粉末冶金难变形材料热静液挤压技术进展

综述了热静液挤压技术在烧结态粉末冶金难变形材料挤压成形与粉末体高致密化固结方面的研究进展。简述了热静液挤压工艺原理、工艺特点与适用范围,分析了热静液挤压润滑层形成的影响因素,介绍了热静液挤压润滑介质研制和热静液挤压技术在粉末冶金高比重钨合金、γ-TiAl基合金材料的挤压成形以及纳米晶铝合金、弥散强化铜合金、NdFeB永磁合金等金属粉末体材料的高致密化固结成形方面的应用,指出了热静液挤压工艺的技术优势与发展前景。     

医用多孔金属的制备及其生物活化研究进展

医用多孔金属材料,特别是多孔钛及钛合金能够提供与人体骨组织相匹配的力学性能,并促进骨组织长入以提高其与骨的固定度,在人体硬组织修复与替换方面具有广泛的应用前景。重点围绕多孔钛及钛合金的制备方法及适用于其复杂孔隙结构的表面生物活化方法,综述了各种方法在多孔钛及钛合金上的应用现状。目前适用于多孔钛及钛合金制备的技术主要有粉末冶金法、钛纤维烧结法、自蔓延高温合成法、选区电子束熔化技术和选区激光熔化技术,适用于多孔钛及钛合金表面生物活化的技术主要有溶胶凝胶法、仿生矿化法、电化学沉积法和微弧氧化法。多孔钛及钛合金的力学相容性和表面生物活性需要同时满足临床要求,才能进一步扩大其在医学领域的应用范围。     

Effect of cobalt powder morphology on the properties of WC-Co hard alloys

The effect of cobalt powder morphology on the microstructure of WC-Co hard alloys produced by sintering cobalt + tungsten carbide powder mixtures has been studied using X-ray diffraction, laser diffraction, scanning electron microscopy, density measurements, and Vickers microhardness tests. The results indicate that, under identical sintering conditions, the densest and most homogeneous microstructure is formed in hard alloys sintered using cobalt powders consisting of rounded particles. The use of cobalt powders with dendritic morphologies impedes the homogenization of Co + WC powder mixtures and preparation of pore-free WC-Co hard alloys.     

难变形材料热静液挤压复合精密塑性成形工艺

目的 研究热静液挤压及其复合塑性变形工艺在高密度钨合金、钨铜合金、钛基复合材料及镁合金薄壁细管等难变形材料方面的制备。方法 通过对高密度钨合金难变形材料进行热静液挤压及旋转锻造等塑性成形,分析了材料在成形过程中的微观组织及性能变化规律和强化机制,制备出大长径比穿甲弹弹芯材料。在此基础上,将该复合塑性变形技术拓展至两相不互溶材料钨铜合金、钛基复合材料及大长径比镁合金毛细管等难变形材料方面的制备。结果 热静液挤压及其复合塑性变形工艺在粉末冶金难变形材料的致密化方面具有显著优势,获得材料不仅致密度高,而且有效实现了控形控性;对于镁合金薄壁细管成形而言,也可以实现组织与性能的有效调配,同时材料的精度较高。结论 热静液挤压及其复合塑性变形工艺在难变形材料的制备与成形方面具有独特的优势与广阔的应用前景。     

Electronic mechanism of sintering: Some case studies on real systems

The paper reviews the role of electronic configuration model of condensed state in explaining the sintering behaviour of various alloys. The systems are copper base alloys, ferrous alloys containing phosphorus, tungsten based heavy alloys, Al-refractory carbide composites, 6061 Al-alloy composites, high speed steel composites and tungsten carbide based cemented carbides. These studies cover the research activities of the Powder Metallurgy Laboratory at IIT, Kanpur.     

