晶粒抑制剂对SPS烧结的WC基硬质合金的组织与性能的影响
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摘要
强化牙轮钻头、地质取芯钻头等常用的井下钻具最有效的材料是各种类型的碳化钨材料,因此,开发出高硬度、高韧性、高强度的硬质合金势在必行。本文分析了先进商用套磨铣工具材料的组织和性能,在此基础上设计了针对WC基硬质合金的晶粒抑制剂,通过高能球磨+SPS烧结技术制备出了性能优异的硬质合金。采用EDS、SEM、EPMA和XRD等分析方法研究了不同晶粒抑制剂对硬质合金组织的影响;通过致密度测定、硬度测试和三点弯曲试验评价了这些硬质合金的性能;最后探讨了这些抑制剂的作用机理。
试验结果表明,先进的商用WC基硬质合金中添加的抑制剂包括TaC、TiC和Cr_3C_2等相;因为晶粒抑制剂的作用,商用硬质合金具有较小的平均晶粒尺寸,因而具有较高的硬度,但是大量的晶粒抑制剂会导致棱角块状相的析出以及大量孔隙的形成,所以其韧性不高。
采用高能球磨技术,使原始粉末得到细化和活化,并在这一过程中通过扩散反应机制合成了少量纳米级WC粉末,其晶粒度为20～30nm。
稀土元素Y能够明显减少硬质合金组织的孔隙,使组织均匀致密,密度得到明显提高;虽然稀土元素Y对合金硬度的影响不大,但是能够提高塑性相α-Co的含量,明显改善合金的抗弯性能;TaC/Cr_3C_2和VC/Cr_3C_2这两种抑制剂组合能够明显细化晶粒,对硬度有所改善,但是组织中仍有孔隙;同时添加碳化物抑制剂TaC/Cr_3C_2和稀土抑制剂Y不仅能细化晶粒,组织也十分致密,晶粒一般呈短棒状,尺寸在1μm左右,而且硬度和抗弯强度都较高。其中,硬质合金B_2的组织和综合性能最佳:相对密度为99.40%,硬度为91.7 HRA,抗弯强度为2847 MPa。这些性能均超过了添加普通碳化物抑制剂(VC/ Cr_3C_2)的硬质合金和先进商用硬质合金。
All types of tungsten carbide reinforced materials have been proved to be the most effective materials to strengthen the cone bit, geological core bit and various kinds of downhole fishing tools etc. This suggests a need for the development of cemented carbides with high hardness,high toughness and high intensity. This paper analyzes the microstructure and the properties of advanced commercial milling tools materials, on that basis, new inhibitors combination are developed. High quality cemented carbides are prepared through high-energy ball grinding + SPS technique, so that their microstructure and the properties can exceed those of commercial cemented carbides. It is studied that how these inhibitors to influence the microstructure of cemented carbide by means of EDS, SEM, EPMA, XRD and so on. The properties of cemented carbides are evaluated through the density test, hardness test and 3-point bending test. Finally, action mechanism of these inhibitors combination is discussed.
The experimental results show that, advanced commercial WC based cemented carbides include inhibitors TaC、TiC and Cr_3C_2; Because the addition of a small amount of inhibitors will promotes fine grain size, the hardness of commercial cemented carbides are high; however, a lot of grain inhibitors will lead to the precipitation of edges massive phase and the formation of a great deal of pores, so their toughness are not very high.
Green powders get refining and activation by way of high energy ball grinding technology. And in this process,a small number of nano-WC powders are synthesized mainly through diffusion reaction mechanism, the crystallite size is 20～30nm.
Rare earth elements Y could dramatically reduce pores of microstructure of cemented carbide, make the microstructure uniform and compact, and density gets increased obviously. Rare earth elements Y exerts a little influence on the hardness of alloy,but it enhances the bending capacity of alloy significantly. These two kinds of inhibitors combination TaC/Cr3C2 and VC/Cr3C2 can fine grains obviously and increase the hardness,but there are still pores in the microstructure; Adding carbide inhibitors (TaC/Cr3C2) and rare earth inhibitors (Y) to alloy at the same time, which can not only fine grain size but also make the microstructure dense; the grain is like a long rod commonly, grain size is about 1μm, and the hardness and bending strength of this kind of alloy are higher. Particularly, the microstructure and comprehensive properties of cemented carbide-B2 with combinations of inhibitors ( 0.6 wt % Cr3C2– 4.8 wt %TaC– 0.4 wt %Y ) is the best, its relative density is 99.40%, its hardness is 91.7 HRA, its bending strength is 2847MPa, all of which exceed those of cemented carbide with ordinary carbide inhibitors(VC/ Cr3C2)and advanced commercial milling tools materials.
