We report the effect of plastic deformation on the thermoelectric properties of n-type Bi2Te2.5Se0.5 compounds. N-type Bi2Te2.5Se0.5 powders are synthesized by an oxide-reduction process and consolidated via sparkplasma sintering. To explore the effect of plastic deformation on the thermoelectric properties, the sintered bodies are subjected to uniaxial pressure to induce a controlled amount of compressive strains (-0.2, -0.3, and -0.4). The shaping temperature is set using a thermochemical analyzer, and the plastic deformation effect is assessed without altering the material composition through differential scanning calorimetry. This strategy is crucial because the conventional hotforging process can often lead to alterations in material composition due to the high volatility of chalcogen elements. With increasing compressive strain, the (00l) planes become aligned in the direction perpendicular to the pressure axis. Furthermore, an increase in the carrier concentration is observed upon compressive plastic deformation, i.e., the donorlike effect of the plastic deformation in n-type Bi2Te2.5Se0.5 compounds. Owing to the increased electrical conductivity through the preferred orientation and the donor-like effect, an improved ZT is achieved in n-type Bi2Te2.5Se0.5 through the compressive-forming process.

This study focuses on the fabrication of a WC/Co composite powder from the oxide of WC/Co hardmetal scrap using solid carbon in a hydrogen gas atmosphere for the recycling of WC/Co hardmetal. Mixed powders are manufactured by mechanically milling the oxide powder of WC-13 wt% Co hardmetal scrap and carbon black with varying powder/ball weight ratios. The oxide powder of WC-13 wt% Co hardmetal scrap consists of WO3 and CoWO4. The mixed powder mechanically milled at a lower powder/ball weight ratio (high mechanical milling energy) has a more rapid carbothermal reduction reaction in the formation of WC and Co phases compared with that mechanically milled at a higher powder/ball weight ratio (lower mechanical milling energy). The WC/Co composite powder is fabricated at 900℃ for 6 h from the oxide of WC/Co hardmetal scrap using solid carbon in a hydrogen gas atmosphere. The fabricated WC/Co composite powder has a particle size of approximately 0.25-0.5 μm.

This study focuses on the development of an alkaline leaching hydrometallurgy process for the recovery of tungsten from WC/Co hardmetal sludge, and an examination of the effect of the process parameters on tungsten recovery. The alkaline leaching hydrometallurgy process has four stages, i.e., oxidation of the sludge, leaching of tungsten by NaOH, refinement of the leaching solution, and precipitation of tungsten. The WC/Co hardmetal sludge oxide consists of WO3 and CoWO4. The leaching of tungsten is most affected by the leaching temperature, followed by the NaOH concentration and the leaching time. About 99% of tungsten in the WC/Co hardmetal sludge is leached at temperatures above 90oC and a NaOH concentration above 15%. For refinement of the leaching solution, pH control of the solution using HCl is more effective than the addition of Na2S·9H2O. The tungsten is precipitated as high-purity H2WO4·H2O by pH control using HCl. With decreasing pH of the solution, the tungsten recovery rate increases and then decrease. About 93% of tungsten in the WC/Co hardmetal sludge is recovered by the alkaline leaching hydrometallurgy process.

This study focuses on fabricating silver flake powder by a mechanical milling process and investigating the formation of flake-shaped particles during milling. The silver flake powder is fabricated by varying the mechanical milling parameters such as the amount of powder, ball size, impeller rotation speed, and milling time of the attrition ballmill. The particle size of the silver flake powder decreases with increasing amount of powder; however, it increases with increasing impeller rotation speed. The change in the particle size of the silver flake powder is analyzed based on elastic collision between the balls, taking energy loss of the balls due to the powder into consideration. The change in the particle size of the silver flake powder with mechanical milling parameters is consistent with the change in the diameter of the elastic deformation contact area of the ball, due to the collision between the balls, with milling parameters. The flake-shaped silver particles are formed at the elastic deformation contact area of the ball due to the collision. Keywords: Flake powder, Milling, Ball collision, Elastic deformation

This study is focused on investigating the relation between the particle size of silver flake powder and mechanical milling parameters. Mechanical milling parameters such as ball size, impeller rotation speed and milling time of the attrition ball-mill were controlled to produce silver flake powder. The particle size of the silver flake powder increased with increasing ball size and impeller rotation speed. The change of the particle size of the silver flake powder with mechanical milling parameters was analyzed based on balls motion in the mill container of the attrition ball-mill. The silver flake particles were formed at the elastic deformation area of the ball due to the collision between balls. The change of the particle size of the silver flake powder with mechanical milling parameters well consists with the change of the collision energy of ball with parameters mentioned above.

