Optimizing the synthesis of ultrafine tungsten carbide powders by effective combinations of carbon sources and atmospheres

Nanostructured WC powders can provide technologically attractive properties due to the fine microstructures obtained after sintering. Either W or WO₃ powders are used for the industrial production of WC. In both cases, the contact area between carbon and tungsten precursors has a critical influence on the reaction temperatures, which in turn affects grain growth and agglomeration of particles. Different methods have been studied to increase the reaction rates by enhancing the contact between reactants: carbon coating of tungsten powder, solid-gas reactions of tungsten powders with atmospheres containing CH₄, or mechanical activation followed by thermal activation of tungsten and carbon precursors.In this work WC-powders were obtained by mechanical activation of tungsten and carbon precursors followed by thermal activation of these mixes at temperatures up to 1100 °C. A systematic study has been carried out combining two dissimilar carbon sources (graphite and carbon black), with different atmosphere compositions (Ar, Ar-50H₂, Ar-10CO) and studying the evolution of phases at different stages of the synthesis. The results show how the efficiency of the interaction between carbon sources and atmospheres affects the completion of the synthesis. The synthesis of WC from WO₃ in H₂ containing atmospheres is enhanced when using carbon black sources, however in CO containing atmospheres the most effective interaction is with graphite.     

Study on in-situ WC particles/tungsten wire reinforced iron matrix composites under electromagnetic field

By applying electromagnetic field to a system consisting of tungsten wires and grey cast iron melt, the grey cast iron matrix composite reinforced by either in-situ WC particles or the combination of in-situ WC particles and the residual tungsten wire was obtained. By means of differential thermal analysis (DTA), the pouring temperature of iron melt was determined at 1,573 K. The microstructures of the composites were analyzed by using of X-ray diffraction (XRD), scanning electron microscopy (SEM) equipped with an energy dispersive spectrum (EDS) and pin-on-disc abrasive wear test. The obtained results indicated that, with the enhancing frequency of electromagnetic field, the amount of in-situ WC particles gradually increases, leading to continuous decrease of the residual tungsten wires. When the electromagnetic field frequency was up to 4 kHz, tungsten wires reacted completely with carbon atoms in grey cast iron melt, forming WC particals. The electromagnetic field appeared to accelerate the elemental diffusion in the melt, to help relatively quick formation of a series of small Fe- W-C ternary zones and to improve the kinetic condition of in-situ WC fabrication. As compared with the composite prepared without the electromagnetic field, the composite fabricated at 4 kHz presented good wear resistance.     

采用WC过渡层增加金刚石薄膜附着力的研究

在微波等离子体化学气相沉积装置中，以WC-8％Co为基体，采用氢等离子体脱碳、磁控溅射镀W、碳化等方法，制备了微晶WC过渡层。研究了金刚石薄膜与基体的附着力。结果表明，表面脱碳后再镀W膜，W填充了氢等离子体脱碳时刀具表面因钴蒸发而留下的空洞，形成过渡层，在随后的碳化中和基体WC连接较为紧密，能增加金刚石薄膜与基体附着力，克服单纯的氢等离子体脱碳还原法降低刀具基体硬度、不能完全消除钴的有害影响的缺点。     

超细硬质合金烧结过程中WC扩散-溶解-析出特征与机理研究

以08型WC与Co制成WC-10%Co试样条,脱蜡后分别于1 200﹑1 250﹑1 300﹑1 350℃进行烧结并分别保温1 h和5 h。采用扫描电镜观察烧结过程中WC晶粒形貌的变化,采用差热分析仪研究WC-10%Co的共晶温度。研究结果表明:WC-10%Co在低于共晶温度的烧结过程中发生了WC晶粒形貌由等轴形向棱边平直的多边形变化,并随着温度升高,晶粒尺寸增大。这表明在固相烧结时超细WC与钴相存在溶解析出过程,改变WC晶粒形貌并使晶粒长大。     

水溶化学法制备纳米WC/Co复合粉工艺探索

本文通过实验探索了水溶化学法制备纳米WC/C0复合粉工艺,研究了影响喷雾转换、锻烧、碳化和调碳的工艺因素,找到了满足纳米WC/Co复合粉制备的工艺参数。在Kear等人的经典合成技术中,碳化钨钴纳米复合材料是由喷雾转化水溶液的化学计量量的水溶性钨源和钴源,然后用流化床通氢将钨钴氧化物还原为金属钨和钴,之后在一个充满CO/CO2的气体环境中将金属钨和钴碳化成纳米WUCo复合粉末。本研究不同于Kear等人的处理方法,涉及的WC/C0使用水溶性溶液钨、钴和碳前躯体加工的纳米复合材料,大量的WGCo纳米复合粉体是将钨、钴和碳在分子级水平上混合制备成一个复杂的前驱体粉末的独特方案,前驱体粉末在煅烧炉充满惰性气体约100撕00cC的温度下转化成一个含有W-Co-C-0的预复合粉粉末,随后在碳化炉低于1000℃的温度下碳化。实验表明,水溶化学法生产的纳米WC/Co复合粉较常规方法,具有晶粒细而均匀、流动性好等特点,更适于高性能硬质合金的生产。     