On the structure and properties of wear- and corrosion-resistant nickel-chromium- tungsten-carbon-(silicon) alloys

In some applications, for chemical and physical reasons hard nickel-based alloys have to be used instead of cobalt-based alloys but boron must be avoided. The nickel-chromium-tungsten-carbon system with and without silicon was therefore studied in several concentration ranges at 1050°C with respect to structure, phase, hardness and corrosion and wear resistance. Alloys containing 2% carbon, 10% tungsten and more than 10% chromium are composed of a nickel solid solution and an M₇C₃ carbide in both cast and homogenized (1050°C, 180 h) conditions. On increasing the tungsten content up to 20% the M₂C carbide becomes dominant, and this is associated with a remarkable increase in the hardness of the alloys. Additions of 2% silicon do not change the M₇C₃ and M₂C carbides present. In some cases a carbon-stabilized silicide M₅Si(C) was observed. Silicon additions decrease the liquidus temperature range relatively little, but they affect particle shape and size and the grain size distribution. The relation of various chromium, tungsten and silicon contents to corrosion and wear resistance was studied. The corrosion resistance depends on the chromium content of the nickel solid solution but also on carbide formation (tungsten and carbon content). The silicon content of the nickel solid solution is important too.Because their liquidus temperature is close to 1300°C the alloys cannot be used as self-fluxing and fusing powders for flame spraying but they can be sprayed by plasma torches and they can, of course, be welded.     

粉末注射成形技术及其在难熔钨合金等材料中的应用

粉末注射成形技术是将现代塑料注射成形技术引入粉末冶金领域而形成的一门近净形成形的新技术,有着巨大的发展前景。本文阐述了粉末注射成形技术及其特点,以及在难熔钨合金和硬质合金及其它材料中的应用。     

Grinding behavior of WO3, NiO,Fe2O3 by ultrasonic milling parameters control and preparation of nanocomposite powder

Tungsten-based alloys have been widely applied in various industries due to their excellent mechanical properties. Tungsten-based alloys have a high sintering temperature due to the high melting point of tungsten, so the coarse particles negatively affect the mechanical properties of the alloy. This problem can be solved by increasing the densification by reducing the sintering temperature and time by adding nanoparticles with high surface energy. Herein, we fabricated nanoparticle-sized metal oxides by ultrasonic milling to minimize the influx of impurities to improve the densification of tungsten alloys. The main parameters of the ultrasonic milling experiments were ball density and ball layer. Metal oxides prepared by ultrasonic milling showed an average particle size distribution of less than 200 nm, and metal composite powders prepared through subsequent hydrogen reduction also showed nanoparticle size distributions. We believe that this approach will enable the production of improved sintered tungsten-based alloys.     

High-Resolution Patterning of Organic–Inorganic Photoresins for Tungsten and Tungsten Carbide Microstructures

Tungsten is an important material for high-temperature applications due to its high chemical and thermal stability. Its carbide, that is, tungsten carbide, is used in tool manufacturing because of its outstanding hardness and as a catalyst scaffold due to its morphology and large surface area. However, microstructuring, especially high-resolution 3D microstructuring of both materials, is a complex and challenging process which suffers from slow speeds and requires expensive specialized equipment. Traditional subtractive machining methods, for example, milling, are often not feasible because of the hardness and brittleness of the materials. Commonly, tungsten and tungsten carbide are manufactured by powder metallurgy. However, these methods are very limited in the complexity and resolution of the produced components. Herein, tungsten ion-containing organic–inorganic photoresins, which are patterned by two-photon lithography (TPL) at micrometer resolution, are introduced. The printed structures are converted to tungsten or tungsten carbide by thermal debinding and reduction of the precursor or carbothermal reduction reaction, respectively. Using TPL, complex 3D tungsten and tungsten carbide structures are prepared with a resolution down to 2 and 7 μm, respectively. This new pathway of structuring tungsten and its carbide facilitates a broad range of applications from micromachining to metamaterials and catalysis.     

