含V和Cr纳米W粉碳化热力学分析及实验

根据W、V2O3和Cr2O3碳化反应的热力学分析结果,以含V2O3、Cr2O3各0.5 wt%的纳米W粉为原料,在1100 ℃真空碳化,制备了含晶粒长大抑制剂(VC、Cr3C2)的纳米WC粉末,其平均粒径小于100 nm.实验结果表明抑制剂在碳化过程中可有效抑制WC颗粒长大.     

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。     

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。     

纳米级碳化钨粉末的直接碳化制备

从WO3到WC的直接碳化反应一般遵从WO3→WO272→WO2→W→W2C→WC的顺序。细小的颗粒一般在直接碳化反应WO272→WO2的阶段产生，通过严格控制这个反应步骤可成功制得纳米WC粉末。大量的研究已证明，烧结碳化物的性能如硬度、强度主要受WC粉末粒子尺寸、Co含量及碳含量的影响。最细的工业级碳化物一般加入VC．Cr3C2，TaC来抑制晶粒的长大，烧结后可以获得晶粒约0．5μm的WC硬质合金。为了制备超硬的烧结碳化物，有必要开发纳米级WC粉末粒子及发展纳米WC粉末均匀分布的加工技术，     

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。     

机械化学反应法制备纳米W_2C粉体

用机械化学反应法成功制备单相纳米W2C粉体,方法是将WO3与Mg粉混合,加入石墨粉作为碳源,在N2气氛中高能球磨而成。反应分两步完成：首先是Mg粉还原WO3得到α-W,此步称"爆炸化学反应（EMS）,反应历时5h;其次为α-W通过扩散反应逐渐碳化成W2C,WC;最后都转化为W2C,反应历时47h。继续球磨30h后W2C细化为纳米粒子。样品经HCl溶液洗去MgO后得到的产物为单相纳米W2C粉体,晶粒度为4～20nm。     

碳辅助氢还原与普通氢还原制备W粉的对比研究

在相同的还原工艺参数下,以碳辅助氢还原法和普通氢还原法分别制备W粉,采用XRD、SEM、TEM和HRTEM对不同还原方法制得W粉的物相、形貌和粒度分布进行对比研究,并讨论还原方式对W粉粒径和形貌的影响机理。结果表明:碳辅助氢还原W粉的还原长大机制以固相局部化学反应为主,平均粒径均不超过60 nm,W粉一次颗粒呈均匀细小的球状或椭球状形貌,颗粒间没有明显的团聚或粗化现象;普通氢还原以"挥发-沉积"长大机制为主,所得W粉颗粒粗大,粒径为微米级,发育完全,颗粒呈类球形多面体结构,部分晶粒之间相互交联。     

超细（W，Ni，Fe，Y）复合粉末制备过程中稀土Y的物相形态变化

采用溶胶-喷雾干燥-氢还原法制备稀土Y含量分别为0,0.4%,5%,10%和20%的超细（W,Ni,Fe,Y）复合粉末,采用XRD研究煅烧温度和还原温度以及稀土Y含量变化时复合粉末体在制备过程中的相结构变化规律。结果表明：喷雾干燥前驱体随煅烧温度的升高渐渐从非晶体向复合氧化物晶化转变,添加稀土Y的粉末前驱体经煅烧后,Y与W形成复合氧化物Y2W3O12,且稀土Y可以有效地抑制粉末颗粒长大;随着Y含量的增加,Y和W的复合氧化物明显增加,Y2W3O12在700 ℃才能被还原成低氧复合氧化物相;含5%稀土Y粉末中的Y2W3O12被还原生成新相Y2WO6;当稀土Y增加到10%以上时,不仅生成Y2WO6,还生成另一种新相Y6W2O15。     

超细晶硬质合金中VC／Cr3C2对晶粒长大的抑制作用及机理研究

研究了超细晶硬质合金VC／Cr3C2抑制剂作用及抑制机理。研究发现复合添加VC／Cr3C2可以有效抑制WC—10Co合金烧结过程中晶粒的连续长大，合金平均晶粒尺寸为0．5μm，具有较高TRS（横向断裂强度TransverseRuptureStrength）和硬度。TEM和EDS分析发现抑制剂元素的主要存在方式是溶解在粘结相中且分布均匀，未发现抑制剂元素偏聚和第二相析出，说明抑制机理在于抑制剂元素溶入粘结相Co后，显著降低W，C在Co中的溶解度，使液相烧结阶段WC晶粒的溶解一析出过程受到阻碍，从而抑制液相烧结阶段的晶粒连续长大。     

