复合稀土氧化物对Ti-Al/WC涂层组织和摩擦学性能的影响

采用等离子喷涂方法制备了未添加稀土氧化物以及含有不同复合稀土氧化物的Ti-Al/WC涂层,使用自带能谱仪的扫描电镜、X射线粉末衍射仪和电子天平对各类涂层的磨损表面及截面组织形貌、残余应力和磨损量进行了观察和检测,使用摩擦磨损试验机比较和分析了不同类型涂层的耐磨性能。结果表明:含有稀土氧化物的Ti-Al/WC涂层内部晶粒得到细化,颗粒物含量大幅度减少,孔洞变小,裂纹数量及尺寸显著降低。与只含一种稀土氧化物的涂层相比,复合稀土氧化物对涂层微观组织改善情况更加明显。当同时加入CeO₂、Y₂O₃和La₂O₃后,涂层组织中的显微缺陷最少,各成分分布最为均匀,截面显微形貌最好,此时,涂层的残余应力达到最小值275.7 MPa,且耐磨性最强,总磨损量仅有16.8 mg。与未添加稀土氧化物的涂层相比,二者分别减少了30.3%和69.8%。     

不同超细氧化物掺杂钼合金棒材的拉伸性能及强化机理（英文）

通过水热合成、共沉淀、共分解、粉末冶金和旋锻方法制备了3种掺杂2.0%(体积分数)不同氧化物(Al₂O₃、ZrO₂和La₂O₃)的钼合金棒材。3种纳米氧化物均使钼晶粒细化70%以上，且使合金的断裂模式从脆性断裂转变为韧性断裂，从而显著提高钼合金的综合力学性能，克服强度和韧性之间的矛盾。在3种钼合金中，Mo-ZrO₂合金具有最佳的强度和塑性，这归因于细小的ZrO₂颗粒以及ZrO₂与钼基体之间的半共格界面。此外，建立了与位错密度、氧化物体积分数和尺寸以及钼晶粒尺寸相关的定量强化模型。     

纳米级和微米级稀土氧化物掺杂W-La2O3-Y2O3-ZrO2 阴极尖端的组织和性能

使用粉末冶金法将纳米级(70–80 nm)和微米级(500–600 nm)稀土氧化物(La₂O₃,Y₂O₃)与钨粉混合,随后通过冷等静压、中频感应烧结、旋锻、拉拔等一系列工艺制备了W-1.5La₂O₃-0.1Y₂O₃-0.1ZrO₂(质量分数,%)材料。对含有纳米和微米尺寸稀土氧化物的阴极样品使用相同的焊接电流,分别进行了0.5、1、2 h的氩弧焊。结果表明,具有纳米级稀土氧化物的样品在焊接过程中表现出更高的工作稳定性,烧损同比降低了近85.4%。此外,随着工作时间的延长,阴极尖端不同区域的稀土氧化物聚集度显著增加。结合COMSOL Multiphysics温度模拟发现,第二相的扩散活化能降低了近34%。这是因为更为细小的第二相有效地控制了钨基体组织的演变,保留了大量晶界作为通道,促进了活性物质在电子发射过程中的扩散。     

氧化镧的加入对PREP制备钨粉末性能的影响

采用等离子旋转电极雾化技术(plasma rotating electrode processing,PREP)制备出纯W和W-La合金球形粉末,对比分析了2种类型粉末的化学成分、形貌、物理性能、缺陷和粒度分布。结果表明:PREP法制备的球形纯W粉末表面光滑、球形度高,小于106μm粉末的收得率为70%。在棒料中加入La₂O₃后,大部分La₂O₃在PREP过程中挥发,残余的La₂O₃优先附着于液滴表面,降低了的液态金属钨的表面张力,将小于106μm粉末的收得率提升至90%;但是,表面张力的降低同时也导致W-La合金粉末表面出现少量缺陷。La₂O₃提高粉末收得率的现象为研究提高PREP技术粉末收得率提供了新思路。     

