Effect of vanadium on synthesis of WC nanopowders by thermal processing of V-doped tungsten precursor

The effect of vanadium on the synthesis of WC nanopowders by carbon thermal processing of V-doped tungsten precursor has been discussed. The V-doped tungsten precursor was prepared by a wet chemical method with ammonium tungstate and ammonium vanadate as its starting materials. The precursor was carbonized in the vacuum furnace using phenol formaldehyde resin as a carbon agent. The results of XRD revealed that the tungsten oxide and vanadium oxide obtained from the precursor preparation formed V–O–W bronze with the structure of WO₃ · 0.33H₂O. The carbonization reactions of WO₃ with 1 wt% of vanadium took place in a temperature range from 900 to 1050 °C to obtain V-doped WC nanopowder. The results of particle size measurement and morphological analysis show that the vanadium effectively inhibits the particle growth of tungsten carbide powder during carbonization processes, resulting in the particle size to be within the range from 64 to 184 nm after heat treatment in the temperature range from 900 to 1200 °C. V₂O₃ particles decomposed from V–O–W bronze can act as a nucleation aid for tungsten during reduction, and those on the surface of tungsten powder can hinter the growth of tungsten carbide crystal by the pinning effect.     

直接碳化技术制备碳化钨粉的研究

本文以两种不同形貌的氧化钨和炭黑为原料,采用加酒精湿磨配炭制取混合料,再经干燥,在中频电炉中,于1 000℃、1 250℃、1 400℃直接碳化,分析碳化产物的相成份、形貌、粒度、炭含量、氧含量。研究发现,不同原料在相同温度直接碳化,碳化产物形貌完全不同;薄片状氧化钨所制得的碳化钨在低倍扫描电镜下观察几乎没有超过50μm的团聚颗粒;在高倍扫描电镜下观察是许多小颗粒的团聚体,并且聚集得很紧密。针状氧化钨原料制得的碳化钨在低倍扫描电镜下观察团粒较多,而且保持着原APT的伪晶形貌,在高倍扫描电镜下观察呈松散的细颗粒聚集体。当直接碳化温度达到1 250℃,反应基本完全,化合碳接近碳化钨理论含碳量。碳化钨粒度随温度的升高而增大。     

硬质合金注射成形脱脂过程中的碳含量控制

研究了不同脱脂气氛 (不同比例N2 与H2 的混合气体 )和脱脂方法 (热脱脂、溶剂脱脂 热脱脂、冷凝蒸汽脱脂 热脱脂 )对PIM硬质合金脱脂坯及合金碳含量的影响。结果表明 :N2 热脱脂粘结剂容易以炭黑的形式残留在脱脂坯中 ,造成合金增碳 ;H2 热脱脂导致合金脱碳 ;75 %N2 2 5 %H2 (体积分数 )混合气体热脱脂既能有效地脱除粘结剂 ,又能保证合金碳含量相对稳定 ;溶剂脱脂和冷凝溶剂脱脂能显著缩短脱脂时间 ,而且由于高温保持时间短 ,在后续热脱脂过程中采用H2 作保护气也可获得满意的碳含量 ,说明该方法对工艺条件的适应性强。通过调整热脱脂高温保持时间 ,可在一定范围内对脱脂坯的碳含量进行调整 ,说明过程的可调控性好。与溶剂脱脂相比 ,冷凝蒸气脱脂粘结剂脱除率更高 ,脱脂坯有较高的强度 ,有效地防止了脱脂坯软化变形的现象。     

Investigation of WC-Co Electrospark Coatings with Various Carbon Contents

Electrospark deposition was employed to clad WC-10%Co, W/C1.6-10%Co, and W/C0.5-10%Co hard alloys on steel 1035, and the tribological properties of the coatings obtained were examined. The influence of the W/C ratio in the electrode materials on the decarburization of tungsten carbide was studied. It is shown that the degree of tungsten carbide degradation can be reduced by increasing the concentration of carbon in the WC-Co electrode materials, and also that the WC decarburization reaction is reversible on annealing. Coatings deposited using new electrode materials with an excess of carbon (W/C0.5) and/or tungsten (W/C1.6) have increased microhardness and improved frictional characteristics compared with the conventional coating.     