The effects of B4C on the mechanical properties of WC/Ni-Si hardmetal were analyzed using sintered bod- ies comprising WC(70-x wt.%), Ni (28.5 wt.%), Si (1.5 wt.%), and B4C (x wt.%), where 0 x 1.2 wt.%. Samples were prepared by a combination of mechanical milling and liquid-phase sintering. Phase and microstructure character- izations were conducted using X-ray diffractometry, scanning electron microscopy, and electron probe X-ray micro anal- ysis. The mechanical properties of the sintered bodies were evaluated by measuring their hardness and transverse rupture strength. The addition of B4C improved the sinterability of the hardmetals. With increasing B4C content, their hardness increased, but their transverse rupture strength decreased. The changes of sinterability and mechanical properties were attributed to the alloying reaction between B4C and the binder metal (Ni, Si). ≤ ≤

The present study was focused on the analysis of the electric and thermal properties of spark plasma sintered thermoelectric material. The crystal structure, microstructure, electric and thermal properties of the sintered body were evaluated by measuring XRD, SEM, electric resistivity, Hall effect and thermal conductivity. The sintered body showed anisotropic crystal structure. The c-axis of the crystal aligned in a parallel direction with applied pressure during spark plasma sintering. The degree of the crystal alignment increased with increasing sintering temperature and sintering time. The electric resistivity and thermal conductivity of the sintered body showed anisotropic characteristics result from crystal alignment.

The present study focused on the synthesis of Bi-Te-Se-based powder by an oxide-reduction process, and analysis of the thermoelectric properties of the synthesized powder. The phase structure, chemical composition, and morphology of the synthesized powder were analyzed by XRD, EPMA and SEM. The synthesized powder was sintered by spark plasma sintering. The thermoelectric properties of the sintered body were evaluated by measuring its Seebeck coefficient, electrical resistivity, and thermal conductivity. powder was synthesized from a mixture of , , and powders by mechanical milling, calcination, and reduction. The sintered body of the synthesized powder exhibited n-type thermoelectric characteristics. The thermoelectric properties of the sintered bodies depend on the reduction temperature. The Seebeck coefficient and electrical resistivity of the sintered body were increased with increasing reduction temperature. The sintered body of the powder synthesized at showed about 0.5 of the figure of merit (ZT) at room temperature.

The present study focused on the synthesis of Bi-Sb-Te-based thermoelectric powder by an oxidereduction process. The phase structure, particle size of the synthesized powders were analyzed using XRD and SEM. The synthesized powder was sintered by the spark plasma sintering method. The thermoelectric property of the sintered body was evaluated by measuring the Seebeck coefficient and specific electric resistivity. The powder had been synthesized by a combination of mechanical milling, calcination and reduction processes using mixture of , and powders. The sintered body of the powder synthesized by an oxide-reduction process showed p-type thermoelectric characteristics, even though it had lower thermoelectric properties than the sintered body of the thermoelectric powder synthesized by the conventional melting-crushing method.

Ultra-fine TiC/Co composite powder was synthesized by the carbothermal reduction process without wet chemical processing. The starting powder was prepared by milling of titanium dioxide and cobalt oxalate powders followed by subsequent calcination to have a target composition of TiC-15 wt.%Co. The prepared oxide powder was mixed again with carbon black, and this mixture was then heat-treated under flowing argon atmosphere. The changes in the phase, mass and particle size of the mixture during heat treatment were investigated using XRD, TG-DTA and SEM. The synthesized oxide powder after heat treatment at 700 has a mixed phase of TiO and CoTiO phases. This composite oxide powder was carbothermally reduced to TiC/Co composite powder by the solid carbon. The synthesized TiC/Co composite powder at 1300 for 9 hours has particle size of under about 0.4 m.

The present study focused on the synthesis of a bismuth-antimony-tellurium-based thermoelectric nanopowders using plasma arc discharge process. The chemical composition, phase structure, particle size of the synthesized powders under various synthesis conditions were analyzed using XRF, XRD and SEM. The powders as synthesized were sintered by the plasma activated sintering. The thermoelectric properties of sintered body were analyzed by measuring Seebeck coefficient, specific electric resistivity and thermal conductivity. The chemical composition of the synthesized Bi-Sb-Te-based powders approached that of the raw material with an increasing DC current of the are plasma. The synthesized Bi-Sb-Te-based powder consist of a mixed phase structure of the , and phases. This powder has homogeneous mixing state of two different particles in an average particle size; about 100nm and about 500nm. The figure of merit of the sintered body of the synthesized 18.75 wt.%Bi-24.68 wt.%Sb-56.57 wt.%Te nanopowder showed higher value than one of the sintered body of the mechanically milled 12.64 wt.%Bi-29.47 wt.%Sb-57.89 wt.%Te powder.

Pure WC or WC with low Co concentration less than 0.5 wt.% is studied to fabricate high density WC/Co cemented carbide using vacuum sintering and post HIP process. Considering the high melting point of WC, it is difficult to consolidate it without the use of Co as binder. In this study, the effect of lower Co addition on the microstructure and mechanical properties evolution of WC/CO was investigated. By HIP process after vacuum sintering, hardness and density was sharply increased. The hardness values was using binderless WC.

