Tungsten carbide is widely used in carbide tools. However, its production process generates a significant number of end-of-life products and by-products. Therefore, it is necessary to develop efficient recycling methods and investigate the remanufacturing of tungsten carbide using recycled materials. Herein, we have recovered 99.9% of the tungsten in cemented carbide hard scrap as tungsten oxide via an alkali leaching process. Subsequently, using the recovered tungsten oxide as a starting material, tungsten carbide has been produced by employing a self-propagating high-temperature synthesis (SHS) method. SHS is advantageous as it reduces the reaction time and is energy-efficient. Tungsten carbide with a carbon content of 6.18 wt % and a particle size of 116 nm has been successfully synthesized by optimizing the SHS process parameters, pulverization, and mixing. In this study, a series of processes for the highefficiency recycling and quality improvement of tungsten-based materials have been developed.
An optimum route to fabricate a hybrid-structured W powder composed of nano and micro size powders was investigated. The mixture of nano and micro W powders was prepared by a ball milling and hydrogen reduction process for WO3 and W powders. Microstructural observation for the ball-milled powder mixtures revealed that the nano-sized WO3 particles were homogeneously distributed on the surface of large W powders. The reduction behavior of WO3 powder was analyzed by a temperature programmed reduction method with different heating rates in Ar-10% H2 atmosphere. The activation energies for the reduction of WO3, estimated by the slope of the Kissinger plot from the amount of reaction peak shift with heating rates, were measured as 117.4 kJ/mol and 94.6 kJ/mol depending on reduction steps from WO3 to WO2 and from WO2 to W, respectively. SEM and XRD analysis for the hydrogen-reduced powder mixture showed that the nano-sized W particles were well distributed on the surface of the micro-sized W powders.
The effect of the mixing method on the characteristics of hybrid-structure W powder with nano and micro sizes is investigated. Fine WO3 powders with sizes of ~0.6 μm, prepared by ball milling for 10 h, are mixed with pure W powder with sizes of 12 μm by various mixing process. In the case of simple mixing with ball-milled WO3 and micro sized W powders, WO3 particles are locally present in the form of agglomerates in the surface of large W powders, but in the case of ball milling, a relatively uniform distribution of WO3 particles is exhibited. The microstructural observation reveals that the ball milled WO3 powder, heat-treated at 750oC for 1 h in a hydrogen atmosphere, is fine W particles of ~200 nm or less. The powder mixture prepared by simple mixing and hydrogen reduction exhibits the formation of coarse W particles with agglomeration of the micro sized W powder on the surface. Conversely, in the powder mixture fabricated by ball milling and hydrogen reduction, a uniform distribution of fine W particles forming nano-micro sized hybrid structure is observed.
Effect of oxygen content in the ultrafine tungsten powder fabricated by electrical explosion of wire method on the behvior of spark plasma sintering was investigated. The initial oxygen content of 6.5 wt% of as-fabricated tungsten powder was reduced to 2.3 and 0.7 wt% for the powders which were reduction-treated at 400˚C for 2 hour and at 500˚C for 1h in hydrogen atmosphere, respectively. The reduction-treated tungsten powders were spark-plasma sintered at 1200-1600˚C for 100-3600 sec. with applied pressure of 50 MPa under vacuum of 0.133 Pa. Maximun sindered density of 97% relative density was obtained under the condition of 1600˚C for 1h from the tungsten powder with 0.7 wt% oxygen. Sintering activation energy of 95.85kJ/mol-1 was obtained, which is remarkably smaller than the reported ones of 380~460kJ/mol-1 for pressureless sintering of micron-scale tungsten powders.
