纳米W-Cu复合粉体制备工艺的研究进展

由纳米W-Cu复合粉末制备的W-Cu复合材料具有优异的综合性能,从而受到国内外学者的广泛关注。本文对纳米W-Cu复合粉末的制备工艺进行了总结,并对其发展趋势进行了展望。     

W-Cu复合材料制备新技术与发展前景

W-Cu复合材料具有热膨胀系数低、导电性好、导热性好、高熔点、高硬度以及良好的抗电弧烧蚀性能,在机械加工、电气工程以及电子信息领域被广泛用作电极材料、电接触材料、电子封装材料及靶材等越来越受到国内外的关注。传统粉末冶金方法制备的W-Cu复合材料致密度低、组织结构粗大且均匀性差,严重影响材料性能。采用纳米复合新技术制备的W-Cu复合材料具有很大的技术优势:粉末纳米化使得粉末的烧结活化能大大降低,其烧结活化能在1 420℃时仅为42.1 kJ/mol和29.1 kJ/mol,远低于纯W相同温度范围内的587.9 kJ/mol,同时纳米复合使得W与Cu发生了固溶,从而使得复合粉末表现出良好的烧结活性。采用纳米复合制备的细晶W-Cu复合材料具有非常优异的综合性能,其原因在于经烧结后获得高的致密度和组织结构均匀细小。     

WCu10型纳米复合粉的压制与烧结行为研究

本文对用化学方法制备的WCu10型低Cu含量W-Cu纳米复合粉末进行了压制和烧结性能方面的研究,与传统W-Cu混合粉相比较,发现该粉末具有其特殊的性质。要达到相同的压坯密度,纳米复合粉所需要的压制压力要大的多,几乎是常规W与Cu混合粉所需压力的2.5倍。而由于粉末本身高的氧含量和低的Cu含量,需在很高的烧结温度下才能达到致密化。     

等离子体技术制备具有亚微米颗粒结构的球化W-Cu伪合金微粉（英文）

采用复杂多级方法研究并证实制备具有亚微米/纳米级内部结构的球形W-Cu复合微粉的可能性。首先,采用等离子体化学合成法制备具有核壳结构的W-Cu纳米粉末(W核及Cu壳)。然后,将W-Cu纳米粉末与蔗糖的水悬浮液进行喷雾干燥,形成25～63μm的微粒,收率为50%。最后,用热等离子体射流处理由纳米粉末组成的微粒,形成致密的球形W-Cu颗粒。成品粉末的球化度为90%～95%,体积密度为8.1 g/cm³,流动性约为12 s/50 g,杂质中O、C和H的含量(质量分数)分别为0.7%、0.02%～0.2%和0.03%～0.05%。     

W-Cu材料的应用进展和制备技术

W-Cu材料具有高密度、高强度、低膨胀性、良好导电性、良好的加工性等特点而被广泛应用于高压电器、电子封装、航天、武器装备等领域。近年来,面向等离子体抗热冲击的W-Cu功能梯度材料成为一个研究的热点。制备W-Cu材料有传统的液相烧结法、热压法、熔渗法。传统的制备方法生产的W-Cu材料致密度低、导电性差,而且生产成本高,效率低。采用超细或纳米钨铜混合粉可以在较低温度下直接烧制得到接近完全致密的W-Cu材料,这已成为钨铜材料制取工艺的重点研究方向。由超细W-Cu粉末制备的W-Cu材料具有非常高的导热、导电性能,具有传统方法制备的W-Cu复合材料所无法比拟的优点。因此,超细纳米W-Cu复合技术是最具广阔前景的制备方法。     

钨铜纳米复合粉末的制备技术研究

本文针对纳米钨铜复合粉末的制备方法,从粉末制备原料角度出发,分别以W-Cu、W-CuO、WO3-CuO粉末及盐溶液为原料,阐述了几种工艺的优缺点,并分析、比较了这几种工艺方法。通过对比发现以W-CuO粉末为原料的制备方法具有很好的优越性。     

纳米W-Cu粉末的热机械化学法制备及其烧结性能研究

通过均相沉淀获得Cu2WO4(OH)2/CuWO4·2H2O共沉淀物,并对煅烧该沉淀物所得的W、Cu氧化物进行球磨,然后H2还原,得到了含Cu量为30%的W-Cu复合粉末。对该复合粉末的性能进行了表征,并对其烧结体的密度、微结构和力学性能等进行了测试分析。结果表明,热机械化学法制备的W-Cu复合粉末粒度为纳米级,烧结活性高,其压坯在H2气氛中固相烧结可达到96%的相对密度,液相烧结则可达到高于99%的相对密度,烧结体具有细小均匀的微结构和良好的力学性能。     

