Int.

Journal of Refractory Metals and Hard Materials 42 (2014) 240245

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Int. Journal of Refractory Metals and Hard Materials

journal homepage: www.elsevier.com/locate/IJRMHM

The sintering behavior of ultra-ne MoCu composite powders and the sintering properties of the composite compacts
Dezhi Wang a,b, Xiaojia Dong a, Pan Zhou a, Aokui Sun a, Bohua Duan a,b,
a b

School of Materials Science and Engineering, Central South University, Changsha 410083, China Key Laboratory of Nonferrous Metal Materials Science and Engineering, Ministry of Education, Central South University, Changsha 410083, China

a r t i c l e

i n f o

a b s t r a c t
Nanocrystalline Mo25 wt.%Cu composite powders were synthesized by ball-milling, calcinating and subsequent hydrogen reduction process. MoO3 and CuO powders were used as precursors. The sintering behavior of ultrane MoCu composite powders and the sintering properties of the composite compacts were investigated. The densication, microstructure, hardness, electrical conductivity, thermal conductivity and coefcient of thermal expansion were tested after solid phase sintering and liquid phase sintering. Relative density near 96% was achieved for the specimen which was compacted under a very low pressure of 32 MPa and sintered at 1050 C. It reveals that high-energy ball milling increases the contribution of solid phase sintering of Mo and Cu particles on the densication. The microstructure of the sintered compacts observed by scanning electron microscopy showed homogenous dispersion of Mo and Cu phase. The nal product showed good physical and mechanical properties. Crown Copyright 2013 Published by Elsevier Ltd. All rights reserved.

Article history: Received 8 May 2013 Accepted 16 September 2013 Keywords: MoCu Ball-milling Sintering Microstructure Properties

1. Introduction MoCu composites with 2040% copper are widely used for the heavy duty service contacts due to their excellent properties like low coefcient of thermal expansion, wear resistance, high temperature strength and prominent electrical and thermal conductivity [1]. The conventional processes for fabrication of the MoCu composites are inltration of copper to molybdenum skeleton and liquid phase sintering. However, it is difcult to obtain high-density MoCu composites as a result of the mutual insolubility between Mo and Cu, or the high contact angle of liquid copper on molybdenum [2,3]. The sinterability of MoCu powders can be increased through an activated sintering process by addition of a small amount of metal such as Co, Ni, or Fe. However, such activators exhibit a negative inuence on the electrical and thermal properties of the MoCu alloys [4]. Recently, many investigations have been performed to synthesize the nanoscale MoCu powders, since the sinterability can be improved by decreasing the particle size and enhancing the homogeneity of the starting powders [58]. Modication of particle size and distribution can be achieved by mechanical alloying (MA) [9]. Unlike conventional MoCu powders, the sintering of nanocrystalline MoCu mixtures synthesized by MA is signicantly enhanced at solid phase sintering temperature [4]. In the case of MoCu composites prepared by MA, solid phase sintering could have an adverse effect on the rearrangement process during liquid phase sintering. Although most reports show that the maximum relative
Corresponding author at: School of Materials Science and Engineering, Central South University, Changsha 410083, China. Tel.: +86 731 88877221; fax: +86 731 88830202. E-mail address: msewml@csu.edu.cn (B. Duan).

