溶胶-凝胶法辅助碳热还原氮化反应制备CeN粉末

以柠檬酸（CA）为螯合剂,即以有机物为碳源,通过溶胶-凝胶法辅助碳热还原氮化反应制备了CeN粉末。整个反应过程分为水相过程和热处理过程。水相过程主要是Ce³⁺和CA的螯合和聚酯,形成稳定的Ce³⁺-CA螯合物前驱体。通过水相过程实现Ce源与C源在分子水平上的均匀混合。热处理过程包括原位碳化和碳热还原氮化反应两部分。原位碳化过程形成的CeO₂/C粉末促进了CeO₂和C之间的紧密接触,从而减少Ce源和C源原子的扩散距离,以促进碳热还原氮化过程。     

溶胶-凝胶法合成导电SrVO3 粉末

通过溶胶-凝胶法结合热处理合成了导电SrVO₃粉末。在溶胶配制过程,对Sr:V摩尔比进行精确调控,再通过对凝胶热分解行为的表征,确定其煅烧温度和除去残余碳,从而获得前驱体粉末,再将其在H₂中还原以获得最终产物。研究了煅烧温度、Sr:V摩尔比对产物形貌、结构和组成的影响,并采用标准直流四探针技术对样品的电导率进行测试。结果表明,当Sr:V摩尔比为1:1.06,煅烧温度500 ℃,再在850 ℃氢气还原,可以制备没有残余碳或钒的氧化物杂质的单相SrVO₃粉末。SrVO₃粉末的电导率达到714.3 S/cm,比石墨粉末的电导率（500 S/cm）高。     

碳氢协同还原-碳化法制备纳米WC粉的工艺及机理

针对传统还原-碳化工艺中WC粉颗粒长大的问题,采用碳氢协同还原-碳化法制备纳米级球形WC粉,研究了前驱体配碳比和反应温度对WC粉性能的影响。结果表明,WC粉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转变为WC具有结构遗传性,WC粉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H_2,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粉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粉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。     

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。     

NH4HF2 氟化Al2O3 制备无水AlF3 研究

采用热重-差热分析（TG-DTA）方法对不同NH₄HF₂/Al₂O₃质量比的Al₂O₃+NH₄HF₂混合物的热行为进行了分析,确定了DTA曲线的临界温度。进一步分析了各临界温度前后直接热处理所得产物的形貌和物相。结果表明,质量比对临界反应温度和反应过程没有影响。氟化反应在室温下以(NH₄)₃AlF₆的形成开始,在162.3~162.8 ℃时占主导地位,在180 ℃左右完成。进一步热处理后,(NH₄)₃AlF₆在249.8~250.1 ℃分解为NH₄AlF₄,在356.8~357.7 ℃分解为β-AlF₃;随后β-AlF₃在400~650 ℃向α-AlF₃转变。     

磷-硫-钒-水体系酸性溶液中钒的提取热力学分析

针对含钒酸浸液中钒的有效提取问题，研究了298 K时磷-硫-钒-水溶液酸性体系中钒的提取热力学分析过程。结果表明，在 P(V)-V(V)-H₂O酸性溶液体系中，pH=1~4时VO₂⁺首先转变为磷钒杂多酸阴离子，pH=4~7时磷钒杂多酸阴离子转变为同多酸阴离子；在S(VI)-V(V)-H₂O酸性溶液体系中，pH=0~1时钒主要以VO₂⁺和 VO₂SO₄^-形式存在，pH=2~6时钒逐渐转变为同多酸阴离子；在P(V)-S(VI)-V(V)-H₂O酸性溶液体系中，pH=1~3 时VO₂⁺和 VO₂SO₄^-逐渐转变为磷钒杂多酸阴离子，当pΗ=2时ΣPV₁₄（所有磷钒杂多酸阴离子之和）的摩尔分数最大为88.55%；pH=4~6 时，磷钒杂多酸阴离子消失并逐渐转变为同多酸阴离子，当pΗ=5时ΣV₁₀（所有同多酸阴离子之和）的摩尔分数最大为100.00%。     

