content at

the surface. Even though the influence of interfacial formation on thermal conductivity

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is not yet totally understood, it can be assumed that the very thin interface layer of a

carbide phase can aid necessary heat transfer at the interface and finally dominate heat

conduction of the composites.

In this study, W powders were modified by carburization processing and then

coated by electroless Cu plating. The W-Cu composite with the interfacial layer WC

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was fabricated by vacuum hot-press sintering using W/C/Cu composite powders. The

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density, microstructure and properties of sintered samples were studied.

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2. Experimental procedure

2.1 Pre-modified W powders

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As-received W powders (average particle size was about 10 μm, purity>99.9 %,
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provided by Xiamen Golden Egret Special Alloy Co., Ltd, China) were quickly mixed

with polyvinyl butyral (PVB) in absolute ethanol medium. PVB is cheap in cost and
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was used as a carbon source to synthesized silicon carbide nanocrystals [32-33]. As a

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result, PVB was used as a carbon source in this study. The composition of mixture is
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shown in Table 1. The mixture was rapidly stirred for 8 h in magnetic stirrer and then
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placed in drying oven for another 8 h at 80 ºC to make sure that ethanol solvent
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evaporated completely. After pretreatment, mixture of W powders and PVB was kept

in furnace at 600 ºC for 1h in N2 atmosphere, to transform organic additives PVB into

carbon coating (carburization process).

2.2 Electroless Cu plating process

Copper-coated tungsten powders (W-20 wt.%Cu) were prepared by electroless

plating. Electroless Cu plating process was used to deposit Cu on the surface of

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pre-modified W powders. The solution was maintained at pH 11 and 45 °C. The

pre-modified W powders were continually moved by stirring rod during electroless

plating process to obtain a homogeneous Cu coating. After the electroless plating, the

coated composite powders were washed using deionized water at least five times, then

freeze-dried and finally kept in the tube furnace to remove the possible existence of

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oxide at 400 °C for 1 h in high-purity H2 atmosphere. The composition of electrolysis

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bath solution is shown in Table 2. After washed by deionized water there were no more

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residues from the electroless plating solution in the coated composite powders. The

W/C/Cu coated composite powders are shown in Fig. 2(a). To find out the influence of
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pre-modified process, copper-coated tungsten powders (using unmodified W powders,
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W-20 wt.%Cu) were also prepared by electroless plating as a comparison.

2.3 Fabrication process

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Before hot-pressure sintering, the W-20 wt.%Cu composite powders (modified

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and unmodified) were pressed into green compacts which both appear red of Cu (Fig.
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2(b) and Fig. 2(c)) by using a pressure of 600 MPa. The green compacts were put into
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molds and subsequently vacuum hot-pressure sintered at 950 °C under a pressure of

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100 MPa with a soaking time of 2 h. Fig .2(d) and Fig. 2(e) shows digital pictures of

the sintered compacts. Process flow diagram of WC doped W-20 wt.%Cu composite is

shown in Fig. 1.

2.4 Characterizations

Thermogravimetry (TG) test of the modified W powders was conducted by

synchronous thermo analyzer in N2 atmosphere. The C element content of

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pre-modified W powders and the O element content of sintered compacts were

obtained from elemental analyzer (Vario EL cube). The density of sintered compacts

was measured by Archimedes principle. Field-emission scanning electron microscopy

(FE-SEM, Quan-250) was used to evaluate the morphology of samples and collect

high-sensitivity electron backscatter diffraction (EBSD) map. X-ray diffraction (XRD,

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Rigaku UltimaIII) with Cu Ka radiation (40 kV, 40 mA) was used for phase analysis. A

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High-resolution transmission electron microscopy (JEM-2100F STEM) was used to

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characterize the transition layer. Thermal diffusivity (α) was measured by using

NETZSCH LFA 457 Micro Flash at room temperature. Accordingly, thermal

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conductivity (κ) was calculated from the relationship: κ=cρα, where c and ρ are
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specific heat capacity and actual density of the composite, respectively. CTE was

measured on specimen of the same dimensions using a horizontal Netzsch dilatometer

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DIL402C. The Vickers hardness of W-Cu composites were characterized using

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VWilson Tukon 1202.