density is achieved during liquid phase sintering, it is undeniable that solid phase sintering plays an important role in the densication of the nanocrystalline materials [10,11]. In our previous study [12], we have reported a simple route to synthesize ultra-ne and well-dispersed MoCu nanocomposites. The sintering behavior of ultra-ne composite powders and the sintering properties of the composite compacts are investigated at present research. It is conrmed that the contribution of solid phase sintering on the densication is signicant. 2. Experimental procedures The characteristics of the starting powders are listed in Table 1. MoO3 and CuO powders with a mass radio of 3.6:1 were uniformly blended and then calcined in air atmosphere at 530 C to obtain CuMoO4MoO3 mixtures. Ball milling was carried out in a Planet-BallGrinding machine at a rotational speed of 400 rpm for 20 h in air atmosphere. The ball milled CuMoO4MoO3 mixtures were nally reduced in hydrogen atmosphere (dew point 30 C to 40 C) at 650 C for 1.5 h in a tube-type electrical furnace. The ow rate was 0.8 L min 1, and the height of powder bed was 12 mm. The resultant MoCu nanocomposite powders were compacted in a steel die under the pressure of 32 MPa to produce green parts. Sintering was performed in a tube-type electrical furnace with a heating rate of 10 C min 1 at different temperatures, ranging from 950 C to 1100 C, for 90 min under hydrogen atmosphere. The densities of the sintered compacts were measured according to Archimedes' principle. The hardness of the specimens was determined by a Vickers hardness tester. The scanning electron microscope was used for microstructure

0263-4368/$ see front matter. Crown Copyright 2013 Published by Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.ijrmhm.2013.09.012

D. Wang et al. / Int. Journal of Refractory Metals and Hard Materials 42 (2014) 240245 Table 1 Characteristics of raw powders. Material MoO3 CuO Supplier Tianjin Chemical Development, China Sinopharm Chemical Reagent, China Average particle size (m) 1 5 Morphology Polygon Polygon Purity (%) 99.95 99.0

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evaluation of the sintered samples. Electrical conductivity was examined using a four wire method by a micro-ohmmeter. Thermal conductivity and coefcient of thermal expansion were measured by thermal diffusivity analyzer. 3. Results and discussion The characteristics of the ultra-ne Mo25 wt.%Cu nanocomposite powders synthesized by ball-milling have been reported in detail elsewhere [12]. Fig. 1 and Fig. 2 show SEM and TEM images of the MoCu composite powders. It can be seen that the MoCu powders compose of superne spherical nanoparticles, with particle size ranging from 60 to 180 nm. These spherical particles exhibit high specic surfaces area, regular shape and uniform size distribution, which make the MoCu powders have excellent capability in sintering. Sintering behavior and sintering properties are discussed in this work. 3.1. Sintering behavior Fig. 3 shows the inuence of sintering temperature on shrinkage. As sintering temperature rises, both radial and axial shrinkage of the sintered specimens increase. Moreover, radial shrinkage is always higher than axial shrinkage. This is because radial pressure is invariably lower than axial pressure during the uniaxial pressing process. Hence the green density in compact-pressing direction is higher than that in perpendicular to compact-pressing direction. When sintered at the same temperature, radial shrinkage is always higher than axial shrinkage. The effect of sintering temperature on density and relative density of sintered compacts are shown in Fig. 4. It appears that the density and the relative density of the specimens are increased by raising the sintering temperature when sintered under 1100 C. At the temperature of 950 C, 1000 C and 1050 C, which are below the melting point of copper, the sintering process is known as solid phase sintering. During solid phase sintering, atomic diffusion ability was enhanced and

Fig. 2. TEM image of MoCu composite powders.

pores tended to decrease while the formation and growing of sintering necks were accelerated. Meanwhile Cu element diffused from the bulk to the surface of the composite particles and linked to the other diffused Cu elements from other particles to form a copper network all over the structure. Formation of this network could improve the densication [13,14]. So that an obvious increment in the densication was noticed as the temperature increased. In contrast to solid phase sintering, density and relative density are decreased when sintered at 1100 C (liquid phase sintering). Nevertheless, both radial and axial shrinkage of the MoCu samples are increased at 1100 C (Fig. 3). This phenomenon is quite different from other researches [5,7,13,15]. Reasons for the reverse densication are concluded as follows. Firstly, some impurities existing in powders vaporized into gases at the high temperature. Then the gases were packaged in the specimens under the compacting pressure. During sintering process, expands of these gasses resulted in reverse densication. Secondly, pores which are resulted from the large seepage of liquid copper increased during liquid phase sintering; hence the density decreased, though the shrinkage increased. Under the very low pressure of 32 MPa (most researches choose the pressure of about 100 MPa), relative density of near 96% was achieved for the compacts sintered at 1050 C by using MoCu composite powders which were synthesized by coreduction of mechanical-activated CuMoO4MoO3 mixtures. Owing to the ner MoCu nanoscale particles, composite powders possess large specic surface area, high surface energy and high sinterability. Pores between particles are smaller; this promotes diffusion rate and further facilitates the densication [16]. In addition, the unique coated structure of MoCu composite powders

Fig. 1. SEM image of MoCu composite powders.