Li4SiO4 氚增殖陶瓷的制备及其与14Cr-ODS钢的腐蚀界面行为

Li₄SiO₄小球与ODS钢的化学相容性对聚变反应器的安全运行具有重要意义。研究了在500、600、700 ℃的氩气环境中保温300 h后ODS钢与小球接触界面组织和成分的变化。结果表明,在600~700 ℃时,Li₄SiO₄小球与ODS钢的界面发生了严重的元素互扩散和反应。在Li₄SiO₄小球表面,由于ODS钢中Fe和Cr的扩散,出现了一层薄薄的反应层,这也导致了密度的增加,破碎负荷从51 N （500 ℃）下降到32 N（700 ℃）。XRD图谱显示,ODS钢表面出现了LiCrO₂和LiFeO₂新相,说明Li₄SiO₄小球中的Li和O原子可以扩散到ODS中,与Fe、Cr元素在高温下发生反应形成腐蚀层。在700 ℃时,腐蚀层可分为2个氧化层。最外层是LiFeO₂和LiCrO₂的混合物,下一层主要是LiFeO₂。在ODS钢的表面,700 ℃/300 h条件下氧扩散系数为2.2×10^-14 cm²/s,这说明ODS钢作为一种包层结构材料,在未来的包层设计中需要一层耐腐蚀涂层。     

机械与热综合活化法制备超细WC-Co粉末

研究了WO3、Co3O4和石墨混合粉末经高能球磨活化后再分步进行还原和碳化反应制备超细WC-Co粉末的过程.结果表明:球磨30 h后,粉末粒径达到70～100 nm.450～700℃温度范围内球磨粉在流动H2和Ar混合气体中经2 h还原时,随着还原温度的升高,WO3还原反应顺序为WO3→WO2.9→WO2.72→WO2→W,700℃时可实现完全还原;Co3O4在450℃完全还原为Co,随着温度的进一步升高和时间的延长,Co与W反应转变为Co3W;最终还原产物由W、Co、Co3W和石墨组成;在700～1 000℃温度范围内还原粉在流动Ar中碳化时,随着碳化温度的升高,碳化反应按W(Co3W)→Co6W6C→Co3W3C→W2C→WC的顺序进行,在900℃下还原粉在2 h内可完全碳化,得到WC颗粒尺寸约为200～300 nm的WC-Co复合粉末.     

空气气氛下碳热还原筛分法制备Magnéli相Ti n O2 n -1

介绍了一种在空气气氛中通过碳热还原筛分法制备Magnéli相（Ti_nO_2n-1，4＜n＜10）低价钛氧化物的方法，研究了还原温度和还原时间对还原产物的物相、电阻率的影响。结果表明，提高还原温度和延长还原时间有利于将TiO₂还原为Magnéli相Ti_nO_2n-1。将Magnéli相Ti_nO_2n-1 (n=4，5) 粉末在1350 ℃下干燥20 min，通过扫描电子显微镜观察，其粒径为0.5~8 μm。在还原温度为1350 ℃时，还原产物的电阻率随还原时间的延长而显著降低。在1350 ℃下还原50 min的产物的电阻率最小，为79.3 Ω?cm，其物相组成几乎全部为Ti₃O₅。     

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。     

A low-cost,efficient, and industrially feasible pathway for large scale preparation of tungsten nanopowders