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3. Results and discussion

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3.1 Characterization of the pre-modified W powders

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Fig. 3 is TG curve of the pre-modified W powders prepared at 600 ºC. The TG

curve shows that the mass of tested powders decreased slowly with increasing

temperature (from room temperature to 950 ºC). It is also found that the weight loss is

less than 0.32 % (final value of TG curve is 99.68 %), indicating that most of the

organic additives had finished the pyrolysis process with a few organic residues present

in the powders. Therefore, it can be concluded that the soaking temperature (600 ºC)

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was proper for organic additives transformed into carbon coating on W particle surface.

The C elemental analyzer result shows that 0.4 wt.% C element existed in the

pre-modified W powders. The corresponding SEM micrographs of the above modified

W powders are shown in Fig. 4 (a) and Fig. 4 (b). As can be seen, there was carbon

coating on the surface of polygonal W particles. The TEM micrographs (Fig. 4(c)-(d))

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also indicate thin carbon coating uniformly covered the surface and the thickness of

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carbon coating was approximately 11 nm.

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3.2 Characterization of the W/C/Cu coated composite powders

The coated composite powders with W/C/Cu structure (W-20 wt.%Cu) are
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observed in SEM and interface between W particle and Cu coating is analysized by
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EDS. Fig. 5(a) shows the external morphology and Fig. 5(b) is cross-section

morphology. As can be seen in Fig 5(b), the W particle was uniformly and densely
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coated with a layer of Cu after electroless plating, and the thickness of the coated Cu
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layer was approximately 1.54 µm. The corresponding EDS analysis (Fig. 5(c)) shows
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the element content changes in cross-section of coated composite particle. The result
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indicates higher C content in the interface between W phase and Cu phase.

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3.3 Microstructure of the sintered sample

3.3.1 Microstructure and interface characterization

Fig. 6(a) is the SEM micrograph of polished sample sintered at 950 °C. The grey

domain is W phase, and the black domain is Cu phase that filled in the interstices of W

particles. The microstructure is homogeneous, and the average size of W particles is

approximately 10 μm. There is no pore while a network of Cu matrix formed

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throughout the composite after sintering. Fig. 6(b) shows the fractograph of sintered

sample. The fracture of sample mainly involved ductile failure of Cu and intergranular

fracture of W, while Cu matrix fully covered the surface of W particles, indicating that

bonding strength between W and Cu is strong. Fig. 6(c) is the partial enlargement of

fractograph. The chemical compositions (Fig. 6(d)) of the detected point on W surface

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(Fig. 6(c)) not only include W and Cu, but also a small amount of C.

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Fig. 7 presents SEM-EDS results of the enlargement of interface between the W

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and Cu matrix. Considering mutual insolubility of W and Cu, the interface is almost

obvious according to linear EDS results. The content of C at the interface is much
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higher than that in two phases. Different from the cross-section of coated composite
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powders (Fig. 5(b)), some reactions happened at the interface during sintering at

950 °C. New phase formed between W particles and Cu matrix during sintering. To
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confirm the new phase, XRD analysis was carried out. The XRD pattern in Fig. 8
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reveals that C coating on W particles formed corresponding carbides (WC) as the main
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reaction product in W-Cu composite after hot-pressure sintering.

