Inorganic Materials, Vol. 40, No. 10, 2004, pp. 10431048. Translated from Neorganicheskie Materialy, Vol.

40, No. 10, 2004, pp. 11901196. Original Russian Text Copyright 2004 by Borovinskaya, Ignateva, Vershinnikov, Sachkova.

Preparation of Tungsten Carbide Nanopowders by Self-propagating High-Temperature Synthesis

I. P. Borovinskaya, T. I. Ignateva, V. I. Vershinnikov, and N. V. Sachkova
Institute of Structural Macrokinetics and Materials Research Problems, Russian Academy of Sciences, Chernogolovka, Moscow oblast, 142432 Russia e-mail: itian@ism.ac.ru
Received January 22, 2004

AbstractFine-particle tungsten carbide powders are produced from tungsten(VI) oxide by self-propagating high-temperature synthesis. The starting-mixture composition is shown to have a signicant effect on the phase composition, morphology, and particle size of the WC powder. A procedure is described for recovering tungsten carbide from intermediate products using chemical dispersion. The inuence of the dispersion agent on the morphology and particle size of the resultant powder is examined. The results indicate that the use of organic solvents for chemical dispersion prevents the formation of solid agglomerates, enhances the dissolution rate of impurities and defect-rich intercrystalline layers, and makes it possible to obtain tungsten carbide powders with a predominant particle size no greater than 0.050.2 m.

INTRODUCTION Transition-metal carbides, in particular, tungsten carbide, are now receiving ever increasing attention [1]. These materials offer high melting points, superior hardness, low friction coefcients, low reactivity, high oxidation resistance, and good electrical conductivity. Fine-particle tungsten carbide powders are being used increasingly in manufacturing wear-resistant parts, cutting tools, and Fe-free hard alloys. The most important phases in the WC system are WC and W2C [2]. Although W2C is unstable below 1300C [3], WC materials typically consist of a mixture of WC and W2C. WC powders can be prepared by a variety of processes, including direct carbonizing of tungsten powder. The rst step of this process is the preparation of ne-particle, pure tungsten metal from high-purity WO3 , tungstic acid, or ammonium tungstate [46]. The second step is the carbonizing of tungsten with carbon. The reaction may proceed according to two schemes, 2W + C or W+C WC, W2C

depending on the furnace, atmosphere, and carbon content. WC powders prepared in graphite furnaces under hydrogen atmosphere consist of irregularly shaped particles with smooth surfaces, no less than 35 m in size, containing at least 5% W2C. Reduction conditions have

a signicant effect on the characteristics of the powder metal and carbide [7]. Medeiros et al. [8] described a low-temperature ( 800) process for WC synthesis, which takes 2 h: gassolid reaction between a W precursor (ammonium paratungstate or tungsten oxide) and a mixture of H2 and CH4 . Gao and Kear [9] used a two-step thermochemical process to synthesize WC powder. First, they prepared tungsten nanopowders by reducing different tungsten salts and decomposing volatile tungsten compounds in the vapor phase. In the second step, they used low-temperature carbonizing in a controlled reactive carboncontaining vapor phase to obtain WC powder about 30 nm in particle size. In recent years, self-propagating high-temperature synthesis (SHS) has been widely used to prepare compounds of various classes in a broad range of particle sizes [10, 11]. We undertook systematic studies aimed at producing ultrane and nanostructured powders by SHS. As shown previously by the example of boron nitride [12], the particle size of SHS powders can be varied widely, including the nanometer range, by adjusting SHS parameters and using chemical dispersion (thermal treatment in different solvents) of SHS products. Earlier, Vershinnikov et al. [13] developed an SHS process, involving a reduction step, for producing tungsten carbide. In this paper, we analyze the effects of SHS conditions and chemical-dispersion parameters (compositions of solutions for the chemical dispersion of intermediate and nal products with the aim of preparing single-phase WC nanoparticles) on the particle size of SHS tungsten carbide powders.

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EXPERIMENTAL The starting materials used were 99.98+%-pure WO3 with an average particle size of 1012 m (commercially available material which is used in the production of hard alloys), P804-T furnace black less than 45 m in particle size, and I.PF-1 Mg powder (99.1+%) ranging from 0.25 to 0.50 mm in particle size. In addition, the starting mixtures contained various additives for controlling the combustion temperature: ammonium chloride, magnesium oxide, polyethylene, recycled SHS products, or mixtures of these materials. To mix the components and grind the SHS products, we used ball mills with steel grinding media. Synthesis was carried out in a 30-l SHS reactor under argon atmosphere. The particle size distribution was determined with a Fritsch particle sizer. Particle morphology was examined by electron microscopy on a JCXA-733 SuperProbe. In x-ray diffraction (XRD) studies, we used a DRON-2 diffractometer (u radiation). The specic surface area was determined by low-temperature nitrogen adsorption measurements using a gas chromatograph. The SHS products were analyzed chemically for W, C, and impurities. Carbon (total and free) was determined using a LECO IR-112 analyzer (inductive sample heating), and oxygen was determined by the coulometric titration of the CO2 released upon reduction melting of the sample in a graphite capsule under owing argon. Metal impurities were determined by atomic absorption on an AAS-3 spectrometer.

