Materials Science and Engineering A 490 (2008) 293299

Reinforcing copper matrix composites through molecular-level mixing of functionalized nanodiamond by co-deposition route
Jie He a , Naiqin Zhao a,b, , Chunsheng Shi a , Xiwen Du a , Jiajun Li a , Philip Nash c
School of Materials Science and Engineering, Tianjin University, Tianjin 30072, China b Tianjin Key Laboratory of Composite and Functional Materials, China c Department of Mechanical, Materials and Aerospace Engineering, Illinois Institute of Technology, Chicago, IL 60616, USA Received 20 February 2007; received in revised form 9 January 2008; accepted 9 January 2008
a

Abstract This work reports a chemical method called co-deposition route for fabricating ND (nanodiamond)/Cu composite at a molecular-level mixing. The main procedure of co-deposition route includes four steps. ND particles have been functionalized by HF acid before co-deposition. SEM, HRTEM (high-resolution transmission electron spectroscopy), XRD (X-ray diffraction), EDS (energy-dispersive spectrum analysis) and optical microscope were carried out to characterize the as-prepared composite powders and bulk composites. Results indicated that copper matrix composite with a homogeneous dispersion of functionalized ND particles can be prepared. The modication of ND particles was performed by HF (30 vol%) acid at 70 C, and C F bond was successfully detected by XPS (X-ray photoelectron spectrum) and IR (Infrared spectroscopy). The properties of relative density, microhardness and electric conductivity of ND/Cu composites have been measured. With the comparison of conventional methods, it showed that the as-prepared ND/Cu composites with good combined performances have a promising future for industry application. 2008 Elsevier B.V. All rights reserved.
Keywords: Nanodiamond (ND); Co-deposition route; Copper matrix composite; Molecular-level mixing; Aggregation

1. Introduction Since the rst discovery of ND (nanodiamond) with an average size of 45 nm by detonating an oxygen-decient TNT/hexogen composition in inert media without using any extra carbon source in 1963 [13], ND, also called nanocrystalline diamond (NCD), or ultra dispersed diamond (UDD) of 220 nm in size has attracted an increased research attention. Initially, the studies of ND focus on its preparation technology, physical and mechanical properties [48]. Recently, the incorporation of ND powders into coatings [1,911] or bulk materials [1217] is of considerable interest to impart the remarkable properties of diamond to surfaces and composites. Due to the unique properties of ND, such as highest hardness, highest thermal conductivity, low thermal expansion coefcient, and low friction coefcient, one of the applications of ND is as the reinforcement of composite materials to overcome the performance limits of convention materials. There have been a few reports on UDD/polymer composites [1216] which have

Corresponding author. Tel.: +86 22 27891371; fax: +86 22 27891371. E-mail address: nqzhao@tju.edu.cn (N. Zhao).

shown the potential for improving the strength of polymers, and these studies have encouraged researchers to use ND as reinforcements for metal or ceramic matrices. Among metal-based composites, especially copper-based composites, high strength, high conductivity, resistant to high temperatures, and resistant to wearing, are very important and necessary qualities for electric contact materials, resistance electrode, and many other industrial applications. ND-reinforced metal matrix materials hold the promise of delivering superior composite materials with high strength, high conductivity, and multifunctional properties. Lately, several researchers have attempted to fabricate ND-reinforced copper matrix composite materials by traditional powder-metallurgy process which consists of mixing ND particles with matrix powders by high-energy milling [17,18]. However, it has been well recognized that several fundamental processing challenges must be overcome in order to enable applicable reinforcement by ND. Due to the poor wettability and reactivity between diamond and copper, such composite material could not well manufactured by traditional preparation method. Furthermore, with high surface chemical activity, ND particles tend to form tight aggregations [3] rather than homogeneously disperse in the matrix. The conventional milling process

0921-5093/$ see front matter 2008 Elsevier B.V. All rights reserved. doi:10.1016/j.msea.2008.01.046