Tungsten (W) is the most commonly used high-temperature refractory metal in many critical fields such as aerospace, military and electronic industries etc. This paper proposes a low-cost, efficient, and industrially feasible pathway for large scale preparation of tungsten nanoparticles via the combination of carbothermic reduction and hydrogen reduction processes. The new strategy involves the preparation process of pre-reduction W powder by reducing commercial WO₃ with insufficient carbon black at 1050 °C or 1150 °C to avoid the residue of carbon, and the deep reduction process of pre-reduction W powder by hydrogen 725 °C. By this process, most of the oxygen in WO₃ was reduced by carbon, and W particles with a much smaller size could be obtained owing to the absence of the volatile tungsten oxide, such as WO₂(OH)₂, which leads to the serious increase of particle size during the hydrogen reduction process. Tungsten nanoparticles with average particle sizes of about 40 nm and 75 nm have been successfully synthesized at 1050 °C and 1150 °C, respectively, with the residual carbon content as low as about 0.01%. This process can be readily extended to a large-scale industrial production of W nanopowders. Additionally, this new strategy has great potential to prepare other pure metals (or nanopowders) from their metal oxides via combining of carbothermic reduction (main process) and further reduction of other reducing agents.     

A short and facile process to synthesize WC-Co cemented carbides

WC-Co cemented carbides are widely used in the fields of military, aerospace, mining and cutting industry etc. In this paper, a new two-step method for the preparation of WC-Co cemented carbides was proposed. First, the mixture of yellow tungsten trioxide (WO₃) and cobaltic oxide (Co₂O₃) were reduced by carbon black to remove all the oxygen. Then, the carbothermic reduction products were precisely mixed with an appropriate amount of carbon black to directly prepare WC-Co cemented carbides. The effects of C/WO₃ ratio on the phase composition, morphological evolution, particle size and mechanical properties of products are investigated. The experimental results revealed that when the C/WO₃ molar ratio was above 2.7, all oxygen in the raw material mixture were removed by carbon black and a mixture of W₂C and η-phase were obtained after the first step of carbothermic reduction at 1150 °C for 2 h; then, the mixture of carbothermic reduction product and an appropriate content of carbon black was compacted, and the green compact was first carbonized at 1200 °C for 2 h and then sintered at 1450 °C for 4 h to prepare cemented carbides. With the increase of C/WO₃ ratio at the first stage, the content of η-phase with a low melting point increased, which resulted in the large grain size of WC in the finally prepared cemented carbide. Compared with the traditional method of preparing cemented carbides, the cemented carbides prepared by the current method showed a higher hardness and toughness. Furthermore, the addition of a proper content of the VC in the second stage can significantly inhibit the grain growth of WC and further increase the hardness of cemented carbides.     

Direct solid-state synthesis of tungsten carbide nanoparticles from mechanically activated tungsten oxide and graphite

Solid-state carbothermic reduction of tungsten oxide (WO₃) to nano-sized tungsten carbide (WC) particles was achieved by calcining mechanically activated mixtures of WO₃ and graphite at 1215 °C under vacuum condition. By experiments and thermodynamic calculations, the intermediate phases, WO_2.72, WO₂ and metallic tungsten (W), were observed at 741 °C, which decomposed to synthesize the final product (WC). Homogeneity increase and associated decrease in the diffusion path by mechanical milling and formation of these intermediates are mainly responsible for the successful production of WC. The process indicates that solid-state synthesis of WC nanoparticles directly from as-milled mixtures of tungsten oxide and graphite powder is possible.     

Size-controlled synthesis of high-purity tungsten carbide powders via a carbothermic reduction–carburization process

In this paper, a novel method is proposed to synthesize high-purity tungsten carbide (WC) powders with different sizes via carbothermic reduction of yellow tungsten trioxide (WO₃) followed by the further carbonization process. The effects of the reaction temperature, reaction time and C/WO₃ molar ratio on the phase transition and morphology evolution of the products are investigated in detail. The results reveal that the morphology of the final products is mainly determined at the carbothermic reduction stage, and the particle size of WC is significantly affected by the C/WO₃ molar ratio and reaction temperature. It can be concluded from experimental results that particle size of WC increased with the increased of temperature, but decreased with increased of C/WO₃ molar ratio. When the C/WO₃ molar ratio is 2.7–3.5, the single phase WC with a size of 178–825 nm can be obtained after further carbonization at 1200 °C.     