Synthesis and processing of nanocrystalline tungsten carbide: Towards cemented carbides with optimal mechanical properties

Nanocrystalline tungsten carbide has been obtained by reduction/carburization at low temperature from precursors obtained by freeze-drying of aqueous solutions. Nanocrystalline WC powders with a adequate content of carbon were mixed with submicrometric Cobalt powder (12 wt.%), obtained by same synthesis method, and sintered in vacuum furnace. The cemented carbides fabricated from experimental powders were compared with both commercial ultrafine and nanocrystalline WC-12Co mixtures consolidated by the same route. The synthesised powders were characterized by X-ray powder diffraction, elemental analysis and scanning and high resolution transmission electron microscopy. On the other hand, density, microstructure, hardness and fracture toughness together with X-ray diffraction analysis of the sintered materials were evaluated. The cemented carbides obtained from synthesised powders exhibited a WC platelet-based homogeneous microstructure. This anisotropic growth might be due to the presence of stacking faults parallel to the basal plane in the starting WC powder, which would promote the defect-assisted preferential growth. These materials showed excellent mechanical properties, with a superior hardness/fracture toughness combination compared to materials prepared from commercial mixtures.     

微波合成WCx/MWCNTs及其电催化性能研究

目的制备多壁碳纳米管负载碳化钨的纳米复合材料(WC_x/MWCNTs),探索微波加热温度对WC_x/MWCNTs合成的影响规律。方法利用分子自组装技术与微波加热技术相结合,以钨酸钠为W源,制备了WC_x/MWCNTs纳米复合材料。采用X射线衍射(XRD)和透射电子显微镜技术(TEM)对不同条件下制得样品的物相组成、结构及微观形貌进行了表征;采用循环伏安法在酸性环境下测试了WC_x/MWCNTs对氢和CH3OH的电催化性能。结果当微波加热温度为1000℃时,制备的WC_x/MWCNTs纳米复合材料由WC、WC2和C组成,碳纳米管的多壁结构保留较好,碳化钨颗粒均匀地分布在碳纳米管外表面,粒径为20~50 nm。循环伏安测试结果表明,制备的WC_x/MWCNTs在酸性环境下对氢具有一定的催化作用,但对甲醇没有明显的电催化作用。结论通过控制合理的微波加热温度,可制备出碳化钨粒径小、分布均匀、碳纳米管多壁结构完好的WC_x/MWCNTs纳米复合材料。制备的WC_x/MWCNTs在酸性环境下对氢具有一定的催化作用,可作为催化剂载体来负载其他金属制备复合催化剂。     

粗晶钨粉碳化过程中粒子间的烧结现象

采用Fsss粒度分别为9μm和21μm的两种钨粉在相同的工艺条件下进行高温碳化,利用扫描电子显微镜、金相显微镜等对样品进行了分析。结果表明,高温碳化过程中会发生粒子间的烧结,碳化温度越高,粒子间的烧结越厉害;钨粉粒度越细越容易烧结;粒度较小的钨粉高温碳化烧结后所得的WC晶粒尺寸虽然会明显增大,但是晶粒度的均匀性下降。     

添加TiC对激光粒子沉积WC-Co-Cr 和WC-Ni涂层性能的影响

研究了激光熔覆TiC增强双相不锈钢上WC涂层的机理。分析了激光工艺参数对复合涂层的影响。采用SEM和EDX手段分析了喂料粉末以及复合涂层的形态和微观组织。采用维式硬度计测试了复合涂层的表面硬度,采用动电位曲线法研究了涂层在3.5%NaCl溶液中的耐腐蚀行为。由于激光熔覆处理,在不锈钢表面形成了与基材结合良好的硬陶瓷粒子。添加TiC到WC中得到的复合涂层没有裂缝、孔洞和金属间化合物,没有出现这些对涂层性能不利的缺陷。结果表明,涂层具有较高的显微硬度,且大部分涂层的腐蚀电位变得更负。     

Vacuum sintering of WC-8 wt.% Co hardmetals from WC powders with different dispersity