放电等离子烧结超细晶ODS镍基合金的高温氧化行为研究

通过机械合金化 (MA) 和放电等离子烧结 (SPS) 制备了 Cr₂O₃颗粒强化的超细晶结构镍基高温合金(ODS 合金)。对比研究了不添加氧化物颗粒合金 (Base 合金) 和 ODS 合金样品的微观结构和高温氧化行为。结果表明,在1200 ℃烧结过程中,Cr₂O₃完全转变为Al₂O₃。由于SPS快速烧结及弥散分布的原位Al₂O₃颗粒钉扎,抑制了晶粒长大,ODS合金具有十分细小的晶粒结构,其平均晶粒尺寸为0.98 μm;Base合金平均晶粒尺寸稍大,为1.54 μm。ODS合金在900 ℃下具有较好的抗氧化性能和较低的氧化速率,得益于其表面迅速生成了连续致密的内层α-Al₂O₃膜,能有效地阻止Ti和Cr向外扩散,表面生成少量保护性较差的TiO₂和NiCr₂O₄。而Base 合金表面则生成了以 Al     

溶胶-凝胶/高温氢还原工艺制备Mo-Al2O3-La2O3复合粉末

Al₂O₃协同La₂O₃强韧化的钼及钼合金具有优越的综合力学性能，通过粉末冶金方法制备钼及钼合金的关键在于获得超细或纳米Mo-Al₂O₃-La₂O₃粉末。本文以仲钼酸铵、硝酸铝、硝酸镧和柠檬酸为原料，采用溶胶-凝胶-煅烧-高温氢还原工艺制备Mo-Al₂O₃-La₂O₃复合粉末，利用XRD、SEM、EDS和TEM等分析手段对粉末的微观组织结构进行表征。结果表明：当水浴温度为85℃、p H=1、柠檬酸与钼酸铵的质量比为1.7时，形成了网状结构大分子交联的络合物前驱体，这有利于在后续高温还原过程中制备超细或纳米Mo复合粉末。前驱体粉体在550℃煅烧3 h后，粉末主要由MoO₃和Al₂(Mo O₄)₃组成。采用一步高温氢还原时，还原3 h后MoO<...     

微量Y2O3对细晶W-Ni-Fe粉末烧结行为和显微组织的影响

采用喷雾干燥-热还原的方法制备纳米级93W-4.9Ni-2.1Fe复合粉末和微量稀土掺杂的复合粉末,研究微量稀土掺杂对烧结致密化和晶粒尺寸的影响.结果表明:微量稀土掺杂能有效地降低该复合粉末的晶粒尺寸,并能改善粉末的分散度;纳米级复合粉末在1380～1410℃液相烧结可实现材料的近全致密化,比同种成分的传统钨合金的烧结温度降低了120℃左右,合金的相对密度可达99%以上;但微量稀土掺杂对烧结的致密化有一定的抑制作用;同时微量稀土元素对合金的晶粒尺寸的抑制作用主要发生在液相烧结阶段.     

多孔Ni-Cu-Ti-La2O3复合电极的制备及其析氢性能

采用粉末冶金方法烧结制备了多孔Ni-Cu-Ti-La₂O₃复合电极,讨论不同La₂O₃的掺杂量对电极析氢性能的影响。利用X射线衍射(XRD)、扫描电镜(SEM)、能谱仪(EDS)等测试手段对电极的微观结构和物相组成进行表征。结果表明：Ni-Cu-Ti合金体系中La₂O₃的掺杂可有效提高电极材料的电荷传输速率,多孔Ni-Cu-Ti-La₂O₃复合电极在6 mol/L KOH溶液中表现出良好的析氢催化活性,其整体析氢催化活性明显优于多孔Ni-Cu-Ti、Ni-Cu-W、Ni-Cu-Co、Ni-Cu-Zr和Ni-Cu电极;当烧结温度为1000℃时,成分为Ni-CuTi-9La的多孔复合电极具有最佳的析氢催化性能,其Tafel斜率为63.18 mV/dec,电流密度在10 mA/cm²时过电位为1077 mV(vs Hg/HgO),多孔Ni-Cu-Ti-La₂O₃     