Fig. 3. Effect of sintering temperature on shrinkage of sintered compacts.

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3.2. Microstructure of MoCu compacts Fig. 5 presents the cross-section microstructure of MoCu compacts sintered for 1.5 h at the temperature of 950 C, 1000 C, 1050 C, and 1100 C. Large interparticle pores can be seen on the cross-section of the specimen sintered at 950 C (Fig. 5a). The diffusion of Cu phase is enhanced by increasing the sintering temperature to 1000 C, and the distribution of Cu tends to be more uniform (Fig. 5b). The amount and size of the pores are reduced, and a relatively dense and homogenous microstructure of the MoCu compacts is observed when sintered at 1050 C (Fig. 5c). Increasing the sintering temperature to 1100 C results in signicant copper evaporation, generation of massive pores and a decrease in density of the composite compacts (Fig. 5d). Fig. 6 shows the fractograph of MoCu samples sintered for 1.5 h at 1050 C and 1100 C. A dense and homogenous microstructure can be seen apparently from Fig. 6(a), (c). On the whole, every Mo particle is capsulated in continuous network structure of Cu. This network structure, an ideal sintering state, is favorable to strength, electrical conductivity and thermal conductivity of MoCu alloys. Fig. 6(b) and Fig. 6(d) reveal that the size of particles sintered at 1100 C is larger than that sintered at 1050 C. In addition, a mass of pores come out as a result of the loss of copper. When increasing the copper content, higher temperature (over the melting point of copper) may cause a larger loss of liquid copper. Sintering properties of MoCu compacts.

Fig. 4. Effect of sintering temperature on density and relative density of sintered compacts: (a) density; (b) relative density.

causes a homogeneous distribution of Mo phase and Cu phase, which is benecial to sintering densication. Therefore, a maximum density of near 96% was obtained at solid phase sintering temperature.

Fig. 5. Cross-section microstructure of MoCu compacts at different sintering temperature: (a) 950 C; (b) 1000 C; (c) 1050 C; (d) 1100 C.

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Fig. 6. Fractograph of MoCu compacts at different sintering temperature: (a), (c) 1050 C; (b), (d) 1100 C.

3.2.1. Hardness The effect of sintering temperature on the hardness is shown in Fig. 7. It has been found that the tendency of Vickers hardness with different temperature is similar to that of density (Fig. 4). Evidently, the high density of the sintered samples is the main reason for high hardness. During solid phase sintering, porosity of the sintered samples decreases, and grain size grows as sintering temperature increases. Hence the maximum value of hardness (214 HV) is achieved at the temperature of 1050 C.

3.2.2. Electrical and thermal conductivity Fig. 8 presents the electrical and thermal conductivity of the sintered compacts at different temperature. The electrical conductivity analysis results present that the electrical conductivity increases gradually from 950 C to 1050 C, and the maximum value of electrical conductivity (22.4 MS/m) is gained at 1050 C. When sintered at 1100 C (liquid phase sintering), electrical conductivity of the compacts is lower than that of those samples processed by solid phase sintering. The reason

Fig. 7. Effect of sintering temperature on the hardness of the sintered specimens.

Fig. 8. Effect of sintering temperature on electrical and thermal conductivity of the sintered compacts.