Synthesis of nanostructured tungsten carbide via metal-organic chemical vapor deposition and carburization process

Nanostructured tungsten carbide particles were successfully synthesized by metal-organic chemical vapor deposition in a spouted bed followed by carburization in CH₄/H₂ atmosphere in the temperature range 700–900 °C. The carburization process was a little bit complex, which involved the coating of carbon on the outer surface of the decomposed W(CO)₆ precursor particles and then followed by carbon diffusion into the particles, leading to the formation of nanostructured WC via an intermediate metastable phase W₂C. The carbon deficient phase W₂C was formed initially at lower carburization temperature and then transformed to stable WC phase by increasing the temperature and holding time.     

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。     

氧化钨/碳SPS原位合成WC硬质合金的XPS研究

以WO3＋14.5%C（质量分数,下同）的混合粉作为原始粉末,采用放电等离子烧结（SPS）在不同温度下烧结保温3 min,直接一步合成致密WC硬质合金.借助于X射线光电子能谱（XPS）分析了合成样品的元素价态变化,探讨了SPS原位合成的过程和机理.结果表明：随着烧结温度的升高,样品中的W元素的价态逐步由氧化态的W＋6,W^＋5,W^＋4过渡到单质W^0＋和碳化物态的W^＋2;而样品中的碳元素价态却逐步由单质碳转变为化合碳,氧化物态的晶格氧强度逐渐降低,以碳氧键存在吸附的氧强度逐渐增强.XPS分析结果表明,在SPS原位合成中,WO3首先被碳还原,并经历了一系列中间钨氧化物状态后得到金属钨,然后金属钨进一步发生碳化反应最终形成WC.     

Synthesis of Al2O3／WC powder by aluminothermic reduction and carbonization method

Al2O3/WC powder was synthesized by means of aluminothermic reduction-carbonization with metallic Al powder, yellow tungsten oxide and carbon black or graphite as raw materials under the protection of coke granules.The effects of Al2O3 content, temperature, C/WO3 molar ratio, and atmosphere on the synthesis of Al2O3/WC powder were studied. The results show that the relative content of WC and W2C is strongly influenced by the factors mentioned-above. Carbon black has higher reactivity than graphite. Al2O3-WC composite is easier to obtain under the protection of coke granules than under argon atmosphere. The CO in the coke layer can easily react witht ungsten to form WC and to transfer from W2C to WC.     

钨钴复合粉在流态化床中的碳化反应过程研究

将钨钴复合氧化物置于自主研发的高温流态化床中,采用氢气作为还原剂,经过还原反应后得到类金属化合物-钨钴复合粉(Co7W6和W),再加入炭黑进行碳化反应,得到最终产品碳化钨钴复合粉。试验过程进行实时在线取样,对样品进行相组成和Co、C、O、N等元素含量分析。研究结果发现,碳化过程非常迅速,其中类金属化合物Co7W6按照Co7W6→Co6W6C→Co3W3C→WC进行碳化,单质金属W是按照W→W2C→WC进行碳化,并且W2C比Co3W3C更易碳化。同进还发现,不需要经过CoW3C相可以实现完全碳化。     

两步碳化制备纳米WC粉末及其合金性能

研究了两步碳化工艺对氢还原/碳化制备的纳米WC粉末及其WC-Co合金性能的影响。结果表明,WC粉末的晶粒聚集和异常粗大颗粒主要是由于碳化初期钨颗粒因烧结合并增粗,而钨粉碳化不完全主要是由于碳化后期的温度偏低,利用先低温碳化后高温碳化的两步碳化工艺不仅能够有效抑制纳米颗粒烧结合并增粗,而且可以使钨粉充分碳化,得到颗粒细小、均匀,W2C含量极少的WC粉末;采用1120℃碳化加1180℃碳化的两步碳化工艺制备出的138 nm的WC粉末,W2C含量少于0.5%(质量分数),以其为原料制备的WC-Co烧结体显微组织结构均匀,为超细晶硬质合金,综合性能优良,洛氏硬度HRA高达93.7,抗弯强度高达4380 MPa。     

