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。     

WC/Co纳米复合粉质量特性的研究

本文探讨了喷雾转换法制备WC/Co纳米复合粉的生产工艺特点、粉末的物理化学特性以及在超细合金中的应用效果。各方面的实验数据表明:WC/Co复合粉中WC碳化完全、粒度细而均匀,钨钴元素达到分子级均匀混合,Co对WC形成纳米级包覆,粉末颗粒外形多呈球状,球体由部分合金化的WC/Co粒子聚合而成,粒子之间存在明显的烧结颈,其亚晶尺寸在100nm以下。复合粉经强化球磨后制取的超细合金较传统工艺制备的合金的WC相晶粒更加均匀,具有更好的物理力学性能和更高的使用寿命。即使不添加抑制剂,复合粉制备的合金仍具有晶粒细而均匀的特点。     

乙二胺四乙酸在纳米WC／Co复合粉制备中的应用

本文在喷雾转换法制备WC／Co纳米复合粉的基础上,采用乙二胺四乙酸与碳酸钴复合法制备高钴含量的WC／Co纳米复合粉,突破了原有技术的钴含量质量分数上限7％的瓶颈限制。采用DSC—TG分析、SEM分析、XRD分析等方法,对乙二胺四乙酸和碳酸钴的参与反应的机理进行了研究,并确定了采用新工艺制备WC／Co纳米复合粉的相关参数。实验结果表明：乙二胺四乙酸与碳酸钴反应所得有机钴盐为一种溶解度较高的螯合物,在较低温度下煅烧可分解,适用于WC／Co纳米复合粉前驱体溶液中钴含量的调节,避免了Cl-、NO3-等杂质离子的引入。通过新的复合‘工艺制备得到了适用于高温流态化床生产的前驱体粉末,最终制备得到钴含量质量分数8％的WC—Co纳米复合粉。     

WC—Co合金的固态烧结

本文探讨了常规烧结和场助烧结时WC－Co合金的固态烧结行为。在常规烧结中,纳米和超细WC－Co合金的密度比粗晶及细晶合金增加得更快。在纳米／超细和粗WC－Co粉之间出现最大致密化速率的温度差别在50℃以上。添加晶粒长大抑制剂特别是Cr3C2也能阻滞固态阶段的致密化。在场助烧结中,在更低的固态烧结温度下,WC－Co合金就可获得比常规烧结更高的密度。常规和场助烧结之间密度的差别随温度的增高而降低。     

用喷雾转化法制备的纳米晶粉末烧结的WC—10Co硬质合金的力学性能

研究了纳米晶WC－10Co硬质合金的力学性能和显著结构。这种纳米晶WC－10Co硬质合金粉末是将含有偏钨酸铵（AMT）和硝酸钴的溶液喷雾干燥制得的纳米晶前驱体粉末再经过还原和碳化制备的。直径约100nm的WC粉末与Co炽结相混合均匀，并在1毫乇压力和1375℃下进行烧结。为了与纳米晶料WC－10Co的显微结构和力学性能相比较，将直径范围为0．57－4μm的工业用WC粉末与Co粉混合，并在与纳米晶粉末相同的条件下进行烧结，在纳米晶WC－10Co硬质合金中加入不同量的TaC、Cr3C2和VC作为晶粒长大抑制剂。为研究WC－10Co硬质合金中Co粘结相的显微结构，以WC－10Co硬质合金烧结温度下制备了Co-W-C合金。WC－10Co硬质合金随着WC粒度的减小而增加的硬度因而符合霍尔－佩奇型关系式。WC－10Co硬质合金的断裂韧性随着Co粘结相的HCP（密排六方相）／FCC（面心六方相）比的增大（由于HCP／FCC相引起的）而提高。     

EFFECTS OF SIZE COMBINATION AND CONTACTING STATE OF RAW POWDER PARTICLES ON SPARK PLASMA SINTERED ULTRAFINE CEMENTED CARBIDES

本文采用亚微米WC粉和纳米Co粉、亚微米WC粉和高能球磨后具有纳米晶组织的微米级Co粉这两种具有不同粒径匹配的混合粉末作为原料粉末，利用放电等离子烧结（SPS）技术制备超细晶WC-10Co硬质合金。对不同原料粉末的SPS过程及烧结试样的显微组织和性能进行了系统的对比分析。实验结果表明，以两种混合粉末为原料均获得了平均晶粒尺寸在200nm以下的超细硬质合金材料，其中，采用亚微米WC粉和高能球磨的微米级Co粉利用SPS技术制备的材料相对密度达到98%以上，硬度达到HRA94.5，断裂韧性达到13.50MPa•m1/2，表明具有优良的综合性能。而采用亚微米WC粉和纳米Co粉利用SPS技术制备出的超细晶硬质合金的组织均匀性和性能较差。根据SPS技术的特殊烧结机理，对采用不同粒径匹配和结合状态的WC和Co混合粉末的SPS致密化机制进行了分析。     