PREPARATION OF TUNGSTEN CARBIDE POWDERS To prepare tungsten carbide, we used the exothermic reaction between tungsten oxide, carbon (black), and magnesium metal: WO3 + C + 3Mg WC + 3MgO + Q.

The temperature of this process exceeds 3000C, which may cause decomposition of the forming tungsten carbide. To reduce the combustion temperature, we introduced different additives, inert or decomposing in the combustion wave to form gaseous products. The unstable additives also acted as dispersants, ensuring a small particle size of the SHS product. The sinter cake obtained in this way consisted of tungsten carbide and magnesium oxide. The latter was removed by etching in H2SO4 (1 : 4) or HCl (1 : 1) solutions: WC MgO + H2SO4 WC MgO + 2 HCl WC + MgSO4 + H2O, WC + MgCl2 + H2O.

The phase composition and particle size of the resultant powder were found to depend on the startingmixture composition: the carbon content inuenced the phase composition of the product (W2C content), while the magnesium content inuenced the particle size of the tungsten carbide recovered from WC MgO by etching. If the starting mixture contained a stoichiometric amount of magnesium, we obtained coarser particles (Fig. 1a), whereas a signicant excess of magnesium led to the formation of a material with a predominant particle size in the range 0.10.2 m (Fig. 1b).

(a)

10 m

(b)

10 m

(c)

10 m

Fig. 1. Microstructures of tungsten carbide powders: (a) stoichiometric amount of Mg in the starting mixture, (b) excess of Mg in the starting mixture, (c) after treatment in chromic acid mixture and alkaline solutions. INORGANIC MATERIALS Vol. 40 No. 10 2004

PREPARATION OF TUNGSTEN CARBIDE NANOPOWDERS N, % 10 100 (a) 80 Intensity, % 5 60 40 20

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0 0.1 10 0.51 (b) 5 10 50 100

32 38

41 50

56

62 68 2, deg

0 0.1 15 10 5 0 0.1 0.5 1 5 10 50 100 d, m

Fig. 2. Particle size distributions in WC powders: (ac) same as in Fig. 1.

0.5 1 (c)

10

50 100

Fig. 3. XRD pattern of puried WC powder (excess of Mg in the starting mixture).

The changes in the phase composition, elemental composition, and particle size of WC powder as a result of chemical dispersion in chromic acid mixture and alkaline solutions are illustrated in Table 1 and Figs. 1c, 2, and 3. As seen in Fig. 1c, the agglomerates break into small particles of hexagonal tungsten carbide. Figure 2 illustrates the effects of the starting-mixture composition and purication procedure on the particle size distribution in WC powders. It can be seen that purication markedly reduces the average particle size of the powder. The puried product consists of WC only, with no traces of oxides (Fig. 3). CHEMICAL DISPERSION WC is widely used in the production of cermets by sintering hard WC granules with a Co binder. Such materials contain a large percentage of hexagonal WC (high-melting component) embedded in a rigid Co matrix (low-melting component). The properties of WCCo alloys (hardness, density, durability, wear resistance, and thermal conductivity) depend strongly

The WC powder recovered from WC MgO by acidic enrichment consisted of large agglomerates of ne particles (Fig. 1b) and contained 0.5 to 2.5 wt % unreacted (free) carbon. To remove the free carbon, the powder was treated in a chromic acid mixture solution (5 g K2Cr2O7 in 100 ml H2SO4). As shown by XRD and chemical analysis, this step led to partial oxidation of WC to tungsten oxides, primarily to WO3 , which could easily be dissolved in a dilute alkaline solution.

