粗晶WC-Co硬质合金的制备工艺研究
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摘要
在Co含量相同的条件下,与传统的中、细晶粒硬质合金相比,粗晶粒硬质合金具有极高的热导率,较好的抗热疲劳与抗热冲击性能,主要用于极端工况条件下软岩连续挖掘用矿用工具、冲压模、冷镦模、轧辊等,具有非常广阔的市场前景。而目前WC晶粒度≥4.5μm的硬质合金属国内空白。本文的研究目的是探索晶粒度≥4.5μm的高性能粗晶WC-Co硬质合金的制备工艺。
本研究分三部分,首先通过原料与制备工艺参数对合金中WC晶粒度的影响规律,探讨了传统湿磨工艺制备WC-Co硬质合金中WC晶粒度的最粗极限；随后通过干混合工艺研究,探讨了WC-Co硬质合金中WC晶粒度的提高途径；在上述研究基础上,开发了化学包裹粉工艺制备晶粒度≥4.5μm WC-Co硬质合金的新技术。采用扫描电镜观察粉末与合金中WC晶粒的形貌,采用x射线衍射仪分析粉末的物相组成,采用金相显微镜观察合金的组织结构。本研究得到以下结论：
(1)传统湿磨工艺虽然保证了WC与Co两相的均匀混合,但因WC属脆性材料,湿磨过程中WC二次颗粒与一次颗粒容易破碎,采用费氏粒度(FSSS)高达28.3μm的WC原料,即使湿磨时间缩短至24h也难以制备出晶粒度≥4.5μm的粗晶WC-Co硬质合金。
(2)与传统湿磨工艺相比,干混合工艺不会对WC粉末产生破碎作用。以FSSS为6.26μm的低团聚WC粉为原料,采用干混合工艺制备出了晶粒度≥5μm的粗晶WC-Co硬质合金；但干混合制备的混合料中WC颗粒粗大、形状不规则、存在大量硬团聚体,压坯中易产生大孔洞与未压好等缺陷,这类缺陷难以通过液相烧结得到有效消除,严重影响了合金的力学性能。
(3)采用化学包裹粉工艺制备粗晶WC-Co硬质合金,不但克服了传统湿磨工艺制备混合料过程中WC粒度显著减小的问题,而且改善了WC、Co两相分布的均匀程度,改变了WC与Co的结合方式—Co呈现多孔泡沫状纳米组装结构形式包裹在WC粉末表面。以FSSS为6.26μm经过特殊预处理的WC粉为原料,采用化学包裹粉工艺成功地制备了WC-Co硬质合金。结果表明,合金组织结构均匀,WC晶粒结晶完整,晶粒呈现边角圆化特征；合金中WC平均晶粒度≥4.8μm。制备的WC-20%Co合金的横向断裂强度达2750MPa,洛氏硬度HRA达83.4,达到了Sandvik同类产品的质量水平。
Compared with medium/fine cemented carbides, coarse-grained cemented carbide has a higher thermal conductivity, better thermal fatigue resistance and thermal shock resistance under the condition of the same Co content, mainly applied in mining tools used in continuous excavation in extreme working conditions, punching dies, cold punching dies, rollers and so on. This kind of cemented carbides has very broad market prospects. At present, no production of cemented carbide has been reported with WC grain size above 4.5μm in China. The purpose of this paper is to explore the preparation technique of coarse-grained WC-Co cemented carbide with WC grain size above 4.5μm and high-performance.
This study includes three parts. Firstly, the limit of size of WC grain in cemented carbide prepared by traditional wet mixing was studied, according to the effects of raw materials and process parameters on the WC grain size of cemented carbide; Secondly, method of increasing WC grain size in WC-Co cemented carbide was explored through the study of dry mixing; Finally, on the basis of the investigations mentioned above, a novel technology called "chemical-powder-wrapping" is developed, for the preparation of coarse-grained cemented with a WC grain size above 4.5μm. The morphology of the powders and the WC grain in alloys was observed by scanning electron microscopy (SEM); phase composition of the powders was analyzed by X-ray diffraction (XRD), and microstructure of alloys was observed by metallographic microscope. The results are as follows:
(1) Although traditional wet mixing ensures Co distributes in WC uniformly, primary particles and secondary particles of WC are so easily crashed that WC grain size is reduced, as WC is brittle material. Thus, reducing wet mixing time to only 24 hours can not prepare coarse-grained cemented carbide with WC grain size above 4.5μm, even if WC powder which has a particle of FSSS 28.3μm is ued.
(2) Compared with the traditional wet mixing, dry mixing has no fragmentation effect on grain size of WC in slurry, thus ensures the grain size of WC in alloys. Coarse-grained cemented carbide with WC grain size above 5μm is prepared by dry mixing using WC powder which has a particle size of 6.26μm (FSSS) as starting material; nevertheless, because of bigness, roughness, irregular shape and hard aggregate of WC powder in the slurry prepared by dry mixing, defects in the green compact, e.g. big voids and uncompacted will be present and remain in the alloy, decreasing the mechanical properties of cemented carbide.
(3) The "chemical-powder-wrapping" technology does not only overcome the defect of wet mixing reducing WC grain size remarkably, but also improves the distribution of Co in WC and changes the manner of combination of WC and Co, Co is wrapping WC by means of nano-phased self-assembly form structure. WC-Co cemented carbide is prepared by "chemical-powder-wrapping" technology using WC powder which has a particle size of 6.26μm (FSSS) as starting material successfully. Before that, the WC powder has a special pretreatment. The results show that the alloy has a homogeneous microstructure with crystalline perfection of WC whose rims are rounded. The cemented carbide has a average grain size of WC above 4.8μm. WC-20%Co cemented carbide was prepared with this method with transverse rupture strength 2750 MPa and Rockwell hardness 83.4, reaching the level of similar products produced by Sandvik Corporation.