机械热化学法制备纳米W-Cu复合粉末及其烧结性能研究

WO3和CuO原料粉末经气流粉碎后,在H2气氛中进行共还原,制得了Cu含量为20%(wt%)的纳米W-Cu复合粉末;通过X射线衍射,透射电镜和扫描电镜等方法研究分析所制备W-Cu粉末的烧结行为和烧结体性能.结果表明:气流粉碎可以明显地降低WO3和CuO的粒度;通过对气流粉碎氧化物粉末进行共还原,可获得粒度为50～100nm的W-Cu复合粉末.该粉末烧结活性较高,其成形压坯在1200℃下于H2气氛中烧结后相对密度可达98%以上,且烧结体晶粒细小均匀.其抗弯强度和维氏硬度分别超过1000MPa和300MPa,电导率高于35%IACS.     

机械合金化制备的纳米晶W—Cu电解头材料

采用真空高温7热压熔渗烧结工艺制备出密度为99．5％的纳米晶W-Cu电触头材料，其组织结构和晶粒大小采用SEM，TEM和XRD观察，同时就纳米晶W-Cu电触头材料的硬度，电导率，耐电压强度和抗电弧烧蚀性与传统粉末合金工艺制备的进行了对比分析，结果表明，纳米晶W-Cu电触头材料的硬度，抗电弧烧蚀性及耐电压稳定性远优于传统熔渗法的W-Cu合金，而电导率两者相差不大。     

纳米W-Cu粉末的均相沉淀法制备及其烧结性能

采用湿化学工艺--蒸氨均相沉淀法,制备了纳米CuWO4·2H2O/Cu2WO4(OH)2均相沉淀物,然后煅烧、还原,得到含Cu 30%的W-Cu复合粉.将该复合粉压坯在H2气氛中于不同温度下烧结后,对烧结体的微结构和物理、力学性能等进行了测试分析.实验结果表明:蒸氨均相沉淀法制备的W-Cu复合粉体具有纳米粒度和均匀的化学组成,其烧结活性高,在较低温度下烧结即可达很高的致密化程度.由上述W-Cu粉体所制备的烧结体具有良好的物理、力学性能.     

Micro metal powder injection molding of W-Cu nanocomposite powder

Increasing attention is being paid to micro metal injection molding as a manufacturing technology for miniature part. W-Cu nanocomposites have been used as heat sink and packaging materials in microelectronic devices. A micro injection molding technique will provide and appropriate tool to fabricate W-Cu nanocomposite materials for microcomponents. In the present study, a fundamental investigation of micro metal injection molding using W-Cu nanocomposite powder is reported. The densification behavior of W-Cu nanocomposite was examined in order to confirm the shape stability of microcomponents.     

Effect of ball-milling time on structural characteristics and densification behavior of W-Cu composite powder produced from WO3-CuO powder mixtures

Understanding the microstructure of W–Cu nanocomposite powder is essential for elucidating its sintering mechanism. In this study, the effect of milling time on the structural characteristics and densification behavior of W-Cu composite powders synthesized from WO₃-CuO powder mixtures was investigated. The mixture of WO₃ and CuO powders was ball-milled in a bead mill for 1 h and 10 h followed by reduction by heat-treating the mixture at 800 °C in H₂ atmosphere with a heating rate of 2 °C/min to produce W-Cu composite powder. The microstructure analysis of the reduced powder obtained by milling for 1 h revealed the formation of W–Cu powder consisting of W nanoparticle-attached Cu microparticles. However, Cu-coated W nanocomposite powder consisting of W nanoparticles coated with a Cu layer was formed when the mixture was milled for 10 h. Cu-coated W nanopowder exhibited an excellent sinterability not only in the solid-phase sintering stage (SPS) but also in the liquid-phase sintering stage (LPS). A high relative sintered density of 96.0% was obtained at 1050 °C with a full densification occurring on sintering the sample at 1100 °C. The 1 h-milled W-Cu powder exhibited a high sinterability only in the LPS stage to achieve a nearly full densification at 1200 °C.     

Arc erosion behavior of a nanocomposite W-Cu electrical contact material

The erosion behavior of a nanocomposite W-Cu material under arc breakdown was investigated. The arc erosion rates of the material were determined, and the eroded surfaces and arc erosion mechanisms were studied by scanning electron microscopy. It is concluded that the nanocomposite W-Cu electrical contact material shows a characteristic of spreading arcs. The arc breakdown of a commercially used W-Cu alloy was limited in a few areas, and its average arc erosion rate is twice as large as that of the former. Furthermore, it is also proved that the arc extinction ability and arc stability of the nanocomposite W-Cu material are excellent, and melting is the major failure modality in the make-and-break operation of arcs.     

