以石墨烯为碳源的硬质合金制备与性能

以N-甲基吡咯烷酮分散的石墨烯代替常规的冶金炭黑作为碳源,采用短流程原位还原碳化反应制备出纳米晶WC-Co复合粉末。采用放电等离子烧结系统对复合粉末进行快速烧结致密化。结果表明,石墨烯作为碳源可显著降低原位还原碳化反应温度,复合粉末粒径细小且分布均匀。得到的超细晶硬质合金块体材料平均晶粒尺寸约为290 nm,HV_(30)硬度值为13.877±0.131 GPa,断裂韧性KIC值为8.3±0.1 MPa·m~(1/2)。通过HRTEM观测表明,试样中WC/WC晶界、WC/Co相界、WC/C相界具有很高的匹配度。     

以石墨烯为碳源的硬质合金制备与性能研究

以N-甲基吡咯烷酮分散的石墨烯代替常规的冶金炭黑作为碳源,采用短流程原位还原碳化反应制备出纳米晶WC-Co复合粉末,石墨烯作为碳源可显著降低原位还原碳化反应温度,复合粉末粒径细小且分布均匀。采用放电等离子烧结系统对复合粉末进行快速烧结致密化,得到平均晶粒尺寸为~290nm的超细晶硬质合金块体材料,具有硬度值HV30为1387.7±13.1kg/mm2,断裂韧性KIC值为8.3±0.1MPa?m1/2的良好力学性能,通过HRTEM观测得到试样中WC/WC晶界、WC/Co相界、WC/C相界具有很高的匹配度。     

VC添加量对纳米晶硬质合金的制备及性能影响

以钨钴氧化物、炭黑和VC为原料,采用原位还原碳化法制备WC-Co复合粉末,将复合粉末进行放电等离子烧结致密化制备WC-Co硬质合金块体材料。研究了不同VC添加量的复合粉末和块体材料的相组成、显微组织和性能,结果表明:VC的添加量对复合粉末的相组成、合金的晶粒尺寸和性能具有重要的影响,原料中添加2.0%VC(质量分数)时可获得平均晶粒尺寸为101 nm,相组成仅为WC和Co且具有高硬度和良好韧性的硬质合金块体材料。     

纯相低氧纳米WC-Co复合粉的制备

以紫钨、四氧化三钴、炭黑为原料,在高真空度条件下利用原位反应合成技术制备出物相纯净、平均粒径约为80 nm的WC-Co复合粉。研究了制备工艺参数对纳米复合粉相组成、粒径、氧含量及最终烧结硬质合金块体材料组织性能的影响。结果表明,纳米复合粉中氧含量较高时,会导致后续烧结过程中发生脱碳反应,使烧结制备的块体材料致密度和力学性能明显下降。将纳米复合粉在800℃下真空热处理2.5 h可有效降低粉末中的氧含量,同时热处理后的粉末颗粒无明显长大,平均粒径为85 nm。向复合粉中加入1.1%TiC与0.9%VC进行SPS烧结,烧结块体平均晶粒尺寸为105 nm,且尺寸分布均匀,致密度达99%以上,硬度(HV30)为21 450 MPa,断裂韧性达到9.81 MPa·m~(1/2)。     

纳米Al2O3p化学镀铜复合粉末的烧结致密化

化学镀是制备纳米颗粒增强金属基复合材料的有效方法.对纳米Al2O3p化学镀铜粉末的烧结致密化特点进行了研究,分析了化学镀粉末的预处理、成型压力、烧结温度、保温时间、复压复烧工艺等对致密化的影响.在优化各影响因素的情况下,对Al2O3含量为10%的化学镀铜粉末采用常规粉末冶金工艺得到了相对致密度达94%的试样.     

机械合金化PM304粉末的烧结特性

采用高能球磨方法制备了PM304复合粉末。研究了纳米PM304粉末的真空烧结致密化和显微组织演化现象，并与未球磨粉末的烧结试样进行了比较。结果表明，提高烧结温度和延长烧结时间有利于提高相对密度，同时组织长大。1100℃，2h是最佳烧结工艺。机械合金化导致粉末纳米化，使真空烧结后的显微组织结构明显细化，使试样的相对密度和抗拉强度比未球磨粉末烧结后的试样有显著提高。     

碳化帆颗粒尺寸对纳米晶硬质合金组织和性能的影响

利用原位还原碳化反应制备纳米尺度的WC-Co复合粉体,应用放电等离子烧结(SPS)技术制备出纳米晶WC-Co硬质合金块体材料。分析了晶粒长大抑制剂碳化钒(VC)颗粒尺寸对纳米晶硬质合金的显微组织、晶粒尺寸及分布和力学性能的影响。结果表明:当VC的粒径减小到100 nm以下时,利用快速烧结技术可制备得到平均晶粒尺寸约为70 nm的致密WC-Co硬质合金块体材料,其物相纯净,晶粒尺寸分布均匀,维氏硬度为19.84 GPa,断裂韧性达到12.10 MPa·m1/2。     