液相烧结纳米WC／Co合金晶粒长大的抑制

新一类晶粒长大抑制剂合金已被开发出来．它使得在液相烧结纳米相WC／Co粉末压坯时WC晶粒的粗化得到较好的控制。这一类新合金是所选择的抑制剂碳化物(VC或／和Cr3C2)和钴金属的固溶体。这种方法使抑制剂碳化物在纳米复合物材料中分散得非常均匀，从而保证了烧结时WC晶粒长大得到更加有效的控制。加有抑制剂相的富Co基体熔点的明显降低．有助干WC晶粒长大速度降低，另一个有利的且可能是决定性的因素是液相Co中形成了稳定的金属／非金属原子团，即W、V、Cr／C原子团。可以认为，这种原子团阻碍了W和C原子从一个晶粒向另一个毗连晶粒的液相迁移，从而进一步降低WC的长大速度。     

含板状WC晶粒硬质合金制备方法的研究

以市售W粉,Co粉和石墨粉末为原料,采用普通工艺制取WC-12wt%Co合金。合金显微组织正常,含有大量板状WC晶粒。研究表明,使用板状W颗粒粉末、提高烧结温度和延长烧结时间都有助于合金中板状WC晶粒的形成。     

W+Co+C(碳黑)制备板状晶硬质合金及其性能研究

采用经球磨扁平化处理的W粉末为原料,添加适量Co、C(碳黑)、成型剂及纳米W粉制备板状晶硬质合金,研究了烧结温度、时间和添加纳米W粉,对板状晶硬质合金显微组织结构和性能的影响。结果表明,球磨预处理中颗粒W粉末可获得扁平化程度高的薄片状W粉末,以其为原料制备的WC-12%Co(质量分数)板状晶合金相对密度达97%,合金硬度呈现出明显的各向异性;添加纳米W粉或提高烧结温度、延长烧结时间,均有利于压坯烧结收缩致密化,生成更多的板状WC晶粒。     

超细碳化钨粉末特性对金刚石锯片刀头显微结构的影响

采用超细WC粉末和工业级的Sn、Ni、Co、Cu粉末以及金刚石为原料，经真空烧结后制备成金刚石锯片刀头。用扫描电镜（SEM）观察了WC粉末和合金的形貌，用能量散射谱（EDS）测试了合金的微区成分分布。研究结果表明，超细WC粉末的添加能改善Sn-Ni-Co-Cu结合金刚石锯片刀头的显微结构，超细WC含量的增加有利于材料晶粒的细化和强度提高，Cu是烧结中产生液相和使成分偏析的重要影响因素，Co对晶粒异常生长影响很大，Sn的添加有利于晶粒的细化。     

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。     

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.     

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。     

超细WC-Co硬质合金及其磨损性能研究

采用低温化学镀方法在超细WC颗粒表面进行金属钴包覆,烧结包覆后的复合粉体制备新型硬质合金NYG（WC-3%Co）.研究了超细WC-Co硬质合金的力学性能、断口形貌和显微结构,在销盘式磨损试验机上进行干滑动磨损实验.结果表明,在硬质合金烧结过程中,沿WC晶界均匀分布的金属钴不仅起粘结剂作用,也起抑制剂作用阻碍晶粒的长大;新型硬质合金的抗弯强度、断裂韧性、硬度和耐磨性能均得到较大提高;在干滑动摩擦条件下,新型WC-Co硬质合金的失效以塑性变形及细小碳化钨相颗粒脱落为特征.     

高能球磨制备纳米WC-Co复合粉末及其SPS烧结

本文采用高能球磨法制备纳米结构WC-Co粉末,并采用放电等离子体烧结方法(SPS)对该纳米粉末进行致密化。使用X射线衍射、SEM等手段分析了高能球磨对WC-Co复合粉末中WC晶粒尺寸和粒度的影响。发现经过90h左右的高能球磨,WC-Co的粉末粒度可以达到300nm左右,而WC的晶粒尺寸可以细化到8nm左右。经过SPS烧结后,合金中的WC相的晶粒尺寸可以保持在300nm左右,而Co多以fcc结构出现。     

Microstructure and properties of ultrafine WC-10Co composites with chemically doped VC