纳米稀土氧化物对陶瓷结合剂的强韧化

为提高CBN砂轮用陶瓷结合剂的强度与韧性,以不同体积分数的纳米CeO₂、Sm₂O₃、Y₂O₃、La₂O₃、Er₂O₃与基础结合剂形成复合结合剂,并通过X射线衍射仪和扫描电子显微镜表征其物相和显微结构,通过三点弯曲、单边切口梁等测试方法测试其机械性能。实验结果表明:添加体积分数2%的纳米CeO₂或纳米Er₂O₃后,试样的抗折强度分别为187 MPa和194 MPa,比基础结合剂的165 MPa分别提高了13.3%和17.6%,而其他3种纳米稀土氧化物没有表现出增强作用。5种纳米稀土氧化物均可增加基础结合剂的韧性,但Er₂O₃的效果最明显,在体积分数为2.5%时,试样的断裂韧性为2.7 MPa·m1/2,比基础结合剂的1.3 MPa·m1/2提高了108.2%。以含纳米Er₂O₃体积分数2%的复合结合剂与CBN磨料（浓度200%）混合制备试样,发现该复合结合剂对CBN颗粒的润湿良好,试样的抗折强度为102 MPa。      

ZrO_2增强钨基复合材料制备工艺与性能

采用共沸蒸馏法结合粉末冶金法制备了ZrO_2增强钨合金(W-ZrO_2)。利用XRD、SEM、EDS、TEM等研究了初始溶液的p H值、还原工艺及ZrO_2掺杂量对W-ZrO_2复合粉末粒径及形貌的影响,观察了钨合金的显微组织及其物相组成,测定了复合钨粉的粒度、钨合金的密度、显微硬度及其磨损性能。结果表明:初始溶液的p H值对掺杂钨粉的形貌和尺寸有着显著影响,随着初始溶液的p H值增大,复合粉末颗粒尺寸逐渐增加;经750℃×2 h+850℃×4 h两段还原工艺后所得的复合粉末粒径细小;ZrO_2对复合钨粉颗粒及钨合金晶粒细化作用明显,进而对钨合金密度及硬度产生显著影响,随着ZrO_2含量的增加,钨合金密度与显微硬度降低,耐磨性呈先增加后降低趋势,其中W-3%ZrO_2钨合金的耐磨性较纯钨提高了20%~40%。     

Mechanical alloying of lanthana-bearing nanostructured ferritic steels

A novel nanostructured ferritic steel powder with the nominal composition Fe–14Cr–1Ti–0.3Mo–0.5La₂O₃ (wt.%) was developed via high energy ball milling. La₂O₃ was added to this alloy instead of the traditionally used Y₂O₃. The effects of varying the ball milling parameters, such as milling time, steel ball size and ball to powder ratio, on the mechanical properties and microstructural characteristics of the as-milled powder were investigated. Nanocrystallites of a body-centered cubic ferritic solid solution matrix with a mean size of approximately 20 nm were observed by transmission electron microscopy. Nanoscale characterization of the as-milled powder by local electrode atom probe tomography revealed the formation of Cr–Ti–La–O-enriched nanoclusters during mechanical alloying. The Cr:Ti:La:O ratio is considered “non-stoichiometric”. The average size (radius) of the nanoclusters was about 1 nm, with number density of 3.7 × 10²⁴ m^?3. The mechanism for formation of nanoclusters in the as-milled powder is discussed. La₂O₃ appears to be a promising alternative rare earth oxide for future nanostructured ferritic steels.     

Mechanical behaviors of alumina ceramics doped with rare-earth oxides

The effects of three types of additives Y₂O₃, La₂O₃, and Sm₂O₃ on the sintering and mechanical behaviors of alumina ceramics were investigated. The bending strengths of alumina ceramics with Sm₂O₃ and Y₂O₃ additions were 455 and 439 MPa, respectively, higher than that with La₂O₃ addition. The fracture toughness of the ceramics with Sm₂O₃ and Y₂O₃ were also higher than that with La₂O₃ addition. The fracture mode of rare earth oxides doped alumina ceramics exhibited obvious transgranular fractures as well as intergranular fracture. The results of research show that the improvement of bending strength and fracture toughness of alumina ceramics with rare earth oxides was achieved by refining the grain size and strengthening the grain boundary.     

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.     