纳米及超细复合粉添加对超粗晶硬质合金晶粒长大的影响及机制

在粗颗粒WC/Co混合粉末中分别添加平均粒径为100、250、400nm的WC-8Co复合粉,经球磨混合压坯后在不同温度进行Ar气保护烧结。针对烧结块体的形貌、晶粒尺寸及其分布进行了研究,并分析了复合粉添加对不同烧结阶段WC晶粒长大的影响机理。研究发现,在WC/Co混合粉中加入纳米和亚微米复合粉末均可制备得到超粗晶硬质合金,且添加纳米复合粉烧结的试样平均晶粒尺寸达到9.3μm。烧结初期,纳米和亚微米复合粉通过增加混合粉末的表面能而有效促进WC晶粒长大;当达到液相烧结温度时,添加纳米复合粉的烧结块体中,由于小晶粒具有更大的溶解驱动力,促使小晶粒溶解并在周围大晶粒表面析出,进一步增大烧结块体的晶粒尺寸;添加亚微米复合粉的块体中,小晶粒WC呈集中分布,使其溶解驱动力较小,且析出主要发生在周围细小晶粒之间,达到溶解析出动态平衡,从而使烧结块体的平均晶粒尺寸增长缓慢。     

纳米晶Mo-Cu复合粉末烧结行为的研究

采用溶胶-喷雾干燥-煅烧-氢气还原的方法制备了纳米晶Mo-18Cu、Mo-30Cu、Mo-40Cu复合粉末,研究了纳米晶Mo-Cu粉末的烧结行为以及Cu含量对致密化的影响.结果表明,纳米晶Mo-Cu复合粉末致密化程度高,速度快,在1050～1200 ℃烧结,Mo-30Cu和Mo-40Cu的相对密度可达98%以上,且合金晶粒细小,而Mo-18Cu在1350 ℃以上烧结,相对密度也可达98%以上,但晶粒聚集长大到5 μm左右.研究发现Mo-Cu复合粉末形成了亚稳态的超饱和Mo(Cu)固溶体,随着烧结温度的升高,Cu相逐渐从亚稳态的超饱和Mo(Cu)固溶体颗粒中析出.     

放电等离子烧结法制备ITO靶材

采用单相的ITO复合粉末经放电等离子烧结法(SPS)快速制备了ITO靶材.研究了SPS的主要工艺参数对ITO靶材致密化的影响.结果表明:靶材的相对密度随着烧结温度的升高而增大,在1000 ℃时达到最大值;在1000 ℃下烧结,延长保温时间使相对密度降低;在较低的温度下烧结时,延长保温时间有利于提高靶材的致密度;相对密度随着烧结压力的增加而增大;升温速率过快不利于靶材的致密化.对烧结试样的相组成和化学成分研究表明:不同温度下制备的ITO靶材均有少量的SnO_2相析出,并有不同程度的失氧,铟锡的质量分数略大于ITO原粉中铟锡的质量分数.     

Study on the diamond/ultrafine WC-Co cermets interface formed in a SPS consolidated composite

Nanocrystalline WC-Co composite powder and coated tungsten diamond by using vacuum vapor deposition were consolidated by the spark plasma sintering （SPS） process to prepare diamond-enhanced WC-Co cemented carbide composite materials. The interface microstructures between coated tungsten diamond and WC-Co cemented carbide matrix were investigated by scanning electron microscopy （SEM） and energy dispersive X-ray spectroscopy （EDXS）. The results showed that there is a transitional layer between the diamond and the matrix, in which the carbon content is 62.97wt.%, and the content of cobalt in the transitional zone is 6.19wt.%; the content of cobalt in the WC-Co cemented carbide matrix is 6.07wt.%, in which the carbon content is 15.95wt.%, and the content of cobalt on the surface of diamond is 7.30wt.%, in which the carbon content is 80.38wt.%. The transitional zone prevents the carbon atom of the diamond from spreading to the matrix, in which the carbon content does coincide with the theoretical value of the raw nanocomposite powders, and the carbon content forms a graded distribution among the matrix, transitional zone, and the surface of diamond; after the 1280℃ SPS consolidated process the diamond still maintains a very good crystal shape, the coated tungsten on the surface of the diamond improves thermal stability of the diamond and increases the bonding strength of the interface between the diamond and the matrix.     