Ti6Al4V微弧氧化TiO2/W复合膜的制备及摩擦学性能

目的提高Ti6Al4V合金的摩擦学性能。方法在硅酸盐-磷酸盐电解液中添加不同浓度的纳米W粉,利用微弧氧化技术在Ti6Al4V基体表面制备出氧化陶瓷膜。利用FE-SEM、EDS和XRD研究了在不同浓度W粉参与下的微弧氧化膜表截面微观形貌、元素分布及膜层相组成。通过旋转摩擦磨损试验评估了膜层的摩擦学性能。结果电解液中加入纳米W粉可以促进膜厚增长,尤其在含0.5～2 g/L纳米W粉时,膜厚呈近似线性增长;但W粉在膜层表面的附着会导致粗糙度的增大。在纳米W粉参与下,微弧氧化膜中除了锐钛矿、金红石和Al_2TiO_5相之外,W含量也随电解液中颗粒含量的增加而提高。在6 g/L纳米W粉复合下,微弧氧化膜的摩擦系数、比磨损率分别减小了约13.33%和3.53%。结论 W粉颗粒以机械啮合附着在氧化膜表面,部分颗粒随熔融氧化物包裹进入膜层并发现熔化迹象。W粉含量为6 g/L时,制备的氧化膜表面质量有所改善,即微孔和裂纹等有所减少,耐磨性较佳,摩擦系数和比磨损率较不含W粉的膜层均有所减小。     

溶胶-凝胶法制备铁酸铋及其可见光催化性能

为了获得新型的窄带隙半导体BiFeO3,以硝酸铁、硝酸铋为主要原料,以无水乙醇和冰醋酸为溶剂,采用溶胶-凝胶法制备干凝胶,然后将干凝胶在氮气条件下、马弗炉中煅烧1h得到BiFeO3粉末样品。采用X射线衍射光谱(XRD)、差热(DTA)分析和漫反射吸收谱(DRS)对BiFeO3的物性进行表征,并以偶氮染料甲基橙作为模拟污水研究BiFeO3的可见光催化性能。结果表明:BiFeO3接近纯相、在832℃附近有一个相变峰,带隙为2.03eV,具有良好的可见光催化活性,是一类具有广泛应用前景的新型窄带隙半导体可见光催化剂。     

机械合金化和添加微量Y2O3对制备细晶钨合金

采用机械合金化、添加微量Y2O3和冷等静压、液相烧结工艺制备Ф25mm的晶粒度为3～4μm的细晶93W-4.9Ni-2.1Fe(质量分数%,下同)合金棒材,研究粉末机械合金化、添加微量Y2O3、烧结温度和保温时间对合金棒材烧结致密化和显微组织的影响。结果表明:在1480℃液相烧结时钨晶粒发生明显球化,在此温度下降低保温时间对控制钨晶粒长大有较大影响,保温时间为30min时,钨晶粒尺寸为5～8μm;保温时间为60min时,钨晶粒为8～10μm。添加微量稀土氧化物Y2O3可以进一步有效地抑制晶粒的长大,降低合金的钨晶粒尺寸和提高组织均匀性,在1480℃烧结60min时,钨晶粒为3～4μm,而且晶粒尺寸分布更均匀。     

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.     

溶胶-凝胶法制备α-Al_2O_3纳米粉体

以工业氧化铝溶胶为原料,通过溶胶-凝胶法制备了-αA l2O3纳米粉体。研究了解胶条件、晶种加入量、矿化剂种类及加入量、煅烧温度及保温时间对产物的影响。结果表明:溶胶解胶后的粒度越小,产物的粒度越小,得到产物所需的煅烧温度越低;晶种和矿化剂的引入,可以促进过渡型氧化铝向-αA l2O3的转化,降低相转变温度;煅烧温度对α-A l2O3的生成影响比较大,在温度恒定时,延长保温时间对产物物相的影响不大。溶胶-凝胶法制备-αA l2O3纳米粉体的最佳条件是分散剂三乙醇胺用量为1%(质量分数),晶种加入量为5%,NH4NO3加入量为5%,煅烧温度为1000℃,保温时间为2 h。所得-αA l2O3纳米粉体外观呈球形,粒度分布均匀,粒径在50 nm左右。     