Vanadium carbide is the most effective grain growth inhibitor for ultrafine WC-Co composites due to its high solubility and mobility in the cobalt phase at relatively low temperatures;however,there are still some debates over the best way to introduce it into the WC-Co formulation.In this paper,the differences between admixed and chemically doped grain growth inhibitors on the microstructural development and properties of an ultrafine WC-10Co composite are discussed.The densification rate of chemically doped samples is slower in the early stage of sintering and the WC grain sizes of the sintered alloys are finer than those of admixed samples,leading to the increase of hardness and transverse rupture strength of the sintered alloys.The effectiveness of the chemically doped inhibitor is attributed to the formation of vanadium rich layers on the surfaces of tungsten carbide powders during reduction and carbonization,which alters the surface and interface energies of WC grains,impedes the contact with each other of WC grains and contributes to the resistance to W diffusion across the layer during sintering,resulting in the inhibition of nanosized particle coalescence.     

SintClad: A New Approach for the Production of Wear-Resistant Tools

Tools used in the mineral processing industry are required to feature high wear resistance to facilitate an adequate cost efficiency. These kinds of tools are made of composite materials based on a low-alloyed substrate material and a high-alloyed coating. The coatings can be applied in different ways using production processes like HIP cladding, deposit welding, and composite casting. The article is concerned with the problem of a novel and cost-effective coating alternative: sinter cladding, using the principle of super-solidus liquid-phase sintering (SLPS). Usually SLPS represents a sintering technique, which is used for the compaction of high-alloyed metal powders. However, no recognizable efforts were made to use the SLPS-process for applying a PM-coating on a bulk substrate material. Sinter cladding for the first time uses SLPS to combine the process of powder compaction with the application of a coating to a solid steel substrate into one single step. Another advantage of the process is the possibility to produce massive bulk coatings with thicknesses exceeding 20 mm. This article is original in the scope of question and investigation methods in terms of microstructure, hardness profiles, EDX measurements, diffusion calculations, and computational thermodynamics.     

Study of nanostructured WC-Co composites

Nanostructured materials, also termed nanocrystalline materials, have emerged upon the horizon in the past few years. In the present research, a preliminary study has been performed regarding sintering, grain growth, and mechanical properties of nanostructured WC-Co. It was found that densification of nanostructured WC-Co powder could be completed in 5 min, or 15 min if grain growth inhibitors are added. Grains grow extremely rapidly, very likely via coalescence, during heating and the first few minutes (< 5) at temperature. After the initial rapid stage, grain growth followed the linear relationship of coarsening. It was also found that samples made from nanostructured powder had better surface crack resistance than samples made from standard submicron powder.     

超细WC-Co硬质合金的制备与性能研究

利用高能球磨法制备纳米级WC-Co混合粉末,采用脉冲电流烧结技术进行烧结。用能谱分析仪(EDX)对球磨后的粉末进行成分分析,用X射线衍射(XRD)对比分析球磨前后WC-Co混合粉末的衍射峰变化,用透射电子显微镜(TEM)和扫描电子显微镜(SEM)对所制备的粉末及烧结材料进行了组织形貌观察,并测定了烧结试样的硬度。结果表明:随着球磨时间的延长,WC-Co纳米粉末的粒度逐渐变小,当球磨时间超过30h后获得了粒度为100nm以下的WC-Co纳米粉末。脉冲电流烧结后获得超细WC-Co硬质合金,与传统的WC-Co硬质合金相比,超细WC-Co硬质合金具有更高的硬度(HRA92.5～94)和耐磨性。另外通过实验获得了最佳的烧结工艺参数。     

Densification and sintering shrinkage of Zinc Reclaimed WC-Co

Zinc Reclaimed WC-Co powder exhibits faceted WC crystal shape while virgin WC-Co powder can have rounded WC particles. During sintering, the WC grains in Zinc Reclaimed WC-Co powder remain faceted while virgin WC-Co retains its rounded WC shape until the later stages of sintering. The effect of the shape of WC grains in Zinc Reclaimed WC-Co on its densification behavior is not fully understood. The effect of WC crystal shape on the densification of Zinc Reclaimed WC-Co during sintering is investigated. The shrinkage of Zinc Reclaimed WC-Co is measured by dilatometry and found to lag behind the shrinkage of virgin WC-Co after the first densification stage during solid state sintering. There is a greater lag in the shrinkage of coarse grained Zinc Reclaimed WC-Co than fine grained Zinc Reclaimed WC-Co relative to the corresponding virgin WC-Co. The role of packing density on the densification of Zinc Reclaimed WC-Co during solid state sintering is discussed.