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（英文）

在WO_3-Mg-C-Na_2CO_3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(Na_2CO_3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200~350 nm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(Na Cl的摩尔数),m=0.125,l=2.25为制备单相WC的工艺条件。     

NaCl含量对盐助燃烧合成超细硼化钨粉体相组成和粒度的影响及其作用机制

在W-B_2O_3-Mg体系中引入不同含量的稀释剂NaCl,盐助燃烧合成了超细硼化钨粉体,利用XRD、SEM和EDS对合成粉体的相组成及粒度进行了分析。结果表明未加入NaCl时,燃烧合成产物浸出前主要是W_2B_5和MgO的混合团聚物,颗粒形貌接近于椭球形;加入NaCl后,除了W_2B_5和MgO外,还出现了新相WB,颗粒形貌不规则且有微弱团聚现象;浸出后产物主要由大量的小尺寸硼化钨颗粒组成,粉体组成由W_2B_5转变为W_2B_5+WB+B的复合物。浸出产物W与B元素的总含量均达到了98%以上,当NaCl含量k=5时达到了最大值98.51%;其平均粒度随NaCl含量的增加而减小,当k=20时达到粒度的最小值0.85μm。     

熔盐法制备NaNbO_3纳米粉体的研究

以Na2CO3和Nb2O5为反应物,NaCl为熔盐,在800℃温度下熔盐反应4h成功获得了纯钙钛矿结构NaNbO3(NN)纳米粉体。利用XRD对合成粉体的物相进行表征,利用TEM和SEM观察合成粉体颗粒的微观形貌,并与固相法合成的粉体进行比较。结果显示,熔盐法所合成的粉体为无团聚的立方块状的单晶NaNbO3颗粒,其平均尺寸约200nm。NaNbO3形成机制为溶解-析出机制。     

高纯超细钨和碳化钨粉体的制备（英文）

提出一种两步法制备高纯度W或WC粉体的工艺,该工艺包括碳热预还原WO_(2.9),以及后续的对还原产物进行H_2还原或CH_4+H_2混合气体碳化。研究C/WO_(2.9)摩尔比和反应温度对不同阶段产物的相组成、形貌、粒径及杂质含量的影响。结果表明,当C/WO_(2.9)摩尔比为2.1:1-2.5:1时,碳热预还原产物的物相由W和少量WO_2组成。随着C/WO_(2.9)摩尔比从2.1:1增加到2.5:1,碳热预还原产物的粒径逐渐减小。因此,采用相对较高的C/WO_(2.9)摩尔比和较低的反应温度有利于获得超细W或WC粉体。经过第二阶段的反应,可以制备高纯度W粉和WC粉。     

成型压力对盐助燃烧合成超细CeB6粉体粒度和纯度的影响及其作用机制

在B_2O_3-CeO_2-Mg体系中引入发热剂KClO_3,利用盐助燃烧法制备超细高纯度CeB_6粉体,研究成型压力对盐助燃烧合成超细CeB_6粉体粒度和纯度的影响。借用SEM、EDS、TEM和XRD探讨了盐助燃烧合成法制备CeB_6粉体的形成机理。结果表明,燃烧合成的主要产物为CeB_6,且随着成型压力的增大,浸出后产物的平均颗粒尺寸略微有增加,平均尺寸为0.830～0.930μm,整体粒度分布较为均匀;浸出产物的纯度随着成型压力的增加呈现出先增加后减小的趋势,当压力为20 MPa时,纯度达到最大值99.0%,但不同压力下各试样纯度均在98.0%以上。     

化学气相法低温合成纳米WC-Co-VC粉体

利用H2／C2H2混合气体在850℃下还原碳化高表面活性的纳米WO3（CoO,V2O5）先驱粉体,合成了平均粒度为20～50nm的WC-Co-VC复相粉体。制备过程分3步完成：制备先驱体溶液、合成超细WO3（CoO,V2O5）粉体及其还原碳化过程。当温度低于800℃时,还原碳化产物为WC,W2C,W,VC和Co3W3C的混合物。高于900℃的温度下,先驱体完全碳化为六方WC、立方Co和立方VC的纳米复相粉体。结果表明,WO3（CoO,V2O5）先驱体在H2／C2H2气流下的还原碳化行为与其初始结晶状态、碳化温度、气流速度等工艺参数密切相关。     

