利用纳米晶W、Co、C过渡相粉末制备硬质合金的研究
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摘要
纳米晶硬质合金具有高强度和高硬度等一系列优异的力学性能,可广泛应用于航天、信息、模具、切削刀具等领域。然而,纳米硬质合金粉末烧结过程中WC晶粒的快速长大行为使得难于获得真正意义上的纳米晶硬质合金块体材料。
为此,本研究探索了以高能球磨法制备的纳米晶W、Co、C过渡相粉末为原料来制备超细晶/纳米晶硬质合金的新工艺。利用X-ray,SEM等分析测试技术对该过渡相粉末固相烧结时的相转变特征、WC晶粒长大特性、WC晶粒长大的抑制、碳含量的控制及性能等进行了研究。
结果表明纳米晶W、Co、C过渡相粉末在烧结过程中转化为W_2C,Co_6w_6C,Co_3W_3C过渡相。烧结温度升高或烧结时间延长,有助于该过渡相将转化为WC和Co。1375℃烧结30min,可获得密度为14.46g/cm~3,收缩率为27.2%的致密YG10硬质合金。
改性纳米ZrO_2粉体可有效细化WC晶粒,促进烧结致密化,并显著提高硬质合金的硬度,是一种有效的WC晶粒长大抑制剂。而利用外加0.3-0.42wt%的碳黑可有效弥补烧结时合金碳含量的损失,获得碳含量位于5.37-5.53wt%间,相组成为WC和β-Co,强度、硬度分别为2763MPa和91.1HRA的硬质合金。烧结合金中WC晶粒为长棒状结构,1375℃烧结30min时其径向尺寸约为100nm左右,长度约为1.2μm。
利用纳米晶W、Co、C过渡相粉末为原料有望获得原位生成的长棒状WC晶粒增强的硬质合金,是一种可行的制备高性能硬质合金的新工艺。
Nano-grained cemented carbides possess a series of excellent mechanical performances such as high transverse rupture strength and high hardness, which can meet the urgent demands in aerospace, information technology, mould and cutting application. However, the rapid intrinsic growth characteristic of nanometer WC grain during sintering process lead nano-grained cemented carbides with excellent mechanical performances is not acquired.Therefore, the purpose of this dissertation was explored the preparation of superfine grain or nano-grained cemented carbide, which used nano-grained W、 Co、 C transitional phase powders as raw materials through high energy ball milling W-Co-C mixed powders.In this paper, phase transformation, WC grain growth characteristic and WC grain growth inhibiting during sintering of W、 Co、 C transitional phase powders were studied by X-ray and SEM. Carbon content control, performances of sintered alloys was also studied.During sintering process, nano-grained W、 Co、 C transitional phase powders transformed into transitional phases such as W_2C, Co_6W_6C and Co_3W_3C. These transitional phases would be completely transformed into WC and Co by the diffusion of carbon when sintering temperature increased or sintering time prolonged. So, YG10 cemented carbides with sintering density 14.46g/cm~3 and shrinkage rate 27.2% were obtained when W、 Co、 C transitional phase powders compacts sintering at 1375℃ for 30min.Research showed that modified nanometer ZrO_2 could effectively decrease the size of WC grain, promote sintering densification and remarkable improve the hardness of cemented carbides, which was a kind of effective WC grain growth inhibitor. And introduction of 0.3-0.42wt% carbon black excess effectively balanced the carbon loss due to the absorption of O_2. And cemented carbides with carbon content 5.37-5.53wt%composed of WC and β-Co phase, which strength and hardness were 2763MPa and 91.1HRA respectively, were acquired.Rod-like WC grains with 100nm in radial dimension and 1.2 am in length were formed as sintering at 1375℃ for 30min. In-situ formation of
nanometer rod-like WC reinforced cemented carbide is hopeful being obtained using nano-grained W> Co> C transitional phase powders as raw materials, and which is a feasible new method of fabrication high performance hardmetal alloy.