水热合成钨前驱体-碳热还原-碳化制备超细纳米级碳化钨

提出了一种以水热合成的PbWO₄为原料,然后通过碳热还原-碳化获得超细WC的方法。以PbWO₄为钨中间产品,避免了氨氮试剂的引入;采用碳还原的方式可避免水蒸气的产生,抑制了钨粉的长大。结果表明：在初始pH为7.0、反应温度为160 ℃,反应时间为4.5 h的条件下,Na₂WO₄溶液中99.9%（质量分数）以上的W以PbWO₄的形式回收。然后采用低温碳还原PbWO₄,在C:W摩尔比为5、950 ℃的条件下还原3 h,获得了W和C的混合物,该混合物中预加富余的C有助于抑制钨粉的团聚。然后将W和C混合物高温碳化,在1200 ℃下反应6 h,获得了粒径约为60 nm的WC粉末。     

A facile pathway to prepare ultrafine WC powder via a carbothermic pre-reduction followed by carbonization with CH4-H2 mixed gases

In the present work, ultrafine tungsten carbide (WC) powder with a high purity has been prepared by first roasting yellow tungsten trioxide (WO₃) and carbon black powder under argon atmosphere followed by the further carbonization reaction with CH₄-H₂ mixed gases. The effects of C/WO₃ molar ratio, CH₄ percentage in the CH₄-H₂ mixed gases on the phase composition, morphology and particle size of the products were discussed. The results revealed that when the C/WO₃ molar ratios were 2.5 and 2.6, nano tungsten carbide powder with the average particle sizes of 93 nm and 77 nm could be prepared. Whereas, when the C/WO₃ molar ratio was in the range of 2.7–3.5, the finally prepared WC has the particle size of 446–192 nm, and became smaller with the increase of C/WO₃ molar ratio. The percentage of CH₄ should be <15% to prepare WC with a low free carbon content. From the results of thermodynamic calculation, X-ray diffraction (XRD), FE-SEM, and infrared carbon‑sulfur analyzer, it was concluded that ultrafine tungsten carbide powders with a high purity could be successfully prepared by this method.     

常压下碳热还原制备碳化钒(V_8C_7)粉末的研究

为了实现小批量连续化制备碳化钒粉末,以工业级V2O5和纳米碳黑为原料,在常压下氩气保护的碳管炉中高温反应得到了V8C7。采用X射线衍射仪(XRD)、扫描电镜(SEM)、LECO碳氧分析仪对反应产物进行了分析。结果表明:碳化温度为1 450℃时,可得到有序V8C7,但是杂质含量较高;提高温度有利于粉末纯度的提高,而不利于粉末的细化;最终在1 600℃保温4 h的条件下,制备出游离碳质量分数为0.31%、氧质量分数为0.69%、平均粒径为2μm的V8C7粉末。     

Synthesis of (Ti,W, Mo,V)(C,N) nanocomposite powder from novel precursors

(Ti, W, Mo, V)(C, N) nanocomposite powders with globular-like particle of ∼10–100 nm were synthesized by a novel method, namely carbothermal reduction–nitridation (CRN) of complex oxide–carbon mixture, which was made initially from salt solution containing titanium, tungsten, molybdenum, vanadium and carbon elements by air drying and subsequent calcining at 300 °C for 0.5 h. Phase composition of reaction products was discussed by X-ray diffraction (XRD), and microstructure of the calcined powders and final products was studied by scanning electron microscopy (SEM) and transmission electron microscope (TEM), respectively. The results show that the synthesizing temperature of (Ti, W, Mo, V)(C, N) powders was reduced greatly by the novel precursor method. Thus, the preparation of (Ti, 15W, 5Mo, 0.2V)(C, N) is at only 1200 °C for 2 h. The lowering of synthesizing temperature is mainly due to the homogeneous chemical composition of the complex oxide–carbon mixture and its unusual honeycombed structure.     

Nitrogen Contents on Tribological Properties of Magnetron Sputtered SICN Coatings

SiCN COATINGS have stimulated wide interestbecause they exhibit many good properties for potentialindustrial applications,such as high opticaltransparency in Infrared(IR)region,wide bandgap,chemical inertness and high refractive index,goodinsulating property,good mechanical and tribologicalproperties(high hardness,elastic modulus,low friction,etc.)[1-4].Amorphous and/or hydrogenated SiCNcoatings can be prepared by various depositionmethods,such as laser ablation[5],plasma-assistedchemica…     