Coated WC powders by sputtered nanostructured Ni and stainless steel

The efficiency of the powder surface modification depends on their surface characteristics. Sputtering has been revealing an important skill for the coating of powders with metal and metal alloys, with important consequences on the surface properties. However, some modifications in the holder of this particulate substrate have obliged to set up some changes in a non-conventional sputtering system. The aim of the present work is to demonstrate the efficiency of the prototype developed and the influence of deposition parameters in the quality of coated powders; tungsten carbide powders and austenitic stainless steel (SS) and nickel targets have been selected. These types of materials are used in tungsten carbide parts/devices as binders to promote the technological process; as coatings they decrease the interparticle friction reducing the pressure of shape forming as well as the temperature of sintering process.     

The ceracon process for P/M technology: A review of recent developments

The Ceracon process, CERAmic CONsolidation, was originally developed in the mid 1970's to consolidate powder metals. The process has been successfully applied to near-net-shape production of oil drilling and other mechanical tools using conventional materials such as steel or tungsten carbide. The basic concept of the Ceracon process to consolidate powder material is still applicable in the preparation of fully dense forms, but there are a number of new applications for the Ceracon process which have emerged over the past few years. In this article, the latest developments in the Ceracon technology will be reviewed. These developments include the consolidation of oxide enclosed P/M materials such as environmentally sensitive superconducting powders, aluminum 6061 alloy and rapidly solidified Ti-48%A1 alloys.     

Novel Flow-Softening and Flow-Anisotropy Approaches to Developing Improved Tungsten Kinetic Energy Penetrator Materials

The penetration performance of uranium alloy kinetic energy (long rod) projectiles are superior to that of equivalent projectiles manufactured from high-density tungsten-based composites. Prior research efforts seeking improvements in the penetration capabilities of tungsten penetrator materials have focussed on increases in the strength, ductility, and toughness of the composites and have not been successful.

Recent studies at the U.S. Army Research Laboratory, however, have established that it is the rate at which the penetrator material softens, under the high-rate, high-pressure deformation it must undergo in the penetration process, not the material's initial strength or ductility, which governs its performance. The rapid flow-softening behavior of uranium alloys, a function of both their mechanical (strain-hardening, strain rate-hardening) and thermal (thermal-softening, etc.) properties, was shown to be responsible for their superior ballistic performances. Other tests demonstrated analogous differences in the performance of different orientations of monocrystal tungsten penetrators, due to the anisotropics in their flow-strengthening and flow-softening behaviors. These results have indicated two novel and promising directions for tungsten penetrator research, broadly categorized as (1) flow-softening and (2) flow-anisotropy approaches. The flow-softening approach seeks to develop an isotropic, plastically unstable behavior, similar to that exhibited by uranium alloys, in new tungsten composites. This approach relies primarily on modifications or replacements of the nickel-based matrix in the currently produced tungsten composites with thermomechanically less stable alloys. Critical issues include the roles and interactions between matrix and tungsten particle phases in the thermomechanical properties of the overall composite, and the nucleation and growth of plastic localizations in these materials. The flow-anisotropy approach seeks to develop directional flow-softening behavior in tungsten-based composites by orienting the tungsten phase.

These efforts to develop tungsten penetrator materials, with performance equalling or surpassing that of depleted uranium, but without the environmental and political concerns associated with producing and fielding uranium ammunition, are reviewed.     

钨基高比重合金的制备研究进展综述

综述了当前国内外钨基高比重合金制备的研究进展,介绍了WHAs制备工艺中存在的问题和当前的研究方向.采用机械合金化制取纳米预合金粉是WHAs制备取得突破性进展的新工艺之一;活化烧结和二步烧结可显著改善其力学性能;纳米粉末烧结技术的关键就是在得到全致密合金的同时,保持材料的纳米结构才能对性能作出很大的贡献.     

Specific features of structure formation of synthetic hard tool materials in the SHS compacting process

The basic specific features of structure formation and properties of a number of transient metal carbide and boride-base alloys produced by self-propagating high-temperature synthesis (SHS) of compact uniform compositions and synthetic gradient materials are considered. The main effects of the ultrasonic field on SHS compacting are emphasized. Ultrasonic oscillations are one of the effective means of controlling the structure of hard alloy materials.Institute of Structural Macrokinetics, Russian Academy of Sciences, Chernogolovka. Translated from Inzhenerno-Fizicheskii Zhurnal, Vol. 63, No. 5, pp. 558–576, November, 1992.     