本研究分三部分,首先通过原料与制备工艺参数对合金中WC晶粒度的影响规律,探讨了传统湿磨工艺制备WC-Co硬质合金中WC晶粒度的最粗极限；随后通过干混合工艺研究,探讨了WC-Co硬质合金中WC晶粒度的提高途径；在上述研究基础上,开发了化学包裹粉工艺制备晶粒度≥4.5μm WC-Co硬质合金的新技术。采用扫描电镜观察粉末与合金中WC晶粒的形貌,采用x射线衍射仪分析粉末的物相组成,采用金相显微镜观察合金的组织结构。本研究得到以下结论：
(1)传统湿磨工艺虽然保证了WC与Co两相的均匀混合,但因WC属脆性材料,湿磨过程中WC二次颗粒与一次颗粒容易破碎,采用费氏粒度(FSSS)高达28.3μm的WC原料,即使湿磨时间缩短至24h也难以制备出晶粒度≥4.5μm的粗晶WC-Co硬质合金。
(2)与传统湿磨工艺相比,干混合工艺不会对WC粉末产生破碎作用。以FSSS为6.26μm的低团聚WC粉为原料,采用干混合工艺制备出了晶粒度≥5μm的粗晶WC-Co硬质合金；但干混合制备的混合料中WC颗粒粗大、形状不规则、存在大量硬团聚体,压坯中易产生大孔洞与未压好等缺陷,这类缺陷难以通过液相烧结得到有效消除,严重影响了合金的力学性能。
(3)采用化学包裹粉工艺制备粗晶WC-Co硬质合金,不但克服了传统湿磨工艺制备混合料过程中WC粒度显著减小的问题,而且改善了WC、Co两相分布的均匀程度,改变了WC与Co的结合方式—Co呈现多孔泡沫状纳米组装结构形式包裹在WC粉末表面。以FSSS为6.26μm经过特殊预处理的WC粉为原料,采用化学包裹粉工艺成功地制备了WC-Co硬质合金。结果表明,合金组织结构均匀,WC晶粒结晶完整,晶粒呈现边角圆化特征；合金中WC平均晶粒度≥4.8μm。制备的WC-20%Co合金的横向断裂强度达2750MPa,洛氏硬度HRA达83.4,达到了Sandvik同类产品的质量水平。
Compared with medium/fine cemented carbides, coarse-grained cemented carbide has a higher thermal conductivity, better thermal fatigue resistance and thermal shock resistance under the condition of the same Co content, mainly applied in mining tools used in continuous excavation in extreme working conditions, punching dies, cold punching dies, rollers and so on. This kind of cemented carbides has very broad market prospects. At present, no production of cemented carbide has been reported with WC grain size above 4.5μm in China. The purpose of this paper is to explore the preparation technique of coarse-grained WC-Co cemented carbide with WC grain size above 4.5μm and high-performance.
This study includes three parts. Firstly, the limit of size of WC grain in cemented carbide prepared by traditional wet mixing was studied, according to the effects of raw materials and process parameters on the WC grain size of cemented carbide; Secondly, method of increasing WC grain size in WC-Co cemented carbide was explored through the study of dry mixing; Finally, on the basis of the investigations mentioned above, a novel technology called "chemical-powder-wrapping" is developed, for the preparation of coarse-grained cemented with a WC grain size above 4.5μm. The morphology of the powders and the WC grain in alloys was observed by scanning electron microscopy (SEM); phase composition of the powders was analyzed by X-ray diffraction (XRD), and microstructure of alloys was observed by metallographic microscope. The results are as follows:
(1) Although traditional wet mixing ensures Co distributes in WC uniformly, primary particles and secondary particles of WC are so easily crashed that WC grain size is reduced, as WC is brittle material. Thus, reducing wet mixing time to only 24 hours can not prepare coarse-grained cemented carbide with WC grain size above 4.5μm, even if WC powder which has a particle of FSSS 28.3μm is ued.
(2) Compared with the traditional wet mixing, dry mixing has no fragmentation effect on grain size of WC in slurry, thus ensures the grain size of WC in alloys. Coarse-grained cemented carbide with WC grain size above 5μm is prepared by dry mixing using WC powder which has a particle size of 6.26μm (FSSS) as starting material; nevertheless, because of bigness, roughness, irregular shape and hard aggregate of WC powder in the slurry prepared by dry mixing, defects in the green compact, e.g. big voids and uncompacted will be present and remain in the alloy, decreasing the mechanical properties of cemented carbide.
(3) The "chemical-powder-wrapping" technology does not only overcome the defect of wet mixing reducing WC grain size remarkably, but also improves the distribution of Co in WC and changes the manner of combination of WC and Co, Co is wrapping WC by means of nano-phased self-assembly form structure. WC-Co cemented carbide is prepared by "chemical-powder-wrapping" technology using WC powder which has a particle size of 6.26μm (FSSS) as starting material successfully. Before that, the WC powder has a special pretreatment. The results show that the alloy has a homogeneous microstructure with crystalline perfection of WC whose rims are rounded. The cemented carbide has a average grain size of WC above 4.8μm. WC-20%Co cemented carbide was prepared with this method with transverse rupture strength 2750 MPa and Rockwell hardness 83.4, reaching the level of similar products produced by Sandvik Corporation.
引文
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