Table 1. Effect of chemical dispersion on the elemental composition of tungsten carbide powder Dispersion solution Dispersion time, h 3.0 3.0 0.5
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Weight percent Ctotal 6.85 6.12 6.13

2004

Cfree 0.60 0.03 0.03

O 0.09 0.24 0.03

Mg 0.063

Cr

H2SO4(1 : 4) 5% K2Cr2O7 in H2SO4(conc) Aqueous 1% KOH

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0.005

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(a)

1 m

(b)

1 m

(c)

1 m

Fig. 4. Micrographs of WC powders treated in a mixture of HCl and HNO3 diluted with (a) water, (b) ethanol, or (c) butanol.

on the particle size of WC. As shown recently [14, 15], reducing the particle size of WC markedly improves the mechanical properties of WCCo, such as hardness, wear resistance, and strength. To obtain high-performance composites, the particle size of WC powder must be reduced to a submicron or nanometer level. At present, the particle size of commercially available WC powder ranges from 0.5 to 50 m. One promising approach to producing nanopowders is chemical etching of microparticles, which causes no dramatic changes in the structure and properties of the material [16]. The key feature of this approach is uniform material dissolution in acid or alkaline solutions. Previous work has shown that, by etching a ground SHS cake in appropriate solutions, one can dissolve defect-rich intercrystalline layers and remove impurities [17]. As a result, the sinter cake breaks into singlecrystal particles close in size to the primary SHS crystallites (down to 0.10.2 m), without compositional changes. This process is termed chemical dispersion.

We used this procedure to reduce the particle size of puried SHS WC powder to a nanometer level. According to XRD studies [18], storage of WC powder in water rst leads to oxidation of the particle surfaces, but in later stages of the process the thin WO3 lm fully dissolves according to the scheme WO3 + H2O WO 4 + 2H+.
2

To accelerate the rate of this process, WC powder recovered from the intermediate SHS product and puried in chromic acid mixture and alkaline solutions was treated in a 3 : 1 mixture of HCl and HNO3 diluted with water or an organic solvent (ethanol, isopropanol, butanol, or isoamyl alcohol). This procedure was found to markedly increase the specic surface of WC powders (Table 2). In view of the small average particle size, optical examination was carried out at very high magnications, up to 20000.

Table 2. Effect of chemical dispersion (3 : 1 mixture of HCl and HNO3 diluted with a solvent) on the specific surface S and composition of WC powder Solvent Water Ethanol Isopropanol Butanol Isoamyl alcohol
Note: S = 1.1 m2/g before etching. INORGANIC MATERIALS Vol. 40 No. 10 2004

S, m2/g 1.3 13.3 3.5 9.3 12.5

wt % Ctotal 6.13 4.59 5.92 5.16 4.93

wt % O 0.07 4.6 1.15 3.0 4.4

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(a)

1 m

(b)

1 m

(c)

1 m

Fig. 5. Micrographs of WC powders dispersed in different solvents and then etched in an alkaline solution: (ac) same as in Fig. 4.

The micrographs of such powders (Fig. 4) show that the surfaces of WC particles recovered from alcoholic solutions are covered with needle-like tungsten oxide crystallites, in contrast to aqueous solutions. This is also evidenced by chemical analysis and XRD. It seems likely that the alcoholic solutions prevent dissolution of the tungsten oxides formed during chemical dispersion, and the oxides adsorb on the surface of the WC particles. In view of this, the powders were again treated in alkaline solutions. Microstructural examination showed that the average particle size changed from 0.3 1.0 m for the WC powder recovered from aqueous solutions to 0.050.3 m for the powder recovered from the solution in butanol (Fig. 5). Note that the fraction of coarse particle after this step was smaller in the case of aqueous solutions as compared to organic solvents. The particles were oval in shape, with smooth surfaces, and were oriented at random.

Thus, the particles obtained by chemical dispersion in HCl + HNO3 solutions consist of a WC core 0.05 0.3 m in size and a dense tungsten oxide shell. The oxides act as surfactants, preventing tungsten carbide agglomeration. The particle size of WC crystallites depends on the nature of the diluent, in particular, on the length and degree of branching of its alkyl chain: increasing the chain length of the organic radical increases the solubility of WC powders and reduces their particle size. This can be accounted for by the better wettability of particle surfaces and penetration of the solution deeper into the pores in the particles in going from water to isoamyl alcohol. We assessed the sinterability of ne-particle SHS WC powders. Table 3 compares the physicochemical properties of a WCCo alloy prepared with the use of SHS WC and the commercial alloy VK6-OM (containing tungsten carbide produced by a furnace process).