Nickel-based wear-resistant coatings by vacuum melting

In various coating processes nickel-based hard alloy powders are applied in either an atomized or a mechanically pulverized form. The coatings show good corrosion resistance, a high abrasion resistance and a relatively low melting point. Since boron is sparingly soluble in nickel, the boride Ni₃B forms a low melting eutectic at about 1000 °C with the nickel solid solution. Boron and silicon act simultaneously as deoxidizers and improve both the properties of the coating and the bonding to the substrate. Diffusion into the substrate occurs during the coating procedures.In this paper we discuss the behaviour of heterogeneous powder compounds with nickel hard alloys. For many applications mixtures with various carbides are used. During coating, reactions take place between the Ni-Cr matrix and the added carbides. These heterogeneous or quasi-alloys, which are used because of their abrasion resistance, are metastable.The abrasion resistance depends primarily on the phases as well as on their grain size, the grain size distribution and alterations to the matrix. When carbidic quasi-alloys are exposed to abrasion and corrosion at high temperatures, reactions of the existing phases during use cannot be completely excluded. Heat treatment causes changes in the structure and abrasion resistance of carbide-containing quasi-alloys.It is difficult to follow reactions which take place during coating either in the fused mass of quasi-alloys or in heterogeneous compounds. Because of their relatively low melting points nickel-based hard alloys can be coated by furnace melting. Hence carbide compounds with Ni-Cr-B-Si powder alloys are most suitable for research also. In these mechanical alloys segregation, of relevance to practical applications, can be studied as well as the formation of various phases during the coating or heat treatment processes.The behaviour of mixtures of Ni-Cr-B-Si powder alloy with different amounts of a number of carbides is reported. The structures of the resulting phases were studied and we tried to correlate these with the results of our abrasion tests.For tungsten carbide-nickel hard alloy mixtures the formation of the ? phase is influenced by the coating parameters and the matrix as well as by the diffusion of iron from the substrate into the coating.We also investigated mixtures of an Ni-Cr-B-Si matrix with TiC (Ti, W)C and NbC. The wear resistance against steel and SiC was measured. Various wear mechanisms and the properties of the carbide-matrix interface the wear results.     

Chemical processing of nanophase WC–Co composite powders

Abstract

The future development of advanced engineered materials for structural, electrical, magnetic, catalytic, and other applications will depend to an increasing extent on improved control of the size, distribution, and morphology of the constituent phases of the materials. In advanced materials systems, this development is in the direction of diminishing scale and increasing uniformity of the structure, extending into the nanoscale regime. The capabilities for synthesising novel nanophase structures are now becoming available in the laboratory and efforts are being made to scale up these processes to produce the quantities required for prototype development, field testing, and commercial applications. This paper addresses the scientific and technical issues relating to the chemical processing of nanophase WC–Co composite powders and the integration of the various processing steps into a new spray conversion processing technology. The new technology involves three coordinated steps: preparation and mixing of starting solutions; spray drying to form chemically homogeneous precursor powders; and fluid bed thermochemical conversion of the precursor powders to nanophase WC–Co powders. Both spray drying and fluid bed conversion are proven scalable technologies and offer the potential for producing bulk quantities of cemented carbide powders at lower manufacturing cost.