Cobalt coated tungsten carbide-cobalt composite powder has been prepared through wet chemical reductionmethod. The cobalt sulfate solution was converted to the cobalt chloride then the cobalt hydroxide. The tungsten carbidepowders were added in to the cobalt hydroxide, the cobalt hydroxide was reduced and coated over tungsten carbidepowder using hypo-phosphorous acid. Both the cobalt and the tungsten carbide phase peaks were evident in the tungstencarbide-cobalt composite powder by X-ray diffraction. The average particle size measured via scanning electron micro-scope, particle size analysis was around 380 nm and the thickness of coated cobalt was determined to be 30~40 nm bytransmission electron microscopy.
Cemented tungsten carbide has been used in cutting tools and die materials, and is an important industrial material. When the particle size is reduced to ultrafine, the hardness and other mechanical properties are improved remarkably. Ultrafine cemented carbide with high toughness and hardness is now widely used. The objective of this study is synthesis of nanostructured WC-Co powders by liquid phase method of tungstate. The precursor powders were obtained by freezen-drying of aqueous solution of soluble salts, such as ammonium metatungstate, cobalt nitrate. the final compositions were WC-10Co. In the case of liquid phase method, it can be observed synthesis of WC-10Co. The properties of powder produced at various temperature, were estimated from the SEM, BET and C/S analyser.
Ultrasonic-milling of metal oxide nanopowders for the preparation of tungsten heavy alloys was investigated. Milling time was selected as a major process variable. XRD results of metal oxide nanopowders ultrasonic-milled for 50 h and 100 h showed that agglomerate size reduced with increasing milling time and there was no evidence of contamination or change of composition by impurities. It was found that nanocomposite powders reduced at in a hydrogen atmosphere showed a chemical composition of 93.1W-4.9Ni-2.0Fe from EDS analysis. Hardness of sintered part using 50 h and 100 h powder samples was 399 Hv and 463 Hv, respectively, which is higher than the that of commercial products (330-340 Hv).
Particles of high strength material when coated with silver offer a means of obtaining desirable electrical properties and high strength. The coating process employed aqueous ammoniacal silver-nitrate electrolytes with a formaldehyde solution as the reductant. Modifying additives were also applied. The reduction and subsequent deposition of silver occurred selectively on the surface of the tungsten particles. The morphologies of the coated particles were assessed by SEM imaging. The silver was uniformed coated on tungsten powder and its thickness was estimated to be approximately 100nm on the basis of a mass account.
This is about the effects deoxidization, carbonization and alloying preparation on fine grain W, WC, and grade YG8 powder reduced by "yellow tungsten oxide" and "blue tungsten oxide". The result indicates that yellow tungsten has single composition and blue tungsten oxide has complex composition. With this feature, yellow tungsten oxide got better uniformity and concentration distribution on fine particle size W and WC powder than blue tungsten oxide's. The grade alloy YG8 that made of this W or WC powder has uniform alloy construction, concentrated WC grain distribution and better alloy properties.
Vacuum carbonization of nanometer tungsten powder was investigated in a simple designed apparatus. An X-Y recorder was used to plot differential thermal analysis (DTA) curves to determine starting temperature of carbonization of four samples with different specific surface area. The product was detected by X-ray Diffraction (XRD) and small angle X-ray scattering (SAXS). The results show that finer tungsten powder has lower starting temperature of carbonization. Tungsten powder, which BET surface area is , is completely carbonized to tungsten carbide at , although the starting temperature is . Particle grows sharply before carbonization.
Ultrasonic-milling of metal oxide nanopowders for the preparation of tungsten heavy alloys was investigated. Milling time was selected as a process variable. XRD results of metal oxide nanopowders ultrasonic-milled for 50 and 100h showed that mean crystallite size reduced with increasing milling time and there was no evidence of contamination or change of composition by impurities. It was found that nanocomposite powders reduced at in atmosphere had a composition of 93.1W-4.9Ni-2.0Fe by EDX analysis. Hardness of sintered samples of 50 and 100h was 390 and 463 Hv, respectively, which corresponds to the hardness of commercial products.