熔盐碳热/镁热还原低温合成ZrB_2-SiC复合粉体

以氧化锆、氧化硅、氧化硼及活性炭粉为起始原料,以镁粉为还原剂,以Na Cl-KCl为熔盐介质,采用熔盐碳热/镁热还原的方法合成了Zr B_2-Si C复合粉体。采用X射线衍射仪分析了合成粉体的物相组成,并研究了锆/硅摩尔比、氧化硼用量、镁粉用量及炭粉用量等因素对熔盐碳热/镁热合成Zr B_2-Si C复合粉体的影响。结果表明:在摩尔比为1:1的Na Cl-KCl复合熔盐体系中,固定锆/硅摩尔比为1:1,当B_2O_3加入量120%、C加入量120%、Mg粉加入量150%(摩尔分数)时,可以在1200℃反应2 h的条件下合成纯度很高的Zr B_2-Si C复合粉体,复合粉体中Zr B_2及Si C的含量分别为59%和35%(质量分数)。FE-SEM结果表明,合成的Zr B_2-Si C复合粉体存在团聚现象,其粒径约为0.5μm。相较于常规的碳热/镁热方法,该方法可以降低Zr B_2-Si C复合粉体的合成温度约200℃左右。     

碳氢协同还原-碳化法制备纳米WC粉的工艺及机理研究

针对传统还原-碳化工艺中WC粉颗粒的长大问题,采用碳氢协同还原-碳化法制备纳米级球形WC粉,研究前驱体配碳比和反应温度对WC粉性能的影响。结果表明,WC的碳含量与前驱体的配碳比密切相关,最佳配碳比（即n(C)/n(W)值）为3.6。W向WC的转变具有结构遗传性,WC的平均粒径与还原温度和碳化温度密切相关。随着还原温度由680 ℃升高至800 ℃,还原水蒸气与碳反应生成CO和H2,显著降低体系中水蒸气的分压,从而抑制中间产物W颗粒的挥发-沉积长大,WC的平均粒径随还原温度升高而减小。碳化过程中的高温促进WC颗粒的晶界迁移和纳米W颗粒之间的烧结合并长大,WC的平均粒径随碳化温度的升高而增大。n(C)/n(W)为3.6的前驱体粉末经800 ℃还原和1100 ℃碳化后,得到平均粒径为87.3 nm的球形WC粉。     

送粉激光熔覆合成制备WC/Ni硬质合金涂层及其耐磨性

借助同轴送粉法将W／C／Ni元素混合粉末送入熔池，利用激光熔池中热力学和动力学条件，在优化材料威分和激光熔覆工艺参数条件下可以直接反应合成出WC颗粒，形成以WC／Ni为主的复合涂层。熔覆层中含有WC，CW3，α-W2C，W2C，Fe6W6，C,FeW3C，W3O，C等相。添加2wt％的Cr3C2可以细化涂层中的WC颗粒尺寸，颗粒平均尺寸为4～6μm，硬度值为85HRA左右。激光合成制备的WC／Ni硬质合金涂层的耐磨性尚不及YG8硬质合金的耐磨性，但比渗氮处理试块的耐磨性提高了7．9倍。激光直接合成硬质合金涂层的成本低，可在零件能任何部位原位合成，形状尺寸不受限制。     