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The high-resolution TEM images at the interface between W and Cu (obtained

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from the fabricated WC doped W-Cu sintered sample) are shown in Fig. 9 (with and

without transition layer). In Fig. 9(a), there is a clear transition layer (about 10 nm)

between W phase (b-1) and Cu phase (b-3). The interfacial phase, nano-crystalline WC,

in situ formed during sintering and adhered well to the surface of W particles. The EDS

results give some important information concerning the elemental distributions. EDS

results at the b-2 point show that chemical compositions at the transition layer include

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W, Cu and C. Different from the rest EDS results especially b-1 and d-1, intensities of

W peak and Cu peak are both high at b-2 point. These results suggest that Cu diffusion

into the transition layer happened after the sintering. Obviously, the reaction of

forming WC led to better bonding between W phase and Cu phase. The WC phase is

also beneficial to the wettability between the two phases. While taking into account the

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very low solubility of Cu in WC phase, we conclude that the transition layer is a

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mixture of WC and Cu. A similar phenomenon was reported in diamond/Cu system

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with Cr or B alloying element in the metal matrix [29]. The TEM results tend to

indicate a continuous interfacial layer and uniformity of WC phase.

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It is difficult to identify the WC phase by SEM-EDS. The EBSD investigation of
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phase distribution is another evidence to confirm TEM observations regarding WC

phase. The acquired EBSD map (Fig. 10) presents a satisfactory indexing rate with
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almost 81% of the area indexed and obviously shows location of WC phase
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surrounding W particles.
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3.3.2 Schematic description of the formation of interfacial WC phase

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The improvement of interface in this work is shown in the schematic description

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of the formation of interfacial WC phase as shown in Fig. 11. As mentioned in

introduction, WC is a potential addition to enhance interfacial thermal conductivity

between W and Cu phases. During the pretreatment, organic additive PVB transformed

into C coating on W powders. Hence, the interface was different after electroless Cu

plating process and composite particles with W/C/Cu structure were obtained. After

hot-pressure sintering, Cu network structure formed and interfacial structure turned

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into W/WC/Cu with the in situ formation of WC phase. Therefore, the interface

between W and Cu in sintered composite was improved by adding transition layer.

3.4 Properties of W-Cu composites

Density value of the W-Cu composite without interfacial layer WC is 15.57 g/cm3,

however lower density value of 15.03 g/cm3 corresponds to the one with interfacial

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layer WC (refer to Table 3). The density deviation may be caused by the interfacial

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layer WC formed by the direct reaction of the W and C. Reported density value of WC

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(14.90 g/cm3) is much less than the density value of W (19.32 g/cm3) [34].

The properties of W–Cu composites with or without interfacial layer WC (in this
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work) fabricated using coated composite powders and by other methods are listed in
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Table 4. By comparing the W-Cu composites with and without modification, the

thermal conductivity increases obviously from 235.0 W/(m·K) to 287.5 W/(m·K), by

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almost 20.3 %. Besides, the measured CTE of the samples decreases from 7.38 ppm/K
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to 4.40 ppm/K.
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The thermal conductivity of sintered sample is quite influenced by two main

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factors: the Cu network structure and interfacial bonding between the matrix Cu and W.
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The W-20Cu and W-20CuWC composites were both fabricated by Cu coated powders

and thus a perfect Cu network was obtained as expected. The continuous Cu coating on

W formed a net-shaped Cu matrix which increased heat transfer ability of composites

and provided the foundation for high thermal conductivity. The interfacial bonding in

pure W-Cu composite was weaker than that in WC doped W-Cu composite. This can

be explained by no chemical affinity between W and Cu and therefore no strong

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interfacial bonding for an optimum thermal transfer at the interface. The amorphous

carbon coating reacted with W particles and formed in situ WC phase. In situ WC

phase formed a strong chemical bonding strength with W particles during hot-pressure

sintering. Besides, the W-Cu composite with WC interfacial layer contains less oxygen

compared to the one without interfacial layer (refer to Table 3). A better wettability was

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related to the effect of C on reducing the oxygen content at the surface [31]. The WC

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interfacial modification layer can be an effective phase to improve interfacial wetting.

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As has been reported, improved interfacial wetting can increase the bonding between

the reinforcement and matrix [36-38]. Different from the weak interface caused by
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mutual insolubility of W and Cu, the interface in W-Cu WC was enhanced by combined
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methods of both chemical reaction bonding and wetting improvement. Improved

bonding results in both increased heat transfer and improved load transfer between the
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matrix and the reinforcement. This explains the increase in thermal conductivity and
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the drop in CTE [29]. Overall, the high thermal conductivity of the composite can be
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explained by the combined effects of the network structure of Cu matrix and improved
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bonding between the two phases.