机械活化-反应热处理制备纳米晶WC-Co复合粉末的研究

以W、C、Co为原料粉末,经机械活化-反应热处理工艺制备纳米晶WC-Co复合粉末。实验发现活化粉末的固相反应具有以下特征:反应温度低,反应速度快。在800℃热处理时已有大量的WC生成。在850℃保温25minW2C就完成了向WC的转化。经900℃保温35min制备了晶粒尺寸为30.5nm的WC-Co复合粉末。     

Control of exaggerated tungsten carbide grain growth at the diamond-substrate interface of polycrystalline diamond cutters (PDC)

Exaggerated tungsten carbide grain growth is common at the interface between the diamond table and the cobalt-cemented tungsten carbide (WC-Co) substrate in polycrystalline diamond cutters (PDC). The exaggerated WC grains at the interface can grow as large as 50 μm with an aspect ratio of 50:1. These large grains can also grow as clusters. The presence of large WC grains/clusters creates weakness at the diamond-substrate interface and impairs the strength of the PDC tool. In the present investigation, we tried to understand the root cause of exaggerated WC grain growth at the interface. Our findings show that WC grain growth at the interface decreases with a decrease in the carbon/tungsten (C/W) ratio. By adding 5 wt.% pure tungsten powder to the diamond, the C/W ratio decreased and we found no WC grain growth. By adding fully stoichiometric WC, which has 6.13 wt.% carbon, grain growth was reduced but still observed. Sintering on a substrate having η-phase (carbon deficient phase) also decreased the C/W ratio, and we did not observe WC grain growth.     

Effect of carbon source on the carbothermal reduction nitridation for synthesis of (Ti, W, Mo, V)(C, N) nanocrystalline powders

The effect of carbon source on the carbothermal reduction-nitridation during synthesizing (Ti, W, Mo, V)(C, N) nanocrystalline powders was investigated. For a systematic comparison, activated carbon, graphite and two kinds of carbon black powder were used as reducing agents in this study. Ultrafine (Ti, W, Mo, V)(C, N) powders with a particle size of ~ 200-500 nm have been produced at 1450 °C for 2 h by using nanosized carbon black source with small particle size. The presence of phases in the reaction products was characterized with X-ray diffraction (XRD) and the microstructure of carbon source powders and final products was studied by scanning electron microscopy (SEM). The results show that the formation of the Ti(C, N) phase is strongly dependent on the particle size of carbon source powders, and the synthesizing temperature of the Ti(C, N) phase decreases significantly from 1750 °C to 1300 °C by using nanosized carbon black, as compared with micron graphite. In addition, activated carbon with a particle size of 5-50 μm does not favor the dissolution of tungsten or molybdenum carbides into Ti(C, N) despite its large specific surface area.     

Synthesis of nanosized tungsten carbide from phenol formaldehyde resin coated precursors

Nanosized tungsten carbide was synthesized from phenol formaldehyde resin (PF) coated tungsten precursors.The process has three steps in which nanosized tungsten particles were first coated with PF,then the precursors were carburized at 950℃,and finally the carburized powders were treated in flowing wet hydrogen atmosphere at 940℃ to remove the uncombined carbon.The obtained powders were characterizedusing X-ray diffraction analysis (XRD),field-emission scanning electron microscopy (FESEM),small angle X-ray scattering (SAXS),andcombustion-gas-volume method.The results indicated that single-phase WC could be synthesized using excessive PF as carburizer at a muchlower temperature compared with using mixed carbon black.After wet hydrogen treating,the mean size of the obtained WC particles was 94.5nm and the total carbon content was 6.18 wt.%.     

Formation of an amorphous phase in thermally sprayed WC-Co

A WC-Co coating was sprayed by the high-velocity oxyfuel process using a feedstock of tungsten carbide clad with cobalt. The structure of the sprayed coating was characterized by x-ray diffraction (XRD), differential scanning calorimetry (DSC), and differential thermal analysis (DTA). It was found that an amorphous phase of Co-W-C ternary alloy observed as a large, broad peak in the XRD pattern can be formed in the as-sprayed WC-Co coating. The DSC, DTA, and XRD analyses revealed that the amorphous phase crystallized at a temperature of around 873 K to metallic cobalt, Co₆W₆C, and tungsten with appreciable precipitation of free carbon. The heat treatment of as-sprayed WC-Co coating at a high temperature of 1173 K suggests that annealing at a temperature higher than about 1104 K will promote the reaction of tungsten and cobalt with carbon to form the complex carbide C₀₆W₆C.