溶胶-凝胶法制备纳米MoCu复合粉体

以硝酸铜和二钼酸铵为原料，采用溶胶-凝胶法制备了纳米MoCu复合粉体，研究了热处理工艺，溶液pH值，添加剂等对纳米粒子形貌及粒径的影响。结果表明，在600℃热处理的钼铜氧化物通过氢气还原之后可以得到粒径小于60nm的纳米MoCu复合粉体；溶液中添加剂的用量影响微粒的粒径，当添加剂用量K为0．5时，能得到尺寸较小，粒度均匀的纳米粉体；不同酸度条件下所得粉体的粒径各不相同，当pH值在1～4之间变化时粒径随pH值的增大而增大，pH值取1较合适。     

An industrially feasible pathway for preparation of Mo nanopowder and its sintering behavior

In this study, a low-cost, efficient and industrially feasible pathway was developed to prepare Mo nanopowder via a two-stage carbothermic reduction of commercial MoO₃ with carbon black at 600 °C and 1050 °C, respectively, followed by deep hydrogen reduction at 800 °C. The sintering behaviors of the prepared Mo nanopowder and micron commercial Mo powder containing different amounts of Mo nanopowder were investigated in the temperature range of 1000 °C–1600 °C. At 1200 °C, the Mo nanopowder was sintered to near-fully densified compact with a relative density of about 95.8%, which was much higher than the value of 70% for commercial Mo powder. For the nanopowder, the grain size dramatically increased when the sintering temperature increased. The hardness of sintered nanopowder at 1200 °C (relative density, 95.8%; average grain size, 1.88 μm) was about 254 HV0.1, which was much higher than the value of 182 HV0.1 as sintering commercial micron sized Mo at 1600 °C (relative density, 93.9%). The addition of Mo nanopowder into micron Mo can noticeably activate its sintering and improve its hardness.     

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.     

Microstructure of tungsten metal alloys produced by Field Assisted Sintering Technology (FAST)

Tungsten (W) refractory alloys are of high importance in the development of high temperature application products seen in furnace elements, the aerospace industry, and many other areas. Traditional manufacturing processes produce tungsten alloys with undesirable mechanical properties due to a large grain microstructure. Commercial sintering techniques yield low density products due to the poor sinterability of tungsten alloys. Field Assisted Sintering Technology (FAST) is used in this work to produce tungsten alloys with high density, and acceptable microstructures. Limited research has been done with hafnium carbide (HfC) as grain growth inhibitors. 100% W, W-1vol%HfC, W-2vol%HfC, and W-5vol%HfC were sintered at 2100 °C, 35 MPa, for 25 min. Microstructure of each composition was characterized and reported. For volume additions of 2% or more of hafnium carbide shows a decrease in grain size of over 67% while increasing the hardness by over 19% when compared with a pure tungsten composition. These results include imaging between the W-HfC interfaces gathered from high resolution transmission electron microscopy (HRTEM).     

晶粒长大抑制剂对超细WC-9%Co硬质合金性能的影响

在复合抑制剂(VC/Cr3C2)的基础上,添加了不同配比的TaC,研究了TaC对超细WC-9%Co硬质合金组织结构和力学性能的影响。结果表明:添加不同配比的TaC制备的WC-9%Co硬质合金的硬度随着TaC质量分数的增加先增大后减小;TaC的加入降低了W在Co相中的固溶度,从而抑制了晶粒长大。在本实验范围内,在复合抑制剂(VC/Cr3C2)质量分数为0.6%的基础上添加质量分数0.3%的TaC,经1 390℃真空烧结后,制备的超细WC-9%Co硬质合金硬度为93.5 HRA,TRS为2 370 MPa,致密度为99.5%,磁饱和强度为13.29 G.cm3/g,矫顽磁力为31.86 kA/m,此时具有较佳的综合力学性能。     

纳米V2O5薄膜的制备与特性

采用溶胶.凝胶法在Si和普通玻璃基底上制备V2O5纳米薄膜.在空气中对样品进行不同温度的退火处理.利用X射线衍射、扫描电子显微镜和分光光度计对制备的V2O5薄膜的结构、形貌和光学特性进行研究.XRD和SEM研究结果表明:可以通过升高退火温度来提高薄膜的结晶程度、颗粒尺寸及其均匀程度,并增强V2O5的择优取向性.透射谱和吸收谱的研究结果表明:随着退火温度的升高,V2O5薄膜的吸收边缘发生红移,光学带隙逐渐变窄.