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In previous papers, the full-density W-23.5 wt.%Cu was prepared by hot-pressure

sintering at 850°C with Zn addition during the activated sintering, but the best thermal

conductivity was only 198 W/(m·K) [20]. The W-20 wt.%Cu composite with thermal

conductivity of 239 W/(m·K) was obtained by mechano-thermochemical process

(MTP) [18]. We have achieved that thermal conductivity of the W–Cu composite with

interfacial layer WC is 287.5 W/(m·K).

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The Vickers hardness of specimens are listed in Table 3. The hardness of the

specimen with interfacial layer WC increases slightly from 224.2 HV to 230.5 HV. The

formation of WC contributes to the hardness of the composite. However, the WC

content in composite is low, so that the improvement of Vickers hardness is not

significant.

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4. Conclusions

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As-received W powders were pre-modified with organic additives via

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carburization process and Cu-coated by electroless plating. The coated composite

powders with W/C/Cu structure are prepared successfully. The amorphous carbon
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coating reacted with W particles and formed in situ WC phase. The uniformity of in
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situ WC phase mainly surrounded W particles. Thermal conductivity, CTE and Vickers

hardness of the W-Cu composite with interfacial layer WC are 287.5 W/(m•K), 4.40
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ppm/k and 230.5 HV respectively. The Cu network structure and WC transition layer
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of composite yielding improved bonding between the W and Cu matrix are the main
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reasons for the excellent thermal properties. The excellent thermal conductivity and
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quite low CTE make the W-Cu composite with promising heat-sink materials.
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Acknowledgement

This work was supported by National Natural Science Foundation of China (Grant No.

51521001 and 51572208), the 111 Project (Grant No. B13035) and the Joint Fund

(Grant No. 6141A02022209).

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[31] N. Eustathopoulos, M.G. Nicholas, B. Drevet, Wettability at high temperatures,

Pergamon, 1999.

[32] P. Kumar, N. Khan, Polyvinyl butyral (PVB), versetile template for designing

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[33] S. Park, J. Kim, B. Kim, D. Kim, Synthesis of Silicon Carbide Nanocrystals Using

Waste Poly(vinyl butyral) Sheet, Journal of American Ceramic Society, 99 (2016)

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[34] Z. Tan, Z. Li, D.B. Xiong, G. Fan, G. Ji, D. Zhang, A predictive model for

interfacial thermal conductance in surface metallized diamond aluminum matrix

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composites, Materials & Design, 55 (2014) 257-262.

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[35] A. Yan, Z. Wang, T. Yang, Y. Wang, Z. Ma, Microstructure, thermal physical

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property and surface morphology of W-Cu composite fabricated via selective laser
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melting, Materials & Design, 109 (2016) 79-87.

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[36] Y. Huang, Y. Su, X. Guo, Q. Guo, Q. Ouyang, G. Zhang, Di Zhang, Fabrication

and thermal conductivity of copper coated graphite film/aluminum composites for

effective thermal management, Journal of Alloys and Compounds, 711 (2017) 22-30.

[37] X.Y. Liu, W.G. Wang, D. Wang, D.R. Ni, L.Q. Chen, Z.Y. Ma, Effect of

nanometer TiC coated diamond on the strength and thermal conductivity of

diamond/Al composites, Materials Chemistry & Physics, 182 (2016) 256-262.

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[38] L.G. Hou, R.Z. Wu, X.D. Wang, J.H. Zhang, M.L. Zhang, A.P. Dong, B.D. Sun,

Microstructure, mechanical properties and thermal conductivity of the short carbon

fiber reinforced magnesium matrix composites, Journal of Alloys and Compounds, 685

(2017) 2820-2826.