静态图像分析法在亚微WC粉末粒度分析中的应用

原料WC粉末粒度是影响WC-Co硬质合金微观结构和性能的关键因素,目前仍没有一个完全精确的方法用于测量亚微WC粉末粒度。本研究采用静态图像分析法得到亚微WC粉末颗粒尺寸,并针对WC06和WC08两种粉末粒度进行表征分析,测得平均颗粒尺寸分别为0.40μm和0.42μm,表明两者一次颗粒粒径相差不大,WC06和WC08是传统粒度测试方法下分类的产物。同时将该结果与常规粒度测试方法（费氏粒度法、比表面积法和激光衍射法）以及常用静态图像分析技术（扫描电镜法、电子背散射衍射法）进行对比分析。结果表明,静态图像分析法能在很大程度上消除团聚的二次颗粒的影响,能迅速完成图像处理,并对粉末颗粒粒度进行定量表征。     

具备Al2O3原位合成特性的WC复合粉末设计与涂层

利用球磨法将Al粉添加到亚微米结构WC-12Co粉末中,设计并制备了具有Al2O3原位合成特性的纳米结构WC-Co-Al粉末。XRD分析显示球磨10h、30h和50h后的粉末中WC平均晶粒尺寸为93.1nm、39.0nm和44.8nm。超音速火焰（HVOF）喷涂时,WC-Co-Al粉末比球磨前WC-12Co粉末扁平化更好,涂层孔隙率为0.57%,比WC-12Co涂层（1.62%）更低。粉末中的Al元素与氧气反应原位生成了Al2O3硬质陶瓷颗粒,有效抑制了WC的氧化脱碳。WC-Co-Al涂层显微硬度为1298?3HV0.1,比WC-12Co涂层高出约36%,这得益于Al2O3颗粒的增强效应,WC晶粒纳米化和孔隙率降低。     

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.     

Fabrication of nanocrystalline WC and nanocomposite WC–MgO refractory materials at room temperature

Reactant material powders of pure WO₃, Mg and graphite have been milled at room temperature using a high-energy ball mill. After a few kiloseconds of milling (11 ks), numerous fresh surfaces of the reactant materials are created as a result of the repeated impact and shear forces generated by the balls. After 86 ks of milling, a mechanical solid state reduction is successfully achieved between the fresh Mg and WO₃ particles to form a product of nanocrystalline mixture of MgO and W. A typical mechanical solid state reaction takes place between the W particles and graphite powders to obtain fine grains of nanocrystalline WC. Towards the end-stage of ball-milling (173 ks), the nanocrystalline MgO grains (10 nm) are embedded into the fine matrix of WC to form fine nanocomposite powders (1 μm in diameter) of WC–18% MgO material with spherical-like morphology. This composite powder was then consolidated under vacuum at 1963 K, with a pressure ranging from 19.6 to 38.2 MPa for 0.3 ks, using a plasma activated sintering method. In addition, pure nanocrystalline WC powders (7 nm in diameter) obtained by removing the MgO from the milled powders, using a simple leaching technique have been also consolidated by the same consolidation technique. The consolidation step does not lead to a dramatic grain growth and the compacted samples that are fully dense still maintain their unique nanocrystalline characteristics. The elastic properties and the hardness of both consolidated samples have been investigated. A model for fabrication of refractory nanocrystalline WC and nanocomposite WC–18% MgO materials at room temperature is proposed.     

堆焊工艺制备金属间化合物复合材料的组织和性能

以WC，NiAl，NiB和Ni粉末等混合球磨、烧结制备复合材料焊条，在球磨过程中，WC颗粒被破碎，NiAl，NiB和Ni反应生成金属间化合物Ni3A1。用氩弧焊将这种复合材料焊条堆焊在1Cr25Ni20Si2不锈钢的表面，形成5mm厚的金属间化合物耐磨复合材料。堆焊过程中，部分WC溶解，析出新碳化物W2C，Ni3Al转变成新金属间化合物Ni3(A1Ti)C。这种复合材料的耐磨性可达45钢的3倍以上。     