为此,本研究探索了以高能球磨法制备的纳米晶W、Co、C过渡相粉末为原料来制备超细晶/纳米晶硬质合金的新工艺。利用X-ray,SEM等分析测试技术对该过渡相粉末固相烧结时的相转变特征、WC晶粒长大特性、WC晶粒长大的抑制、碳含量的控制及性能等进行了研究。
结果表明纳米晶W、Co、C过渡相粉末在烧结过程中转化为W_2C,Co_6w_6C,Co_3W_3C过渡相。烧结温度升高或烧结时间延长,有助于该过渡相将转化为WC和Co。1375℃烧结30min,可获得密度为14.46g/cm~3,收缩率为27.2%的致密YG10硬质合金。
改性纳米ZrO_2粉体可有效细化WC晶粒,促进烧结致密化,并显著提高硬质合金的硬度,是一种有效的WC晶粒长大抑制剂。而利用外加0.3-0.42wt%的碳黑可有效弥补烧结时合金碳含量的损失,获得碳含量位于5.37-5.53wt%间,相组成为WC和β-Co,强度、硬度分别为2763MPa和91.1HRA的硬质合金。烧结合金中WC晶粒为长棒状结构,1375℃烧结30min时其径向尺寸约为100nm左右,长度约为1.2μm。
利用纳米晶W、Co、C过渡相粉末为原料有望获得原位生成的长棒状WC晶粒增强的硬质合金,是一种可行的制备高性能硬质合金的新工艺。
Nano-grained cemented carbides possess a series of excellent mechanical performances such as high transverse rupture strength and high hardness, which can meet the urgent demands in aerospace, information technology, mould and cutting application. However, the rapid intrinsic growth characteristic of nanometer WC grain during sintering process lead nano-grained cemented carbides with excellent mechanical performances is not acquired.Therefore, the purpose of this dissertation was explored the preparation of superfine grain or nano-grained cemented carbide, which used nano-grained W、 Co、 C transitional phase powders as raw materials through high energy ball milling W-Co-C mixed powders.In this paper, phase transformation, WC grain growth characteristic and WC grain growth inhibiting during sintering of W、 Co、 C transitional phase powders were studied by X-ray and SEM. Carbon content control, performances of sintered alloys was also studied.During sintering process, nano-grained W、 Co、 C transitional phase powders transformed into transitional phases such as W_2C, Co_6W_6C and Co_3W_3C. These transitional phases would be completely transformed into WC and Co by the diffusion of carbon when sintering temperature increased or sintering time prolonged. So, YG10 cemented carbides with sintering density 14.46g/cm~3 and shrinkage rate 27.2% were obtained when W、 Co、 C transitional phase powders compacts sintering at 1375℃ for 30min.Research showed that modified nanometer ZrO_2 could effectively decrease the size of WC grain, promote sintering densification and remarkable improve the hardness of cemented carbides, which was a kind of effective WC grain growth inhibitor. And introduction of 0.3-0.42wt% carbon black excess effectively balanced the carbon loss due to the absorption of O_2. And cemented carbides with carbon content 5.37-5.53wt%composed of WC and β-Co phase, which strength and hardness were 2763MPa and 91.1HRA respectively, were acquired.Rod-like WC grains with 100nm in radial dimension and 1.2 am in length were formed as sintering at 1375℃ for 30min. In-situ formation of
nanometer rod-like WC reinforced cemented carbide is hopeful being obtained using nano-grained W> Co> C transitional phase powders as raw materials, and which is a feasible new method of fabrication high performance hardmetal alloy.
引文
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[2] Gillea G, Szesny B, Dreyer K, et al. Submicron and ultrafine grained hardmetals for microdrills and metal cutting inserts. International Journal of Refractory Metals & Hard Materials, 2002, 20(3): 3-22
[3] Asada N, Yamamoto Y. Particle Size of Fine Grain WC by the 'Continuous Direct Carburizing Process'. Metal Powder Report, 1990, 45(1): 60-64
[4] 唐振方.反应性热等离子体合成超细粉体及其特性研究:[博士学位论文].广州:中山大学,2001
[5] 张汉林,刘韩星,欧阳世翕,等.流化床还原碳化法制备超细WC-Co复合粉末.粉末冶金技术,1995,13(3):202-204
[6] 邵刚勤,吴伯麟.用流态化工艺制备WC-Co粉末.金属学报,1999,35(2):144-146
[7] Mohan K, Strutt P R. Microstructure of spray converted nanostruetured tungsten carbide-cobalt composite. Materials Science & Engineering A: Structural Materials: Properties, Microstructure and Processing, 1996, 209(1-2): 237-242
[8] 高荣根.纳米结构WC-Co复合粉末的制备与应用.粉末冶金技术,1995,13(7):49-54
[9] Seegopaul P, McCandlish L E, Shinneman F M. Production capability and powder processing methods for nanostructured WC-Co powder. International Journal of Refractory Metals & Hard Materials, 1997, 15(3): 133-138
[10] Zhong Y Z, Wahlberg S, Ming S W, et al. Processing of nanostructured WC-Co powder from precursor obtained by co-precipitation. Nanostructured Materials, 1999, 12(4): 163-166
[11] Wahlberg S, Crenthe I, Muhammered M. Nanostructured hard material composites by molecular engineering Ⅰ. Synthesis from soluble tungstate salts Nanostructured Materials, 1997, 9(1): 105-105
[12] Srikanth R, David L B.Synthesis and Evaluation of Advanced Nanocrystalline Tungsten-based Materials. Powder Metallurgy Science & Technology Briefs, 1999, 1(1): 9-14
[13] 马学鸣,赵凌,董远达.机械合金化制备纳米硬质合金.上海大学学报,1998,4(2):156-159
[14] Wang G M, Campbell S J. Synthesis and structural evolution of tungsten carbide prepared by ball milling. Journal of Materials Science, 1997, 32(3): 1461-1467
[15] 唐振方,高勇,杨远政,等.WC粉体的高能球磨超细化.中国有色金属学报,2000,10(1):246-249
[16] 毛昌辉.高能机械研磨纳米结构WC-Co复合粉末的研究.稀有金属,1999,23(3):185-190
[17] Goren-Muginstein G R, Berger S, Rosen A. Sintering study of nanocrystalline tungsten carbide powders. Nanostructured Materials, 1998, 10(5): 795-804
[18] 黎文献,唐嵘.用MA制超细WC-Co-Cr_3C_2复合粉.中国有色金属学报,1998,8(增1):90-92
[19] Sherif E E M. Fabrication of nanocrystalline WC and nanocomposite WC-MgO refractory materials at room temperature. Journal of Alloys and Compounds, 2000, 296(5): 175-182
[20] Tan G L, Wu X. Mechanochemical synthesis of nanocrystalline tungsten carbide powders. Powder Metallurgy, 1998, 41(4): 300-302
[21] Ha G H, Kim B K. Synthesis of ultrafine WC/Co powder by mechanochemical process. Powder Metallurgy, 2002, 45(1): 29-32
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