Synthesis of WC-Co composite powders with two-step carbonization and sintering performance study

In this study, WC-Co composite powder was synthesized by two-step carbonization method using W, Co and C as raw materials. X-ray diffraction (XRD) showed that the η phase (Co₆W₆C) was kept at 1100 °C for 1 h under vacuum, and it could be completely carbonized into WC-Co composite powders. The surface morphology of WC-Co composite powders was analyzed by scanning electron microscope (SEM). The effects of η phase and second phase (W phase) on WC morphology and Co phase distribution were investigated. Electron backscattered diffraction (EBSD) was used to analyze WC-10 wt% Co cemented carbide particle distribution. Comparison of transverse rupture strength, hardness and fracture toughness of two kinds of WC-10 wt% Co cemented carbides synthesized by WC-Co composite powders + WC and WC + Co respectively, the cemented carbide of composite powders + WC increases the fracture toughness from 11.4 ± 0.3 MPa·m^1/2 to 12.4 ± 0.3 MPa·m^1/2.     

Synthesis of Cr-doped APT in the evaporation and crystallization process and its effect on properties of WC-Co cemented carbide alloy

WC grain size has significant effect on WC-Co cemented carbide alloy properties. In order to inhibit WC grain growth during sintering process, grain growth-inhibitor Cr₃C₂ is usually added to tungsten carbide powder in advance through mechanical milling. While, homogeneous distribution of Cr₃C₂ in the tungsten carbide powder is difficult to achieve and result in abnormal growth of WC grains. For this purpose of growth-inhibitor uniform distribution, (CH₃COO)₃Cr is added into ammonium tungstate solution during evaporation and crystallization process to prepare Cr-doped APT powder, which can be used as precursor for ultrafine-grained WC-Co cemented carbide alloy preparation. Compared with conventional APT powder, the Cr-doped APT has smaller particle size and bulk density, moreover, chromium is evenly distributed within it. The Cr-doped APT is then used to produce Cr-doped tungsten powder, which also has smaller particle size than that of conventional tungsten powder. Cr-doped tungsten powder is subsequently prepared into tungsten carbide powder and WC-Co cemented carbide alloy through carbonization and sintering process, respectively. Compared with conventional WC-Co cemented carbide alloy, the obtained WC-Co cemented carbide alloy has smaller mean WC grain size (0.36 μm), and more uniform microstructure. Furthermore, the phenomenon of WC grain abnormal growth during sintering process is not observed, because the grain growth-inhibitor Cr₃C₂ is well dispersed in tungsten carbide and cobalt composite powder. Results show that the obtained WC-Co cemented carbide alloy presents better mechanical properties (HRA, bending strength, coercive force) than those of conventional WC-Co cemented carbide alloy. Accordingly, the novel addition of (CH₃COO)₃Cr during the evaporation and crystallization process is the key factor of ultrafine-grained WC-Co cemented carbide alloy production.     

氧化-还原碳化法回收再生高性能硬质合金的研究

以废旧WC-Co硬质合金为原料,采用氧化和原位还原碳化的短流程方法合成再生WC-Co复合粉末,随后对再生复合粉低压烧结得到再生硬质合金。利用XRD、SEM和TEM等对再生复合粉和再生硬质合金的物相和显微组织形貌进行观察和分析,系统研究了原料粉末中配碳量对再生复合粉和再生合金的物相组成和力学性能的影响。配碳量为16.60%时制备的再生WC-16%Co(质量分数,下同)硬质合金的断裂韧性为24.80 MPa·m1/2、横向断裂强度达到3860MPa,并且分析了再生硬质合金的显微组织与性能之间的关系。     

Sintering behavior and mechanical properties of Cr3C2 doped ultra-fine WC-Co cemented carbides: Experment guided with thermodynamic calculations

The influence of Cr₃C₂ doping on the sintering process and mechanical properties of WC-Co cemented carbides was studied. Using differential thermal analysis of green powders and thermodynamic calculations, the disappearing temperature of solid-state binder phase in the ultra-fine WC-Co cemented carbides with different amounts of Cr₃C₂ dopant was first investigated and then verified to descend with the increase of Cr content. Based on these investigations, the sintering temperatures of three alloys with 0.3, 0.5 and 0.65 wt% Cr were selected to high by 50 °C than the phase disappearing temperature of solid-state binder. Compared with the commercial sample with the sintering temperature at 1410 °C for Cr₃C₂ doped WC-Co cemented carbides, the optimized sintering temperatures lead to finer microstructures and better mechanical properties, such as transverse rupture strength and hardness. In addition, the reliability for the performance of WC-Co cemented carbides prepared with the optimized sintering schedule is significantly improved in comparison with the commercial sample. The strategy from the present work can be used to design sintering process parameters during the manufacture of ultrafine WC-Co cemented carbides.     