Preparation of ultrafine tungsten powders by in-situ hydrogen reduction of nano-needle violet tungsten oxide

Ultrafine tungsten powders with a grain size below 0.5 μm are key raw materials for fabricating ultrafine cemented carbides. Conventional hydrogen reduction technique has been utilized to prepare the ultrafine tungsten powders. In the present work, highly pure nano-needles of violet tungsten oxide (WO_2.72) were reduced by dry hydrogen. Nucleation and growth of the metallic tungsten in the early stage of hydrogen reduction have been studied by XRD, FESEM and HRTEM. Mechanism of formation of nano-size tungsten powders is proposed and a concept of in-situ hydrogen of the nano-needle WO_2.72 is presented. Empirical relations between an average diameter of nano-needle WO_2.72 and an average particle size of the resultant tungsten powders in both stage of nucleation and industrial conduction have been established. These empirical relations could be a reasonable guidance for suitably choosing the raw materials of nano-needle WO_2.72 to prepare ultrafine tungsten powders. It has been determined that the BET special surface areas of the in-situ hydrogen-reduced tungsten powders with the average particle size of 0.2 μm and 0.3 μm, which were produced from the raw nano-needle WO_2.72 powders with the average diameter of 60 nm and 80 nm, are 6.03 m²/g and 4.65 m²/g, and the oxygen contents are 0.35% and 0.29%, respectively.     

Fabrication of high temperature oxides dispersion strengthened tungsten composites by spark plasma sintering process

The paper describes the fabrication process of high temperature oxides, such as Y₂O₃, HfO₂ and La₂O₃, dispersed tungsten composites by spark plasma sintering. The oxide contents varied from 0 to 5 wt% and sintering was conducted for 3 min at 1700 °C. Among three kinds of oxides, Y₂O₃ is the most efficient element to consolidate W powder. As dispersed up to 5 wt% Y₂O₃ into the matrix, the relative density of the W composite is increased up to nearly 100% of theoretical value. In order to analyze the effect of Y₂O₃ particles on the densification of W powders, the microstructure of W–Y₂O₃ composite is observed using the transmission electron microscopy. By this experiment, it is found that dark phases, which had been known as Y₂O₃ phase, are composed of W, Y and O. Therefore, during sintering, W atoms move through Y₂O₃ phases as well as W grain boundaries, thereby W and Y₂O₃ are soluble, and so sinterability of W is enhanced. The hardness of the composite is increased from 350 to 510 kg/mm² with increasing Y₂O₃ contents since the relative density is increased and the grain size is reduced from 20 to 4 μm. However, in case of HfO₂ and La₂O₃, the hardness of the composites is decreased even though the grain size is reduced because of their lower relative densities.     

钨涂层及氧化镧合金面对等离子体材料研究

介绍了等离子体喷涂钨涂层和粉末冶金钨氧化镧合金面对等离子体材料的制备,并对其进行了性能分析,主要包括微观结构、杂质含量、气孔大小及气孔率分布、结合强度、热导率以及热负荷疲劳性能和承受能力。结果表明:真空等离子体喷涂钨涂层性能比大气喷涂钨涂层性能优越,是更为合适的钨涂层制备技术。真空喷涂钨涂层具有较低的气孔率、较高的热导率、较低的杂质含量和较优异的热负荷性能,能够承受10 MW/m²、100周次疲劳测试。氧化镧弥散掺杂相具有钉扎作用,能够抑制钨烧结过程中的长大,有效提高钨材料强度,改善热负荷性能,W-1%La₂O₃(质量分数)材料能够承受6MW/m²的热负荷。     

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.     

Inhibition of tungsten particle growth during reduction of V-doped WO3 nanoparticles prepared by co-precipitation method

The effect of vanadium on the tungsten particle growth during hydrogen reduction has been discussed. The nanostructured V-doped WO₃ powder was synthesized by co-precipitation method with ammonium tungstate and ammonium metavanadate as its starting materials and was then reduced in hydrogen atmosphere. The products were characterized by X-ray diffractometry, scanning electron microscopy, thermogravimetric analysis and small angle X-ray scattering. It was observed that the vanadium added to tungsten oxide formed tungsta-vanadate solid solution and was then reduced to V–O–W bronze, V_xWO_3−y, during the early stage of hydrogen reduction and decomposed continuously to α-W and V₂O₃ during the entire WO₂ → W transition. The results of particle size measurement and morphological analysis showed that the addition of vanadium could effectively inhibit the particle growth of tungsten powder during the reduction process. The addition of vanadium mainly effects on nucleation of tungsten at the lower temperatures below 850 °C because the slow decomposition of V–O–W bronze continuously provides the nucleation sites on the surface of WO₂ particles during reduction via impeding the formation of WO₂(OH)₂ and providing of nucleation aids for W deposition from the surrounding WO₂.     

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.