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with micro-sized steel ball could not de-aggregate the strong aggregation of ND effectively. Moreover, high-energy milling cannot proceed without damaging ND and copper particles. Therefore, conventional methods could not take full advantage of the extraordinary properties of ND as reinforcements for metal matrix composites. In present work, we report a ND-reinforced Cu matrix composite, fabricated by a novel fabrication process called co-deposition route mixing at a molecular-level [19,20]. Our strategy for developing a novel fabrication process for ND/Cu composite basically involves molecular-level mixing of the reinforcement (ND) and the matrix material in a solution instead of conventional powder mixing. Besides, we use the ND functionalized by uorination to obtain a stable suspension [21,22] for the co-deposition process, because the uorination can remove the surface functional groups, such as COOH, SO3 H, NH2 , created by the industrial chemical processing of detonation ND, and render solubility to uoronanodiamond in polar solvents [23], e.g., ethanol. Such new fabrication process could well overcome the various barriers to accomplishing reinforcement by ND in copper matrix. 2. Experimental 2.1. Preparation of ND/Cu composite powders Commercially available diamond powders with an average size of 510 nm, shown in Fig. 1, were used in this work. Purication was rst carried out with a mixed solution of H2 SO4 /HNO3 in a 3:1 ratio at 40 C for 30 min. The aim of purication is to remove the impurities, such as S and Si, in raw ND powders. Then, ND powders were functionalized by acid treatment using strong HF (30 vol%) ultrasonic dispersing for 12 h at 70 C. After that, the powders were centrifugal separated and washed with distil water until neutral and dried at room temper-

ature. Consequently, the pre-treated ND particles were dispersed in ethanol (the ratio between ND and ethanol is 1 g:100 ml) by ultrasonication for 1 h to form a stable suspension. Consequently, a salt containing Cu ions, Cu(NO3 )2 3H2 O in the current study was added to the ND suspension, which was ultrasonicated again for 1 h at 40 C. The mass ratio between ND and Cu(NO3 )2 3H2 O is 1:(43374) in this work for different weight percentage (18 wt.%) of ND particles in the composites. The co-deposition process was performed when dripping aqueous ammonia (40 vol%) into the suspension solution with magnetic stirring. Then the solution was vaporized with stirring at 100 C, and the dried powders were calcinated at 300 C for 1 h in air. The calcinated powders were reduced in a tube furnace at 600 C for 1 h under a hydrogen atmosphere (99.99%). The mechanical mixing was also used to prepare ND/Cu composite powders in this work for comparison. It was performed in a WL-IA planetary ball mill, charging 250 ml agate containers with 20 g of a mixture of the pure copper powders (99.9% purity; particle size 38 m) and ND powders, and 40 g of agate balls that are 10 mm in diameter in each container. The milling time is 4 h. Then, composite powders were reduced as above. 2.2. Consolidation of ND/Cu composite powders The ND/Cu composite powders were pre-compacted in a cylindrical mold, 12 mm in diameter, under a pressure of 300 MPa. The pre-compacted powders were sintered at 1000 C for 1.5 h under argon (99%) protecting atmosphere (sintering/cooling rate is 10 C/min) in a quartz boat. The sintered ND/Cu composites were re-pressed in the same mold under a pressure of 1000 MPa for further increasing the relative density. 2.3. Characterization technique The microstructure characterization of the ND/Cu composite powders and composites were carried out by using JEOL JSM6700 eld emission scanning electron microscopy (FE-SEM), high-resolution transmission electron spectroscopy (HRTEM, Philips Tecnai G2 F20, 200 kV) and optical microscopy (Olympus BX51M). Chemical analysis was performed by X-ray diffraction (XRD, Rigaku D/MAX-2500, Cu K radiation), energy-dispersive spectrum analysis (EDS, JEOL JSM-6700), Infrared spectroscopy (IR, BIO-RAD FTS3000) and X-ray photoelectron spectrum (XPS, PHI-1600, Mg K radiation). The microhardness of ND/Cu composites was tested in Vickers hardness tester (MH-6) with 50 g load. The comparative electric conductivity was measured in eddy-current conductivity meter (FQR7501). 3. Results and discussion The HRTEM image of raw ND particles is shown in Fig. 1. The aggregation, including the conglomerates, intermediate aggregates and core aggregates [3,24] with the primary particles of 210 nm could be clearly seen. Such discrete levels of aggregation are not benecial to the co-deposition process and the dispersion in matrix. Therefore, making a stable and ultradis-

Fig. 1. HRTEM image of raw ND particles.