电镀制备WC@W-Cu复合材料与性能研究

W-Cu复合材料因具有低膨胀系数、高强度及导电导热性能而广泛用作电子封装、电极、电触头和炮弹的罩壳等材料。W-Cu复合材料传统制备方法在致密化、微观组织的均匀性等方面难以兼顾,导致材料的导电导热性能不足,难以满足现代电子工业的要求。以W粉及W粉表面碳化得到的WC@W粉为原料,采用复合电镀技术成功制备了W-Cu和WC@W-Cu复合材料。结果表明,W-Cu复合材料表面粗糙,微观组织存在孔洞,而WC@W-Cu复合材料晶粒细化,微观结构组织均匀、致密。WC@W-Cu复合材料的W含量为43.6wt.%,硬度达205HV,相对密度为99.3%,电导率可达54.6MS/m。采用WC@W纳米粉,电镀制备出的WC@W-Cu复合材料不仅增加了W含量,明显提高了硬度,而且在相对密度和导电性方面也优于W-Cu复合材料。     

Effect of heat-treatment on the nanostructural change of W-Cu powder prepared by mechanical alloying

W-30wt.%Cu powder prepared by mechanical alloying (MA) was annealed at various temperatures to investigate the structural change of MA W-Cu powder. From differential scanning calorimeter analysis and transmission electron microscope observation, it was revealed that the recovery of W in MA W-30wt.%Cu powder occurred at 700°C and the W grain started growing also at this temperature. The W grain had grown significantly after annealing at 900°C, and the Cu phase in the MA powder was found to act as liquid melt near 900°C. The microstructure of the sintered specimen was similar to that of the W-Cu alloy via liquid phase sintering. This microstructure, even at temperatures below Cu melting, was the new feature observed in the MA W-Cu powder. This suggests that such a microstructure is closely related to the inherent high diffusivity of the nanosized W crystallites as well as the liquid-like behavior of the Cu phase.     

Electrical breakdown characteristic of a Ce-doped W-Cu contact material

W-Cu composite powder doped with Ce (1.5 wt.%) was prepared by mechanical alloying (MA), and the W-Cu contact material was fabri-cated by hot pressing sintering in an electrical vacuum furnace. The microstructure, electric conductivity, hardness, and breakdown voltage of the Ce-doped W-Cu alloy were measured and compared with a conventional W-Cu alloy prepared by powder metallurgy. The results show that microstructural refinement and uniformity can improve the breakdown behavior and the electric arc stability of the Ce-doped W-Cu contact material. Also, the Ce-doped W-Cu contact material shows the characteristic of spreading electric arc, which is beneficial to electric arc erosion.     

Synthesis and characterization of W-Cu nanopowders by a wet-chemical method

A wet-chemical process was employed to prepare W-Cu nanopowders. Precursors containing some tungstates were obtained by adding precipitants into a complex solution containing ammonium metatungstate and copper nitrate, afterwards spray-drying the complex solutions. The precursor powders were then calcined and hydrogen-reduced to convert into W-Cu powders. Phase constitution and morphology of the precursors, the calcined powders, as well as the reduced powders were characterized. Relations between the ratio of W to Cu in the complex solutions and the phase constitution of the calcined precursors were investigated. The effects of the reduction temperature and H₂ flow rate on the hydrogen reduction kinetics and the crystallite size of the W-Cu powder were also studied. It was shown that the wet-chemical process produces W-Cu powders with nanosized particles of about 100 nm. The composition of the calcined precursors varies with the ratio of W to Cu in the complex solution, and only CuWO₄ was found in the calcined precursors when the ratio of W to Cu is 74:26(wt.%). The reduction temperature and H₂ flow rate have a great influence on the hydrogen-reduction process and the crystallite size of the resulting W-Cu powders.     

Metal injection molding of W-Cu powders prepared by low energy ball milling

Low energy ball milled W/Cu powders were used for metal injection molding (MIM) in order to overcome the low powder volume fraction of MIM parts after debinding as well as the inherently poor sinterability of the W-Cu powder compacts. Ball milling was carried out using commercial fine W and Cu powders to form a powder mixture suitable for injection molding. W powders showed no change in either size or shape during the milling process, but the ductile Cu powders were easily deformed to a three-dimensional equiaxed shape, having a particle size comparable to that of W powders. This modification of powder characteristics by ball milling resulted in an improvement of the solid loading of roughly 58%, maintaining a high and uniform powder packing density in the feedstock. The densification behavior of W-Cu MIM parts is also discussed on the basis of the relationship between Cu composition and W particle size.