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relative density of MoCu composite may increase substantially. Then other properties dependent on the relative density could have a corresponding improvement. 4. Conclusion In this work, we synthesized ultra-ne MoCu composite powders, with nely dispersion and homogenous distribution of Mo and Cu components. The following results were obtained: 1. The superne MoCu powders showed remarkable sinterability at 1050 C which is below the melting point of copper (solid phase sintering). 2. Maximum relative density (near 96%) of Mo25 wt.%Cu composites compacted at the very low pressure of 32 MPa can be achieved at low sintering temperature (1050 C). Homogeneous microstructure and other excellent properties of sintered products were obtained as well. Hardness, electrical conductivity, thermal conductivity and coefcient of thermal expansion of the MoCu composites sintered at 1050 C for 1.5 h are 214 HV, 22.4 MS/m, 147 Wm 1 K 1 and 8.5 10 6 K 1, respectively. 3. Homogeneous microstructure could contribute to enhancing diffusion rate of solid phase densication while the whole densication process is controlled by solid phase diffusion. On the contrary, liquid copper contributes little to densication of the Mo25 wt.%Cu compacts, even produces some adverse effects, such as evaporation and enhanced grain growth. Acknowledgement This work is supported by National Natural Science Foundation of China (No. 51274246). References
[1] Hong SH, Kim BK, Munir ZA. Synthesis and consolidation of nanostructured W10 40 wt.% Cu powders. Mater Sci Eng A 2005;405:32532. [2] Cheng J, Song P, Gong Y, Cai Y, Xia Y. Fabrication and characterization of W15Cu composite powders by a novel mechano-chemical process. Mater Sci Eng A 2008;488:4537. [3] Da Costa FA, da Silvab AGP, Gomes UU. The inuence of the dispersion technique on the characteristics of the WCu powders and on the sintering behavior. Powder Technol 2003;134:12332. [4] Ryu SS, Kim YD, Moon IH. Dilatometric analysis on the sintering behavior of nanocrystalline WCu prepared by mechanical alloying. J Alloys Compd 2002;335:23340. [5] Kim DG, Lee KW, Oh ST, Kim YD. Preparation of WCu nanocomposite powder by hydrogen-reduction of ball-milled W and CuO powder mixture. Mater Lett 2004;58:1199203. [6] Yang N, Wang Zh, Chen L, Wang Y, Zhu Y. A new process for fabricating W15wt. %Cu sheet by sintering, cold rolling and re-sintering. Int J Refract Met Hard Mater 2010;28:198200. [7] Wang Z, Li X, Zhu J, Mo F, Zhao C, Wang L. Dynamic consolidation of WCu nanocomposites from WCuO mixture. Mater Sci Eng A 2010;527:6098101. [8] Amirjan M, Parvin N, Zangeneh-Madar K. Mutual dependency of mechanical properties and contiguity in W Cu composites. Mater Sci Eng A 2010;527:6922 9. [9] Li Z, Jia C, He Y, Chen L. Kinetic characteristics of liquid phase sintering of mechanically activated W15wt%Cu powder. J Univ Sci Technol Beijing 2006;13:33845. [10] Kim JC, Moon IH. Sintering of nanostructured WCu alloys prepared by mechanical alloying. Nanostruct Mater 1988;10:28390. [11] Maneshian MH, Simchi A. Solid state and liquid phase sintering of mechanically ]activated W20 wt.% Cu powder mixture. J Alloys Compd 2008;463:1539.

Fig. 9. Coefcient of thermal expansion of the sintered compacts at different temperature.