苹果酸诱导合成花状WO_3粉体及其光致变色性能

以钨酸钠为钨源,通过添加苹果酸诱导剂,利用水热法合成花状WO3粉体。所得产物用XRD,SEM和TEM等手段进行结构和形貌表征,并用紫外-可见(UV-Vis)漫反射光谱仪及测色计测试光致变色性能。结果表明,未添加和添加苹果酸诱导剂合成的WO3粉体均为六方相,未添加苹果酸的WO3粉体是粒度为200～300nm的无规则块状颗粒,以苹果酸为诱导剂合成的WO3粉体是由许多直径为300～500nm,厚度在20～30nm的纳米片层层叠加,彼此交错而成的花状结构。这种花状结构增大WO3粉体的比表面积,增强其对光子的捕获能力,提高对光的利用率,从而优化WO3粉体的光致变色性能。     

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.     

用季铵盐从模拟钨矿苏打浸出液中直接萃取钨

针对从钨矿碱性浸出液中直接萃取钨制取仲钨酸铵(APT)工艺萃取分相慢、反萃液中WO3浓度偏低的问题,采用季铵盐三辛基甲基氯化铵(Tri-n-octylmethyl-ammonium chloride,TOMAC)为萃取剂,对从钨矿苏打浸出模拟料液中直接萃取钨进行研究,分别考察钨矿浸出液中Na2CO3浓度、反萃剂组成及浓...     

Near-nano and coarse-grain WC powders obtained by the self-propagating high-temperature synthesis and cemented carbides on their basis. Part I: Structure,composition and properties of WC powders

Near-nano WC powders with mean grain sizes of about 200 nm were prepared by the SHS method including the reduction of WO₃ by Mg in the presence of carbon and regulating additives. The chemical leaching and refinement of the SHS reaction products allowed one to obtain stoichiometric WC containing only traces of oxygen and magnesium. The thermal reduction of WO₃ and V₂O₅ by magnesium in the presence of carbon resulted in obtaining two carbide phases of WC and complex carbide (W,V)C with the fcc crystal lattice having a grain size of less than 300 nm. It was established that the tungsten oxide reduction by magnesium in the presence of carbon cannot be used to synthesize coarse-grain WC powders. Coarse-grained WC powders were obtained using the W + C mixture heated to high temperatures by a simultaneous exothermic reaction of interaction between magnesium perchlorate Mg(ClO₄) and magnesium. The coarse-grain WC powder synthesized in such a way is nearly stoichiometric and consists of sintered round-shaped agglomerates with the average grain size of up to 16 μm and containing only traces of magnesium and oxygen. The agglomerates comprise WC single-crystals of roughly 1 μm to 8 μm in size.     

Preparation of ultrafine/nano Mo particles via NaCl-assisted hydrogen reduction of different-sized MoO2 powders

The current study investigated the effects of the amount of NaCl addition, particle size of MoO₂, temperature (under isothermal condition) and heating rate (under non-isothermal condition) on the morphology, particle size and dispersivity of prepared Mo by hydrogen reduction of MoO₂. The formation of sufficient dispersed Mo nuclei and their controllable growth were crucial for transforming the large MoO₂ particles to dispersed ultrafine/nano Mo particles. It was found that in the absence of NaCl, it was hard to control the nucleation and growth of Mo grains, and the morphology and particle size of products still retain those of the raw MoO₂ in the temperature range of 840–1000 °C. However, as the amount of NaCl addition was above 0.05%, it was successful to control the nucleation and growth of Mo. Ultrafine/nano Mo powders with the average particle size from 100 nm to 800 nm were successfully prepared via adjusting the particle size of MoO₂ and temperature under isothermal condition. The use of MoO₂ with small particle sizes can increase the reaction rate and the number of Mo nuclei number, thus improve the particle dispersivity and decrease the particle size. Additionally, after reaction at 900 °C and 1000 °C, the residual Na was reduced to 140 ppm and 33 ppm from the initial value of 380 ppm, respectively. Under non-isothermal condition, the temperatures for the nucleation and growth could be adjusted by changing heating rate and particle size of raw MoO₂ particles. Mo nanoparticles with smaller particle size and better dispersivity were successfully prepared, and the average particle size can decrease to about 80 nm.