Table 3. Physicochemical properties of WCCo alloys prepared using conventional (furnace process) and SHS WC Alloy Density, g/cm3 Hardness HRA Coercivity, A/m Flexural strength, MPa Durability coefficient Porosity, % Percentage of particles less than 1 m in size
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SHS WCCo 14.9 91 270 1700 1.4 0.04 80%

VK6-OM (commercial) 14.7 90.5 280 1300 1.0 0.2 60%

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BOROVINSKAYA et al. 8. Medeiros, F.F.P., Oliveira, S.A., De Souza, C.P., and Da Silva, A.G.P., Synthesis of WC through GasSolid Reaction at Low Temperature, Mater. Sci. Eng., A, 2001, vol. 315, no. 1/2, pp. 5862. 9. Gao, L. and Kear, B.H., Synthesis of Nanophase WC Powder by a Displacement Reaction Process, Nanostruct. Mater., 1997, vol. 9, p. 205. 10. Merzhanov, A.G., Advanced SHS-Ceramics: Today and Tomorrow Morning, Ceramics: Towards the 21st Century, Soga, N. and Kato, A., Eds., Tokyo: Ceramic Soc. of Japan, 1991, pp. 378403. 11. Merzhanov, A.G., Combustion: New Manifestation of an Ancient Process, Chemistry of Advanced Materials, Rao, C.N.R., Ed., Oxford: Blackwell, 1992, pp. 1939. 12. Borovinskaya, I.P., Ignateva, T.I., Vershinnikov, V.I., et al., Preparation of Ultrane Boron Nitride Powders by Self-propagating High-Temperature Synthesis, Neorg. Mater., 2003, vol. 39, no. 6, pp. 698704 [Inorg. Mater. (Engl. Transl.), vol. 39, no. 6, pp. 588593]. 13. Vershinnikov, V.I., Ignateva, T.I., Goziyan, A.V., et al., RF Patent 2200128, Byull. Izobret., 2000, no. 7. 14. Lange, F.F., Powder Processing Science and Technology for Increased Reliability, J. Am. Ceram. Soc., 1989, vol. 72, pp. 315. 15. Schubert, W.D., Bock, A., and Lux, B., General Aspects and Limits of Conventional Ultrane WC Powder Manufacture and Hard Metal Production, Int. J. Refract. Met. Hard Mater., 1995, vol. 13, pp. 281296. 16. Jia, K., Fischer, T.E., and Gallois, B., Microstructure, Hardness, and Toughness of Nanostructured and Conventional WCCo Composites, Nanostruct. Mater., 1998, vol. 10, p. 875. 17. Lee, C.-S., Lee, J.-S., and Oh, S.-T., Dispersion Control of Fe2O3 Nanoparticles Using a Mixed Type of Mechanical and Ultrasonic Milling, Mater. Lett., 2003, vol. 57, pp. 26432646. 18. Borovinskaya, I.P., Chemical Classes of the SHS Processes and Materials, Pure Appl. Chem., 1992, vol. 64, no. 7, pp. 919940. 19. Warren, A., Nylund, A., and Olefjord, I., Oxidation of Tungsten and Tungsten Carbide in Dry and Humid Atmospheres, Int. J. Refract. Met. Hard Mater., 1996, vol. 14, pp. 345353.

The exural strength, durability coefcient, and specic surface of the alloy produced from SHS WC exceed those of the commercial alloy. CONCLUSIONS The present results demonstrate that, using an SHS process with a reduction step, one can produce phasepure WC powder. The particle size of the product depends on the starting-mixture composition (an excess of magnesium leads to the formation of powders less than 1 m in particle size) and the nature of the dispersion agent. Subsequent treatment of the synthesized powder in different solutions ensures the removal of impurities and dissolution of defect-rich intercrystalline layers. As a result, the sinter cake breaks into single-crystal particles close in size to the primary SHS crystallites. The particle size of the powder thus treated depends on the solution composition. The SHS process described in this work is wellsuited to producing WC powders 0.10.3 m in particle size on a commercial scale. REFERENCES
1. Carbide, Nitride and Boride Materials., Synthesis and Processing, Weimer, W.A., Ed., London: Chapman & Hall, 1997. 2. Cottrell, A., Chemical Bonding in Transition Metal Carbides, London: Inst. of Materials, 1995, p. 77. 3. Schrunk, F.A., Constitution of Binary Alloys, New York: Genium, 1991. 4. Schwartzkopf, P. and Kieffer, R., Refractory Hard Metals, Borides, Carbides, Nitrides, and Silicides, New York: MacMillan, 1953. 5. Rieck, G.D., Tungsten and Its Compounds, Oxford: Pergamon, 1967. 6. Brookes, K.J., World Directory and Handbook of Hard Metals and Hard Materials, Hertfordshire: Int. Carbide Data, 1992, p. 8. 7. Tretyakov, V.I., Metallokeramicheskie tverdye splavy (Hard Cermets), Moscow, 1962, pp. 270276.

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