for this phenomenon is that the Cu phase inherently has a much higher electrical conductivity than molybdenum. During liquid phase sintering, a large number of pores reemerge inside the sintered compacts on account of massive losses of copper. Thermal conductivity exhibits a similar trend. From optical micrograph (Fig. 6c), we can clearly nd out that Cu particles are connected together and almost every Mo particle is capsulated in continuous network structure of Cu. Consequently, the heat can be fast transferred between Mo and Cu. Maximum value of thermal conductivity is 147 Wm 1 K 1 for the samples sintered at 1050 C. 3.2.3. Coefcient of thermal expansion Fig. 9 shows the coefcient of thermal expansion (CTE) of the sintered samples at different temperature. The CTE analysis results indicate that the CTE is unstable before 200 C because the temperature of the samples is lower than the actual temperature during the primary heating stage. Obviously, the CTE increases gradually from 200 C to 300 C, and the curves become at when the temperature is above 300 C. It is known that the CTE of Cu is higher than that of Mo. Nevertheless, the higher CTE of Cu is constrained by the lower CTE of Mo in MoCu composite [6]. Particles transportations and interdiffusion are more easily occurring in nanoscaled MoCu composite obtained by MA than those in conventional composite during solid phase sintering. The distribution of Cu phase tends to be homogenous with the increasing of solid phase sintering temperature; hence the CTE increases gradually owing to the effect of Cu. When sintered at 1100 C (liquid phase sintering), the sintered specimens reveal the lower CTE due to the loss of Cu. In summary, the overall performance of the Mo25 wt.%Cu composite sintered at 1050 C is improved slightly compared with other researches [1719]. The comparison of the processing conditions and properties of the composite from the present study to the prior research studies is listed in Table 2. However, it is worth reminding that the compacting pressure in this study is 32 MPa, far lower than that (100380 MPa) of other reports [8,16,20]. Supporting that we raise the compacting pressure to a conventional degree, the density and the

Table 2 Comparison of the processing conditions and properties of the composite from the present study to the prior research studies. Composition Processing conditions Sintering temperature (C) 1050 1350 1250 1250 Sintering time (min) 90 60 90 120 Atmosphere H2 H2 H2 H2 Properties of nal products Relative density (%) 96 90.12 92 99.2 Hardness 214HV 68HRB 52.8HRB 72.5HRA Thermal conductivity (Wm1 K1) 147 143.3 164.36 139 Electrical conductivity (Ms/m) 22.4 24.7 22.27 CTE (10 6 K1) 8.5 9.3 7.4

Mo25Cu Mo30Cu [17] Mo30Cu [18] Mo18Cu1.5Ni [19]

D. Wang et al. / Int. Journal of Refractory Metals and Hard Materials 42 (2014) 240245 [12] Sun A, Wang D, Wu Z, Zan X. Synthesis of ultra-ne MoCu nanocomposites by coreduction of mechanical-activated CuMoO4MoO3 mixtures at low temperature. J Alloys Compd 2010;505:58891. [13] Ardestani M, Rezaie HR, Arabi H, Razavizadeh H. The effect of sintering temperature on densication of nanoscale dispersed W2040%wt Cu composite powders. Int J Refract Met Hard Mater 2009;27:8627. [14] Kim DG, Kim GS, Oh ST, Kim YD. The initial stage of sintering for WCu nanocomposite powder prepared from WCuO mixture. Mater Lett 2004;58:57881. [15] Li Y, Qu X, Zheng Z, Lei C, Zou Z, Yu S. Properties of W Cu composite powder produced by a thermo-mechanical method. Int J Refract Met Hard Mater 2003;21:259 64.

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[16] Kim DG, Lee BH, Oh ST, Kim YD, Kang SG. Mechanochemical process for W15 wt.%Cu nanocomposite powders with WO3-CuO powder mixture and its sintering characteristics. Mater Sci Eng A 2005;395:3337. [17] Zou A, Hua X, Zhou X, Zhang J. Effect of Co on the properties of the MoCu alloys. Spec cast Nonferr Alloys 2009;29:6824 (in Chinese). [18] Zhou X, Zou A, Hua X, Zhang J, Rao Y. Sintering characteristics of mechanically alloyed MoCu powder. Met Sci Heat Treat 2009;30:248 (in Chinese). [19] Guo S, Kang Q, Cai C, Qu X. Mechanical properties and expansion coefcient of MoCu composites with different Ni contents. Rare Met 2012;31:36871. [20] Jia C, He Z, Su X, Yang Z, Zhao J, Xie Z. Microstructures of sintered MoCu alloys with mechanically activated powder. Rare Met 2001;20:1123.