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persed ND suspension is the very important step in our present research. In this work, we used the surface modication of nanoscale diamond (ND) powders by acid treatment of 30 vol% HF acid at 70 C under ultrasonication. Then ND was dispersed in ethanol to make a stable suspension by attaching functional group C F bond onto the ND surfaces. Diamond surface modication has been studied during the past decade [1,25], and uorination was regarded as an efcient way to modify and to control the surface properties [22,26]. However, all previous work was carried either on larger size (micronscale) polycrystalline diamond or on thin lms grown in vacuum chambers, and no further chemistry, utilizing the C F bond reactivity in particular, was pursued after uorination. Successfully, we observed the existing of C F bond and F atom at surface in this experiment (shown in Fig. 2). Fig. 2(a) is the IR spectra of uorinated ND by strong HF acid and raw ND. It shows the presence of OH and C H stretching bands, corresponding to the adsorptions of H2 O and O2 due to the exposure in air. The C O and C O C stretching bands result from ND surface oxidation by nitric acid. The adsorption at 1631 and 1392 cm1 is most likely from the C C and C C stretching

vibrations of ND aggregations, but the intensity of the peaks is very low. It indicates the small amount of ND aggregations. As expected, a new peak at 1124 cm1 of C F stretching band could be found after the uorination. The XPS spectra of the raw ND and functionalized ND were also measured (Fig. 2(b)). The peak F1s at 685 eV was observed after irradiation, as shown in Fig. 2(c). These results suggest that the treatment of HF acid could break some tight functional groups, such as C C, C O, etc. and lead to the formation of a chemical bond (C F) between the uorine and the carbon atoms of the diamond crystals which benets to form a stable suspension: once the functional groups are attached to the ND surface, the electrostatic repulsive force between the ND particles overcomes the Van der Waals force to form a stable suspension within the solvent. The chemical co-deposition process in our work mainly consists of four steps, which are schematically depicted in Fig. 3. The functionalization of raw ND powders is the rst step to make the ND clusters into a stable suspension (Fig. 3(a)). Then copper nitrate is dissolved in the ND suspension to obtain the mixture solution. Additional ultrasonication treatment assists the

Fig. 2. (a) IR spectrum of functionalized ND by HF acid; (b) XPS full spectra of functionalized ND and unfunctionalized ND; and (c) F1s characteristic spectrum of functionalized ND.

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Fig. 3. Schematics depicting strategies and procedures for the co-deposition process of molecular-level mixing to fabricate ND/Cu composite powder.

dispersion of Cu ions among the suspended ND particles and promotes the attachment between the Cu ions and the functional groups on the surface of the ND (Fig. 3(b)) [19]. In some similar preparation process of metal-based composites [19,27], the process was continued by drying the mixture solution directly to obtain composite powders. However, considering the high surface energy of ND particles, the concentration and evaporation of suspension solution should lead to re-aggregation of primary ND particles [3], so we do not dry the suspension solution directly, and therefore develop a new process called co-deposition to fabricate ND/Cu composite powders shown in Fig. 3(c), with slowly dripping aqueous ammonia into the mixture solution,

copper hydroxide is formed and co-deposits with surrounding ND particles at a molecular-level. The nal step is the calcination and reduction process to obtain chemically stable composite powders (Fig. 3(d)).

Fig. 4. XRD patterns for raw ND and products in different preparation steps. (a) Raw ND particles; (b) products after calcination of co-deposition complex; and (c) products after reduction of ND/CuO composite powders under hydrogen atmosphere.

Fig. 5. SEM photograph of ND/Cu composite powders (a) and corresponding EDS analysis of the area in circle (b), and the area in square (c).

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Fig. 6. TEM photograph of single ND particle attaching on the surface of single copper particle in ND/Cu composite powders (a) and the inter-planar distance measurement of small particle (b), and big particle (c).

Table 1 Some physical properties of ND/Cu composites with increasing weight percentage of ND powders Pure Cu Relative density (%) Microhardness (HV) Electric conductivity (% IACSa )
a

1 wt.% 95.0 93.4 132.2

3 wt.% 96.3 116 86.2

5 wt.% 95.6 89.9 134.6

8 wt.% 91.9 128.9 78.7

95.6 86 86.5

IACS, International Annealed Copper Standard, which prescribes the electric conductivity of annealed unalloyed copper is 100% IACS (about 57.8 MS m1 ).