Thermal management technology is a critical element in all new chip generations, caused by a power multiplication combined with a size reduction. A heat sink, mounted on a base plate, requires the use of special materials possessing both high thermal conductivity (TC) and a coefficient of thermal expansion (CTE) that matches semiconductor materials as well as certain packaging ceramics. In this study, nano tungsten coated copper powder has been developed with a wide range of compositions, 90W-10Cu to 10W-90Cu. Powder technologies were used to make samples to evaluate density, TC, and CTE. Measured TC lies among theoretical values predicted by several existing models.
Processing of W-Cu graded materials from attritor-milled W-CuO mixtures is described. The powder reduction steps are investigated by TG and XRD analyses and by microstructural observations (SEM, TEM). Sintering of reduced powder with different compositions is analysed by dilatometry. Sintering behaviour of the graded component processed by co-compaction of a 10/20/30wt%Cu multi-layer material is briefly discussed. Liquid Cu migration is observed and smooths the composition gradient. Perspectives to control this migration are discussed.
The high temperature deformation behavior of the activated sintered W powder compacts was investigated. The W compact showed the relative density of 94% with the average W grain size of by activated sintering at for 1 hour. Compression tests were carried out in the temperature range of at the strain rate range of /sec - /sec. True stress-strain curve and microstructure exhibited the grain boundary brittleness which was dependent on the compression test temperature. The activated sintered W compact showed that the maximum stress as well as the strain at the maximum stress was abruptly decreased as the test temperature increase from to 1000 and regardless of the strain rate. The discrepancy of the microstructure in the specimen center was obviously observed with the increase of the test temperature. After compression test at the W grain was severely deformed normally against the compression axis. However, after compression test at and the W grain was not deformed, but the microcrack was formed in the W grain boundary. The Ni-rich second phase segregated along the W grain boundary could be partly unstable over and affect the poor mechanical property of the activated sintered W compact.
본 연구에서는 산화텅스텐() 분말을 이용하여 여러 금속 기판에 텅스텐 박막을 코팅하는 방법에 관한 연구를 수행하였다. 본 연구에서 언급되는 W 코팅은 Lee 등이 보고한 W, Cu 산화물을 이용하여 W-Cu 복합분말을 제조하는 것으로부터 아이디어가 출발되었으며, 본 연구의 결과는 기존의 6불화 텅스텐 가스() 를 열 분해하여 증착시키는 화학증착법(CVD: chemical vapor deposition)과 순수 텅스텐 target을 sputtering하여
Nanosized tungsten carbide powders were synthesized by the chemical vapor condensation(CVC) process using the pyrolysis of tungsten hexacarbonyl(). The effect of CVC parameters on the formation and the microstructural change of as-prepared powders were studied by XRD, BET and TEM. The loosely agglomerated nanosized tungsten-carbide() particles having the smooth rounded tetragonal shape could be obtained below in argon and air atmosphere respectively. The grain size of powders was decreased from 53 nm to 28 nm with increasing reaction temperature. The increase of particle size with reaction temperature represented that the condensation of precursor vapor dominated the powder formation in CVC reactor. The powder prepared at was consisted of the pure W and cubic tungsten-carbide (), and their surfaces had irregular shape because the pure W was formed on the powders. The and W powders having the average particles size of about 5 nm were produced in vacuum.
In the present study, the effect of Ni content on densification and grain growth in Ni doped W compacts was investigated by using the dilatometric analysis. The Ni-doped W compacts with various amount of Ni activator from 0.02 to 0.4 wt% were sintered in hydrogen atmosphere up to 140. As the amount of Ni and heating rates, the Ni-doped W compacts show a greatly different dilatometric behavior during the sintering. The sintered specimen was densified over 98% of theoretical density by adding only 0.06 wt% Wi in sub-micron W powder and the appropriate heating rate. It was also observed that the microstructure development strongly depended on the change of the Ni amount. In addition, it was found that the critical content of Ni showing large grain growth in microstructure was below 0.1 wt%.