Synthesis of high-purity ultrafine tungsten and tungsten carbide powders

High-purity ultrafine W or WC powder was prepared via a two-step process composed of the carbothermic pre-reduction of WO_2.9 and the following deep reduction with H₂ or carbonization with CH₄+H₂ mixed gases. The effects of C/WO_2.9 molar ratio and temperature on phase composition, morphology, particle size, and impurity content of products were investigated. The results revealed that when the C/WO_2.9 ratio was in the range from 2.1:1 to 2.5:1, the carbothermic pre-reduction products consisted of W and a small amount of WO₂. With changing C/WO_2.9 ratio from 2.1:1 to 2.5:1, the particle sizes were gradually decreased. In order to prepare ultrafine W or WC powder, a relatively high C/WO_2.9 ratio and a lower reaction temperature at this stage were preferred. After the second reaction, the final products of ultrafine W and WC powders with a high purity could be obtained, respectively.     

Carbothermic reduction of scheelite (CaWO4) doped with cobalt or nickel

Pure scheelite (CaWO₄) and carbon black mixtures, containing 0 or 2 wt% cobalt or nickel were prepared by 8 or 24 h planetary ball milling (PBM). The mixtures were studied by thermal analysis (TGA-DTA), isothermal annealing at 950, 1000 and 1100 °C, X-ray diffraction (XRD) and scanning electron microscopy (SEM). Independently of the presence of transition metal (Co or Ni), the carbothermic reaction occurs through several steps, where the Ca:O atomic ratio goes from 1:4 to 1:1 according to the sequence: CaWO₄ → Ca₃WO₆ → CaO, with concomitant development of gaseous CO and formation of metal tungsten. Finally, tungsten is carburized to give nanostructured WC.For the first time we here show that Co and Ni have a noteworthy catalytic effect on the carbothermic reduction of CaWO₄. In particular, these transition metals catalyze both the two-step reduction of scheelite and the subsequent carburization of tungsten. In the latter case, formation of intermediate η phases (Me_xW_yC_z, with Me = Co or Ni) occurs.Doping with Co or Ni allows obtaining an almost quantitative (97%) conversion of scheelite into WC after 12 h at a temperature as low as 950 °C. The catalyst allows to reduce PBM duration as well, in that doped mixtures subjected to just 8 h PBM give WC yields larger than 90% after 1 h at 1100 °C, being W₂C the balance.The doping of CaWO₄:C mixtures with few weight percent of Co or Ni allows to produce nanostructured WC by reducing both the milling time and the annealing temperature. These results are particularly appealing from both industrial and sustainability point of view since they allow performing less energy-intensive syntheses of nanostructured WC powders from scheelite.     

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.     

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.     

In Situ Production of Fe-TiC Nanocomposite by Mechanical Activation and Heat Treatment of the Fe2O3/TiO2/C Powder

In this study, Fe-TiC nanocomposite was synthesized by carbothermic reduction of activated Fe₂O₃, TiO₂, and graphite powder mixture. The effect of 0, 5, and 20?h of high energy ball milling of mixture on the reduction process was also investigated. Comparing the results of the thermogravimetry analysis of milled and un-milled mixtures clearly showed that the reduction temperature decreased due to the milling process. XRD pattern of 20?h milled powder mixture proved that Fe-TiC nanocomposite was formed after the heat treatment of activated powder at 1100°C for 1?h under vacuum. The microstructure studies of the milled mixture by scanning electron microscope revealed homogenous distribution of TiC particles in the Fe matrix.     

Reactive spark plasma sintering of binderless WC ceramics at 1500 °C

Binderless WC ceramics were prepared by reactive spark plasma sintering, using tungsten trioxide, tungsten and carbon black as the starting materials. Phase assemblages and microstructure of the as-sintered ceramics were investigated. It was found that graphite existed as an impurity phase due to the volatilization of WO₃, and W could compensate for the WO₃ loss to form WC with a single phase. Benefiting from the enhanced sinterability, WC ceramics with high relative density and good hardness could be obtained at temperature as low as 1500 °C.