蕾丝状富Co团聚组织与Co粉中硬团聚现象研究

硬质合金顶锤是WC-Co合金大制品与极端服役工况的典型代表。服役过程中硬质合金顶锤的异常失效是困扰超硬材料与硬质合金顶锤生产企业的棘手问题。本文采用扫描电镜、能谱分析以及X射线衍射分析等研究手段对硬质合金顶锤碎片与硬质合金生产用Co粉进行了观察与分析,报道了异常失效顶锤碎片微观组织结构中存在含K、Na、Ca、S、Cl、O等杂质元素、周长超过100μm的脆性蕾丝状富Co团聚组织,以及Co粉中存在因杂质与还原烧结效应导致的、外表光滑、尺度高达10μm的致密硬团聚微观缺陷。其中,富Co团聚组织中K、Na、Ca、S、Cl等杂质元素的总质量分数高达2.8%～3.45%。通过引证关联分析,认为两种缺陷之间存在一定的相关性,建议硬质合金生产企业在采购Co粉时必须重视对粉末微观质量的分析与检测。     

Additive manufacturing of WC-13%Co by selective electron beam melting: Achievements and challenges

Additive manufacturing is a powerful tool for rapid prototyping and fabricating metal articles having a complicated geometry. This method is known to be used almost solely for the manufacture of articles consisting of pure metals and alloys. In the present work the possibility of obtaining dense carbide articles by a single-step process of additive manufacturing based on selective electron beam melting was evaluated. A new technology for fabricating cemented carbide granules suitable for selective electron beam melting was developed. It includes conventional granulating WC-Co powders followed by solid-state pre-sintering and preliminary screening of the granules. After that their liquid-phase sintering and final screening are carried out to obtain a desired fraction needed for the additive manufacturing process. Results of experiments on selective electron beam melting at different scan rates and current values indicated that it was possible to obtain non-porous carbide articles of complex geometry from WC-Co granules initially containing 13 wt% Co. The selective electron beam melting process led to the evaporation of some liquid Co and very intense local WC grain growth resulting in peculiar microstructures of the cemented carbide articles comprising layers with medium-coarse and abnormally large WC grains. A near-surface layer of the cemented carbide articles obtained by additive manufacturing is characterized by a high roughness comparable with the mean size of the original WC-Co granules.     

放电等离子烧结压力对超细WC-Co硬质合金性能的影响

通过分析放电等离子烧结致密化过程,确定了致密化温度;研究了SPS烧结过程中压力对WC-Co硬质合金致密化、显微组织及性能的影响。结果表明,放电等离子烧结粉末在1 130℃时,达到最大收缩率;烧结压力的增加,样品的致密度、硬度增加;断裂韧性的变化集中在11.5~12.1 MPa.m1/2之间,和硬度的变化呈现相反的趋势;烧结压力相对较小时,样品WC晶粒较粗大且不均匀;在40 MPa和55 MPa时,晶粒相对较小且分布均匀。要得到高性能、高致密度的样品,合理的烧结温度在1 200℃以上,烧结压力为40 MPa。     

放电等离子烧结温度对纳米硬质合金性能的影响

采用放电等离子烧结(SPS)这种新的烧结技术制取92WC-8Co纳米硬质合金。主要就放电等离子烧结92WC-8Co硬质合金的烧结温度进行研究探索,对不同的烧结温度进行对比实验,以找出最佳的硬质合金SPS烧结温度。最终发现:1150℃为放电等离子烧结纳米92WC-8Co硬质合金的最佳烧结温度,在该温度下,硬质合金制品可达到14.88g/cm3的致密度,硬度可达到94.2HRA。     

Effect of VC and NbC additions on microstructure and properties of ultrafine WC-10Co cemented carbides

The nanocomposite WC-Co powders were prepared through planetary ball milling method. Effects of grain growth inhibitor addition and the vacuum sintering parameters on the microstructure and properties of ultrafine WC-10Co cemented carbides were investigated using X-ray diffractometer, scanning electron microscope and mechanical property tester. The results show that VC and NbC additions can refine the WC grains, decrease the volume fraction of Co₃W₃C phase in ultrafine WC-10Co cemented carbides, and increase the hardness and fracture toughness of the base alloys. After sintering for 60 min at 1400 °C, the average grain size and hardness of ultrafine-grained WC-10Co-1VC cemented carbide are 470 nm and HRA 91.5, respectively. The fracture toughness of cemented carbide WC-10Co-1NbC alloy is over 7 MN·m^?3/2.