The X-ray diffraction patterns for the products after calcination (Fig. 4(b)) and reduction (Fig. 4(c)) process are shown in Fig. 4 together with that of raw ND powder alone (Fig. 4(a)). It presents clearly that the product is completely oxidized and reduced after calcination and reduction, respectively. The sharp diffraction peaks in Fig. 4(c) suggest that the copper exists as a good crystal in the sample. The absence of the reections from ND in the composite powder (in Fig. 4(b) and (c)) is due to the small amount of ND (3 wt.%) comparing with the intense reections of both CuO and Cu. The morphology of as-prepared ND/Cu composite powder is characterized by SEM (Fig. 5(a)). Well distributed bright spots are assigned to disintegrated ND particles based on EDS analysis: areas rich in the bright spots have high carbon contents (Fig. 5(b)). Dark area consists almost exclusively of copper according to Fig. 5(c). Although there are still ND aggregations on the surface of copper particles, it is a signicant breakthrough to decrease the cluster size to the double-digit nano-range by chemical method, and also a progress to disperse uniformly in the matrix for ND/metal composites. Successfully, as observed in Fig. 6, there is also single ND particle which attaches on the surface of copper particle. By the analysis of inter-planar distance (the average length of one peak in Fig. 6(b) and (c) represents inter-planar distance), we can

conform that the small particle is ND, because the inter-planar distance is about 0.2058 nm which is very close to the d (1 1 1) (about 0.206 nm) of diamond. The inter-planar distance of the big particle is 0.2084 nm closely to 0.2087 nm of the inter-planar distance of Cu (1 1 1).

Fig. 7. Microhardness of ND/Cu composites after annealing at different temperatures.

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Fig. 8. Optical micrographs of (a) 3wt.%; (b) 5wt.%; (c) 8wt.% functionalized ND/Cu composite prepared by co-deposition route; and (d) 3wt.%ND/Cu composite prepared by mechanical mixing.

The ND/Cu composite powders fabricated by co-deposition route were then consolidated into ND/Cu composite. Table 1 shows some properties of ND/Cu composites with different ND contents. The relative densities of ve samples are all higher than 90%, which could well illustrate that the ND/Cu composites are compact enough and the consolidation method used in this research is effective. As expected, the microhardness increases with the increasing contents of ND, and three samples microhardness are above 120 HV. Maybe due to the increasing ND clusters, the microhardness of the composites reinforced by 5 and 8 wt.% ND does not increase signicantly. However, the aggregation of ND is inevitable in such high ND contents (assuming for the density of ND similar to that of bulk diamond, which is 3.5 g cm3 , then 5 and 8 wt.% ND in this work corresponds to 11.9 and 18.2 vol%) [3]. Furthermore, owing to the homogeneous dispersion, the ND as non-conductive reinforcement does not damage the electric conductivity of composite greatly. Even at the high weight fraction of 8 wt.% ND, the comparative conductivity are still more than 70% IACS (International Annealed Copper Standard). The softening temperature is the temperature point at which the material still keeps 85% the original hardness at room temperature. Usually the softening temperature of pure copper is not higher than 200 C. As shown in Fig. 7, due to the reinforcement

of ND, the softening temperature of ND/Cu composites is greatly enhanced. The softening temperature of 1 wt.% ND/Cu composite is about 400 C. When the content of ND is higher than 3 wt.%, the softening temperatures of ND/Cu composites are all higher than 600 C. This good performance at high temperature can have an important application in hot environment. Fig. 8 is the optical micrograph of ND/Cu composites prepared by different methods and different ND contents. From the comparison between Fig. 8(a) and (d), we can see that the microstructure of ND/Cu composite prepared by mechanical mixing is not good. The ND particles aggregate widely, and distribute on the grain boundary, and then seriously effect the combination of matrix grains. However, the ND/Cu composite prepared by co-deposition route has a better microstructure: ND particles uniformly distribute in the matrix, and therefore the matrix has better combination and smaller copper grains. Besides, the ND particles not only exist on the grain boundary but also exist in the grain, which could further enhance the reinforcement effect. So the ND/Cu composite prepared by co-deposition has better performances in electrical conductivity, microhardness and tensile strength than the composite prepared by mechanical mixing, as shown in Table 2. Generally, the difculty of dispersing ND homogeneously in the matrix increases with added ND content. However, with the compar-

J. He et al. / Materials Science and Engineering A 490 (2008) 293299 Table 2 Properties of 3 wt.% ND/Cu composites with different preparation methods Preparation method Properties Density (g cm3 ) Co-deposition route Mechanical mixing 8.184 7.2 Electrical conductivity (% IACS) 86.5 45 Microhardness (HV) 128.9 126.5