试验结果表明,先进的商用WC基硬质合金中添加的抑制剂包括TaC、TiC和Cr_3C_2等相;因为晶粒抑制剂的作用,商用硬质合金具有较小的平均晶粒尺寸,因而具有较高的硬度,但是大量的晶粒抑制剂会导致棱角块状相的析出以及大量孔隙的形成,所以其韧性不高。
采用高能球磨技术,使原始粉末得到细化和活化,并在这一过程中通过扩散反应机制合成了少量纳米级WC粉末,其晶粒度为20～30nm。
稀土元素Y能够明显减少硬质合金组织的孔隙,使组织均匀致密,密度得到明显提高;虽然稀土元素Y对合金硬度的影响不大,但是能够提高塑性相α-Co的含量,明显改善合金的抗弯性能;TaC/Cr_3C_2和VC/Cr_3C_2这两种抑制剂组合能够明显细化晶粒,对硬度有所改善,但是组织中仍有孔隙;同时添加碳化物抑制剂TaC/Cr_3C_2和稀土抑制剂Y不仅能细化晶粒,组织也十分致密,晶粒一般呈短棒状,尺寸在1μm左右,而且硬度和抗弯强度都较高。其中,硬质合金B_2的组织和综合性能最佳:相对密度为99.40%,硬度为91.7 HRA,抗弯强度为2847 MPa。这些性能均超过了添加普通碳化物抑制剂(VC/ Cr_3C_2)的硬质合金和先进商用硬质合金。
All types of tungsten carbide reinforced materials have been proved to be the most effective materials to strengthen the cone bit, geological core bit and various kinds of downhole fishing tools etc. This suggests a need for the development of cemented carbides with high hardness,high toughness and high intensity. This paper analyzes the microstructure and the properties of advanced commercial milling tools materials, on that basis, new inhibitors combination are developed. High quality cemented carbides are prepared through high-energy ball grinding + SPS technique, so that their microstructure and the properties can exceed those of commercial cemented carbides. It is studied that how these inhibitors to influence the microstructure of cemented carbide by means of EDS, SEM, EPMA, XRD and so on. The properties of cemented carbides are evaluated through the density test, hardness test and 3-point bending test. Finally, action mechanism of these inhibitors combination is discussed.
The experimental results show that, advanced commercial WC based cemented carbides include inhibitors TaC、TiC and Cr_3C_2; Because the addition of a small amount of inhibitors will promotes fine grain size, the hardness of commercial cemented carbides are high; however, a lot of grain inhibitors will lead to the precipitation of edges massive phase and the formation of a great deal of pores, so their toughness are not very high.
Green powders get refining and activation by way of high energy ball grinding technology. And in this process,a small number of nano-WC powders are synthesized mainly through diffusion reaction mechanism, the crystallite size is 20～30nm.
Rare earth elements Y could dramatically reduce pores of microstructure of cemented carbide, make the microstructure uniform and compact, and density gets increased obviously. Rare earth elements Y exerts a little influence on the hardness of alloy,but it enhances the bending capacity of alloy significantly. These two kinds of inhibitors combination TaC/Cr3C2 and VC/Cr3C2 can fine grains obviously and increase the hardness,but there are still pores in the microstructure; Adding carbide inhibitors (TaC/Cr3C2) and rare earth inhibitors (Y) to alloy at the same time, which can not only fine grain size but also make the microstructure dense; the grain is like a long rod commonly, grain size is about 1μm, and the hardness and bending strength of this kind of alloy are higher. Particularly, the microstructure and comprehensive properties of cemented carbide-B2 with combinations of inhibitors ( 0.6 wt % Cr3C2– 4.8 wt %TaC– 0.4 wt %Y ) is the best, its relative density is 99.40%, its hardness is 91.7 HRA, its bending strength is 2847MPa, all of which exceed those of cemented carbide with ordinary carbide inhibitors(VC/ Cr3C2)and advanced commercial milling tools materials.
引文
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