MST/1318     

感应等离子体技术制备球形铸造碳化钨粉体及其性能表征

球形碳化钨增强金属基复合涂层具有高硬度、高韧性和优异的耐磨、耐蚀性等特点,可以对材料表面起到有效保护作用。传统铸造碳化钨粉体多呈不规则的片状或多角状,流动性差且硬度低,难以满足高性能涂层材料的要求。本文以多角状铸造碳化钨粉体为原料,采用感应等离子体技术制备球形碳化钨粉体,研究感应等离子体技术工艺参数对碳化钨粉体球化效果的影响规律。采用扫描电子显微镜、X射线衍射仪、霍尔流速计、激光粒度分析仪等对球化处理前后碳化钨粉体的形貌、物相、松装密度、粒度分布进行表征。结果表明:送粉率为110 g/min、载气流量为5.0 L/min时,采用感应等离子体技术可制备颗粒饱满、表面光滑、分散性良好,球化率高达99%以上,且球形度较好的球形碳化钨粉体。球化后碳化钨粉体无孔洞等缺陷,内部组织为典型的细针状WC和W₂C的共晶,组织结构均匀细密。球化后碳化钨粉体的硬度高达3 258HV,提高了408HV;球化后碳化钨粉体的松装密度由8.01 g/cm³提高到9.75 g/cm³,霍尔流速由10.30 s/50 g降低到6.80 s/50 g,粉体的流动性提高。     

Microstructure of alumina reinforced with tungsten carbide

Carbides and nitrides reinforced alumina based ceramic composites are generally accepted as a competitive technological alternative to cemented carbide (WC-Co). The aim of this work was to investigate the effect of dispersed tungsten carbide (WC) on the microstructure and mechanical properties of alumina (Al₂O₃). Micron size alumina and tungsten carbide powders were mixed in a ball mill and uniaxially pressed at 1600°C under 20 MPa in an inert atmosphere. The hardness of WC reinforced alumina was 19 GPa and fracture toughness attained up to 7 MPa m^1/2. It was demonstrated by TEM analysis that coarse, micrometersized tungsten carbide grains were located at grain boundaries of the alumina matrix grains. Additionally, sub-micrometer tungsten carbide spheres were found inside the alumina particles. Crack deflection triggered by the tungsten carbide at the grain boundaries of the alumina matrix is supposed to increase fracture toughness whereas the presence of intergranular and intragranular hard tungsten carbide particles are responsible for the increase of the hardness values of the investigated composite materials.     

The new trends in fabrication of bulk nanostructured materials by SPD processing

During the past decade, fabrication of bulk nanostructured metals and alloys using severe plastic deformation (SPD) has been evolving as a rapidly advancing direction of nanomaterials science and technology aimed at developing materials with new mechanical and functional properties for advanced applications. The principle of these developments is based on grain refinement down to the nanoscale level via various SPD techniques. This paper is focused on investigation and development of new SPD processing routes enabling fabrication of fully dense bulk nanostructured metals and alloys with a grain size of 40–50 nm and smaller, namely, SPD-consolidation of powders, including nanostructured ones, as well as SPD-induced nanocrystallization of amorphous alloys. We also consider microstructural features of SPD-processed materials that are responsible for enhancement of their properties.     

The formation of tungsten carbide in cobalt-base wear-resistant coating alloys

Tungsten carbide-cobalt alloys cannot be produced by melting because of a peritectic reaction in the W-C system; they are produced by sintering. Tungsten carbide-cobalt powders (mixed, agglomerated, sintered) can be plasma sprayed or deposited by other techniques but they cannot be fused afterwards without decomposition of the tungsten monocarbide that provides the best mechanical properties for many applications.Wear-resistant cobalt alloys were developed 60 years ago and are based on cobalt-chromium-tungsten-carbon. During studies of the CoCrWC system with various carbon concentrations and at various temperatures we identified MC, M₂C, M₇C₃, M₂₃C₆, M₆C, M₁₂C and M₂₈C carbides. The solidifying M₆C carbide is unstable over a certain concentration range of chromium and decomposes to form tungsten carbide (WC). On heat treatment the tungsten-containing M₆C forms WC in a cobalt-chromium matrix if the chromium content is less than 5 wt.%. It is therefore possible to produce a sprayed and fused or welded layer of WC-cobalt alloy. The rate of WC formation depends on temperature and time. Time-temperature-decomposition diagrams have been established for four alloys. The structures of the heat-treated alloys are similar to those of sintered tungsten carbide-cobalt alloys.