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Tensile strength (MPa) 275.4 40.4

ison of Fig. 8(b)(d), the advantage of co-deposition method showed clearly that even at higher ND contents, ND particles also have better dispersion in the matrix than 3 wt.% ND/Cu composite prepared by mechanical mixing. 4. Conclusion ND/Cu composites with homogeneously dispersed ND particles within the Cu matrix can be fabricated by means of co-deposition route at a molecular-level mixing, which consists of the co-deposition of copper hydroxide and functionalized ND particles in a solvent. The functionalization of ND is the key step for the dispersion of ND in the matrix. In this work, the uorination by HF acid is effective for the surface functionalization of ND and for the attachment between Cu ions and ND particles. Comparing with other preparation methods, such as mechanical mixing, ND/Cu composites prepared by co-deposition route have very good microstructure and combined performances, and therefore will hold a promising future for industry application. Acknowledgements The authors acknowledge the nancial support by Tianjin Municipal Science and Technology Commission (No. 07ZCGHHZ00800) and Doctor Fund from the Educational Ministry of China (No. 20050056062). References
[1] O.A. Shenderova, V.V. Zhirnov, D.W. Brenner, Crit. Rev. Solid State 27 (2002) 227356. [2] A.E. Aleksenskii, M.V. Baidakova, A.Y. Vul, V.I. Siklitskii, Phys. Solid State 41 (1999) 668671. [3] A. Kr ger, F. Kataoka, M. Ozawa, T. Fujino, Y. Suzuki, A.E. Aleksenskii, u A.Ya. Vul, E. Osawa, Carbon 43 (2005) 17221730.

[4] D.S. Zhao, M. Zhao, Q. Jiang, Diam. Relat. Mater. 11 (2002) 234236. [5] A.V. Kvit, V.V. Zhirnov, T. Tyler, J.J. Hren, Composites B 35 (2004) 163166. [6] K. Iakoubovskii, M.V. Baidakova, B.H. Wouters, A. Stesmans, G.J. Adriaenssens, A.Ya. Vul, P.J. Grovet, Diam. Relat. Mater. 9 (2000) 861 865. [7] A.S. Barnard, S.P. Russo, I.K. Snook, Diam. Relat. Mater. 12 (2003) 18671872. [8] P.I. Belobrov, L.A. Bursill, K.I. Maslakov, A.P. Dementjev, Appl. Surf. Sci. 215 (2003) 169177. [9] V.Y. Dolmatov, G.K. Burkat, J. Superhard Mater. 1 (2000) 8495. [10] V.Y. Dolmatov, L.N. Kostrova, J. Sueperhard Mater. 3 (2000) 8285. [11] Y. Liu, V.N. Khabashesku, N.J. Halas, J. Am. Chem. Soc. 127 (2005) 37123713. [12] J.S. Wang, K. Matyjaszewski, J. Am. Chem. Soc. 117 (1995) 56145615. [13] M. Kato, M. Kamigaito, M. Sawamoto, T. Higashimura, Macromolecules 28 (1995) 17211723. [14] K. Matyjazewski, Curr. Org. Chem. 6 (2002) 6782. [15] T. Nishikawa, T. Ando, M. Kamigaito, M. Sawamoto, Macromolecules 30 (1997) 22442248. [16] K. Matyjaszewski, ACS Symp. Ser. 685 (1998) 258283. [17] V. Livramento, J.B. Correia, N. Shohoji, E. Osawa, Diam. Relat. Mater. 16 (2007) 202204. [18] K. Hanada, K. Yamamoto, T. Taguchi, E. Osawa, M. Inakuma, V. Livramento, J.B. Correia, N. Shohoji, Diam. Relat. Mater. 16 (2007) 2054 2057. [19] S.I. Cha, K.T. Kim, S.N. Arshad, C.B. Mo, S.H. Hong, Adv. Mater. 17 (2005) 13771381. [20] K. Hanada, T. Shoji, M. Mayuzui, T. Sano, Mater. Sci. Tech. 20 (2004) 11031108. [21] S. Ferro, A. De Battisti, J. Phys. Chem. B 107 (2003) 75677573. [22] L. Li, J.L. Davidson, C.M. Lukehart, Carbon 44 (2006) 23082315. [23] V.N. Khabashesku, J.L. Margrave, E.V. Barrera, Diam. Relat. Mater. 14 (2005) 859866. [24] A.E. Aleksensky, M.V. Baidakova, M.A. Yagovkina, V.I. Siklitsky, A.Ya. Vul, H. Naramoto, V.I. Lavrentiev, Diam. Relat. Mater. 13 (2004) 20762080. [25] V.Y. Dolmatov, Russ. Chem. Rev. 70 (2001) 607626. [26] S. Ferro, A. De Battisti, Anal. Chem. 75 (2003) 70407042. [27] J. Ding, N.Q. Zhao, C.S. Shi, X.W. Du, J.J. Li, J. Alloy Compd. 425 (2006) 390394.