The effect of sintering temperature and particle size of tungsten carbide WC on phase composition, density and microstructure of hardmetals WC-8 wt.% Co has been studied using X-ray diffraction, scanning electron microscopy and density measurements. The sintering temperature has been varied in the range from 800 to 1600 °C. The coarse-grained WC powder with an average particle size of 6 μm, submicrocrystalline WC powder with an average particle size of 150 nm and two nanocrystalline WC powders with average sizes of particles 60 and 20 nm produced by a plasma-chemical synthesis and high-energy ball milling, respectively, have been used for synthesis of hardmetals. It is established that ternary Co₆W₆C carbide phase is the first to form as a result of sintering of the starting powder mixture. At sintering temperature of 1100-1300 °C, this phase reacts with carbon to form Co₃W₃C phase. A cubic solid solution of tungsten carbide in cobalt, β-Co(WC), is formed along with ternary carbide phases at sintering temperature above 1000 °C. Dependences of density and microhardness of sintering hardmetals on sintering temperature are found. The use of nanocrystalline WC powders is shown to reduce the optimal sintering temperature of the WC-Co hardmetals by about 100 °C.     

低温机械化学法制备Mo-Cu纳米复合粉末

以CuMoO4-MoO3粉末为前驱体,采用机械化学-氢气共还原的方法制备出Mo-Cu纳米复合粉末。通过DSC对前躯体的制备温度进行研究,通过XRD、SEM及TEM分别对粉末的相组成、形貌和粒度进行表征,从热力学的角度对粉末的还原过程进行分析。结果表明,机械球磨可以有效地降低粉末的颗粒尺寸,增大反应面积,提高粉末还原活性,从而在低温下制备出Mo-Cu复合粉末。通过优化工艺参数,对机械球磨15h的CuMoO4-MoO3混合粉末在680℃下还原,可以得到颗粒尺寸为50～100nm的Mo-25%Cu(质量分数)纳米复合粉末。     

碳化钨和碳化钒在固相钴中的固溶研究

分别以BET粒度为0.15μm和0.23μm的碳化钨粉末与钴湿磨压制制备成WC-90%Co试样条,分别以Fsss粒度为1.0μm和1.5μm的碳化钒粉末与钴湿磨压制制备成VC-95%Co试样条。将以上四种试样条分别于1 100、1 150、1 200℃进行真空烧结,将烧结后的试样条研磨抛光后采用X衍射仪和扫描电镜研究碳化钨和碳化钒在固相钴中的固溶情况。研究结果表明:两种粒度的WC均于1 150℃逐渐溶解到Co中形成γ-固溶体,其固溶度随温度升高而增大,1 200℃固溶完全;两种粒度的VC粉末于1 100℃逐渐溶解到Co中形成γ-固溶体,1 150℃固溶完全。     

纳米钨/碳化钨粉末的形貌遗传特性及其对粉末均匀性的影响

为研究氧化钨的形貌结构对纳米钨粉末制品均匀性的影响,用X射线衍射分析仪和电子扫描电镜对普通黄钨在660℃下还原的过程产物进行了分析、观测。同时分别以普通黄钨和强力球磨分级处理的细黄钨为原料,采用经优化的工艺条件制备出了纳米W、WC粉末,并对粉末及其快速烧结体的显微组织结构进行了观察、分析。结果表明,不同形貌结构原料制备的纳米W、WC粉末,均呈现出不同程度的形貌结构遗传特性,强力球磨分级处理所获细黄钨颗粒细小、形貌结构疏松,更容易制备出结构较疏松,分散性较好的纳米W、WC粉末。     

真空热处理对碳化钒粉末制备的影响

为了制备高纯的碳化钒粉末,对五氧化二钒为原料小批量制备所得碳化钒产物进行了真空热处理。采用X射线衍射仪(XRD)、扫描电子显微镜(SEM)、LECO碳氧分析仪等测试手段对热处理产物进行了表征,重点研究了热处理温度对碳化钒粉末的影响,并用X射线光电子能谱仪(XPS)测试探讨了热处理对碳化钒纯化的机理。结果表明:在1100℃的热处理温度下,可得到有序的V8C7相,游离碳和氧含量分别为0.18%、0.31%;热处理的过程使得碳化钒中的游离碳和氧的下降是粉末中游离碳和剩余的少量钒氧化物发生了进一步的还原反应和粉末中吸附水的消失造成的。     