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Table captions

Table 1 The composition of the mixture

Table 2 The composition of electroless bath solution

Table 3 Comparison of some characteristics between the W-Cu composite with and

without interfacial layer WC

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Table 4 Comparison of thermal conductivity and CTE of W-Cu composites by several

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Figures captions

Fig. 1 Process flow diagram of the WC doped W-20wt.% Cu composite

Fig. 2 Digital pictures, (a) the W/C/Cu coated composite powders, (b) the green

compact without any coating, (c) the green compact with C coating, (d) the sintered

compact without WC interfacial layer, (e) the sintered compact with WC interfacial

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layer

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Fig. 3 TG curve (from room temperature to 950 ºC) and C content of the modified W

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Fig. 4 Micrographs of the pre-modified W powders, (a) and (b) SEM images, (c) and (d)
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Fig. 5 SEM micrographs of the W/C/Cu coated composite powders, (a) external

morphology, (b) cross-section morphology, (c) EDS linear analysis across the interface
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between W and Cu in the cross-section morphology

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Fig. 6 SEM micrographs of the sintered sample, (a) the polished sample, (b) the
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fractograph, (c) enlargement of the fractograph, (d) EDS results of the detected point
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Fig. 7 SEM-EDS results of the interface between W and Cu in sintered sample

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Fig. 8 XRD pattern of the W-Cu sintered sample and the strongest peaks of the WC

phase (a) 28 deg.-95 deg. (b) 28 deg.-40 deg.

Fig. 9 TEM images of the sintered samples, (a) the sample with transition layer, (b)

EDS results of the corresponding detected points (with transition layer), (c) the sample

without transition layer, (d) EDS results of the corresponding detected points (without

transition layer)

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Fig. 10 EBSD analysis showing the phase distribution map of the sintered sample

Fig. 11 Schematic description of formation of the WC interfacial modification layer

and structure of the W-Cu sintered composite (WC doped W-Cu sintered sample)

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Figure 1

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Figure 2

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Figure 3

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Figure 4

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Figure 5

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Figure 6

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Figure 7

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Figure 8

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Figure 9

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Figure 10

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Figure 11

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Table 1 The composition of the mixture

Composition Role Mass fraction

W powders Source W 80 %
Polyvinyl butyral Source C 2%
Absolute ethanol Solvent 18 %

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Table 2 The composition of electroless bath solution

Agent Formula Role Concentration

Copper sulfate pentahydrate CuSO4·5H2O Source Cu 20 g·L-1

Potassium sodium tartrate KNaC4O6H4·4H2O Complexing agent 40 g·L-1

Formaldehyde HCHO Reducing agent 10 ml·L-1

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2,2’-dipyridyl (C5H4N)2 Stabilizing agent 10 mg·L-1

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Table 3 Comparison of some characteristics between the W-Cu composite with and
without interfacial layer WC

Sintered sample Oxygen content (wt.%) Density (g/cm3) Vickers hardness (HV)

W-20Cu (this work) 1.00 15.57 224.2

W-20CuWC (this work) 0.45 15.03 230.5

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Table 4 Comparison of thermal conductivity and CTE of W-Cu composites by several

methods
Sintered sample Thermal conductivity (W/(m·k) CTE (ppm/k)
Activated sinteringa 198 8.8
MTP [18] 239 -
TMM [22] 205 -
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Laser meltingb [35] 121.3 7.02

Infiltration [15] 218 8.8

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W-20Cu (this work) 235 7.38
WC

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W-20Cu (this work) 287.5 4.40
a, b
The composites are W-23.5 wt.%Cu and 80W-5Ni-15 wt.%Cu respectively, while
the other composites are W-20 wt.%Cu.
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The best value found among the papers using that method.
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Graphical Abstract

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Highlights

1. The WC formed in situ doped W-Cu composite was obtained via pyrolysis process,

electroless Cu plating and vacuum hot-press sintering.

2. The interfacial layer WC yield improved bonding between the W and Cu, with

attendant increase in thermal conductivity (239 W/(m·K)).

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