INDUCTION PLASMA REACTIVE DEPOSITION OF TUNGSTENCARBIDE FROM TUNGSTEN METAL POWDER

1. IntroductionIt was reported by Smith et al.[1] and S.ith[2] that tungsten carbide and titaniumcarbide can be formed in d.c. plasma via the reactions of tungsten powder and titaniumpowder with methane, respectively Due to the characteristics of small plasma volume,short particle residence time, and lateral injection of the powders into the d.c. plasma,only a fraction of the fed-in powders were carburized. Actually the deposits are mixturesof WC and W and the composite of TiC and Ti, respe…     

Peculiarities of vacuum annealing of nanocrystalline WC powders

The effect of vacuum annealing temperature on the phase and chemical composition, particle size, and microstrains of nanocrystalline powders of tungsten carbide WC with particles from 20 to 60 nm in size has been studied using X-ray diffraction and electron microscopy methods. It is established that nanocrystalline WC powders stored in air, contain from 1 to 2 wt.% of impurity oxygen. It is found that vacuum annealing of WC nanopowders at a temperature up to 1400 °C is accompanied by appreciable decarburization and variation in the phase composition due to carbon desorption as a result of interaction with impurity oxygen. Annealing leads to coarsening of powder particles caused by intergrowth of aggregated nanoparticles and to decreasing microstrains.     

Effect of WC/W2C on the microstructure and abrasion resistance of high-boron hardfacing alloys

High boron hardfacing alloys reinforced with primary M₂B phases on Q235 steel plates were prepared by the method of flux-cored wire submerged arc welding. The microstructure and boride morphology were investigated using optical microscopy (OM), scanning electron microscopy (SEM) and X-ray diffraction (XRD). The effect of WC/W₂C on the microstructure was discussed. It indicated that the volume fraction of primary M₂B phases has increased due to good nucleated cores of incompletely molten W₂C particles provided by casting tungsten carbide or decarburizing reaction of WC powders. Abrasion resistance was evaluated by wet sand rubber wear tests and the wear mechanism was studied using SEM. It shows that primary M₂B grains play a key role in improving abrasion resistance.     

碳含量对盐助燃烧合成法制备的超细WC粉体形貌、尺寸和相的影响

在WO3-Mg-C-Na2CO3体系中,引入NaCl做稀释剂,通过盐助燃烧合成法制备了超细碳化钨（WC）粉体。利用扫描电镜（SEM）、能谱仪（EDS）和X射线衍射（XRD）对产物进行分析,研究了碳（C）含量对制备的WC粉体的形貌、尺寸和相的影响。结果表明：在m=0.125（Na2CO3的摩尔数）基础上,将原料中碳的摩尔数从l=2增加到2.25和2.5,浸出前产物由少量大尺寸颗粒及大量小尺寸颗粒组成;浸出后产物是由亚微米小颗粒团聚而成,颗粒之间熔化烧结现象很弱,呈弱团聚状态;浸出产物的粒度分布基本符合正态分布,尺寸在200～350nm的范围内;在l=2.25条件下,合成的产物主要为目标产物WC,副产物W2C含量极少。即k=2.0（NaCl的摩尔数）,m=0.125,l=2.25为制备单相WC的工艺条件。     

Co掺杂对粗颗粒、特粗颗粒WC粉末粒度与微观形貌的影响

以粗颗粒与特粗颗粒W粉为原料,研究了Co掺杂对粗颗粒与特粗颗粒WC粉末粒度与微观形貌的影响。结果表明,Co掺杂有利于WC粉末Fsss的提高与游离碳的降低,有利于得到单晶WC粉末。当Co掺杂量为w(Co)=0.035%时,WC粉末颗粒与晶粒形貌发生巨大变化,WC晶粒的结晶完整性明显改善,呈现明显的生长台阶与生长平面,但特粗颗粒WC粉末颗粒形貌的规则度较粗颗粒WC粉末的低。当碳化温度由1900℃提高到2000℃后,Co掺杂特粗WC颗粒表面出现大量WC纳米颗粒依附物。     

High energy milling on tungsten powders

Nanocrystalline tungsten powders were produced by high energy mechanical milling, using both tungsten carbide (WC) and tungsten (W) balls as grinding media. X-ray diffraction study indicated that the lattice parameter of tungsten decreased (from 3.162 to 3.149 Å) with increasing milling time from 0 to 15 h. Considerable decrease in particle size was observed in both W and WC grinding media after 15 h of milling duration. Rietveld analysis of the X-ray data along the Williamson-Hall plots revealed that the crystallite size also decreased with increasing milling time. Chemical analyses showed that the total amount of cobalt and carbon in the milled samples were higher in WC grinding media, as compared to W grinding media. The sintered density increased from 80% to 98% from as received to milled tungsten powders, when sintered at 1790 °C. The mechanical properties of as sintered alloys were evaluated and were found to be strongly influenced by the milling time and grinding media.