The present study was focused on the synthesis of a dispersed copper matrix composite material by the combination of the mechanical milling and plasma activated sintering processes. The mixed powder was prepared by the combination of the mechanical milling and reduction processes using the copper oxide and titanium diboride powder as the raw material. The synthesized mixed powder was sintered by the plasma activated sintering process. The hardness and electric conductivity of the sintered bodies were measured using micro vickers hardness and four probe method, respectively. The relative density of composite material sintered at showed about 98% of theoretical density. The composite material has a hardness of about 130Hv and an electric conductivity of about 85% IACS. The hardness and electric conductivity of composite material were about 140 Hv and about 45% IACS, respectively.

The present study was focused on the synthesis of a zirconium-based alloyed nanopowder by the plasma arc discharge process. The chemical composition, phase structure, particle size and hydrogen sorption property of the synthesized powders under various synthesis conditions were analyzed using XRF, XRD, SEM, XPS and the ASTM-F798 method. The chemical composition of the synthesized Zr-V-Fe-based powders approached that of the raw material with an increasing hydrogen fraction in the powder synthesis atmosphere. The synthesized powder consist of a mixed phase structure of the phases. This powder has an average particle size of about 20 nm. The synthesized nanopowder showed getter characteristics, even though it had a lower hydrogen sorption speed than the getter powder. However, the synthesized Zr nanopowder with an average particle size of 20 nm showed higher hydrogen sorption speed than the getter powder.

The present study is to analyze the thermoelectric properties of thermoelectric materials fabricated by the mechanical grinding process. The powders were prepared by the combination of mechanical milling and reduction treating methods using simply crushed pre-alloyed powder. The mechanical milling was carried out using the tumbler-ball mill and planetary ball mill. The tumbler-ball milling had an effect on the carrier mobility rather than the carrier concentration, whereas, the latter on the carrier concentration. The specific electric resistivity and Seebeck coefficient decreased with increasing the reduction-heat-treatment time. The thermal conductivity continuously increased with increasing the reduction-heat-treatment time. The figure of merit of the sintered body prepared by the mechanical grinding process showed higher value than one of the sintered body of the simply crushed powder.

The p-type semiconductor thermoelectric materials were fabricated by melting, milling and sintering process and their thermoelectric properties were characterized. The compound materials were ball-milled with milling time and the powders were sintered by spark plasma sintering process. The ball milled powders had equiaxial shape and approedmately in size. The figure of meritz of sintered thermoelectric materials decreased with milling time because of lowered electrical resistivity. The thermoelectric properties of materials have been discussed in terms of electrical property with ball mill process.

In the present study, the focus is on the effect of cobalt oxide powder in the carbothermal reduction of the titanium-cobalt-oxygen based oxide powder by solid carbon for the optimizing synthesis process of ultra fine TiC/Co composite powder. The titanium-cobalt-oxygen based oxide powder was prepared by the combination of the spray drying and desalting processes using the titanium dioxide powder and cobalt nitrate as the raw materials. The titanium-cobalt-oxygen based oxide powder was mixed with carbon black, and then this mixture was carbothermally reduced under flowing argon atmosphere. Changes in the phase structure and thermal gravity of the mixture during carbothermal reduction were analysed using XRD and TGA. Titanium-cobalt-oxygen based oxide powder desalted at had a mixture of . And the one desalted at had a mixture of . In the case of the former powder, the reduction of cobalt oxide powder in the titanium-cobalt-oxygen based oxide powder occurred at lower temperature than the latter one. However, the carbothermal reduction of titanium dioxide powder in the titanium-cobalt-oxygen based oxide powder with a mixture of occurred at higher temperature than the one with a mixture of . And also, the former powder showed a lower TiC formation ability than the latter one.

In the present study, the focus is on the analysis of carbothermal reduction of oxide powder prepared from waste WC/Co hardmetal by solid carbon under a stream of argon for the recycling of the WC/Co hard-metal. The oxide powder was prepared by the combination of the oxidation and crushing processes using the waste hardmetal as the raw material. This oxide powder was mixed with carbon black, and then this mixture was carbothermally reduced under a flowing argon atmosphere. The changes in the phase structure and gases discharge of the mixture during carbothermal reduction was analysed using XRD and gas analyzer. The oxide powder prepared from waste hardmetal has a mixture of . This oxide powder reduced at about , formed tungsten carbides at about , and then fully transformed to a mixed state of tungsten carbide (WC) and cobalt at about by solid carbon under a stream of argon. The WC/Co composite powder synthesized at for 6 hours from oxide powder of waste hardmetal has an average particle size of .

In the present study, the focus is on the analysis of the effect of the mold dimensions on the temperature distribution of a die during plasma activated sintering. The temperature distribution of a cylindrical mold with various dimensions was measured using K-type thermocouples. The temperature homogeneity of the die was studied based on the direction and dimensions of the die. A temperature gradient existed in the radial direction of the die during the plasma activated sintering. Also, the magnitude of the temperature gradient was increased with increasing sintering temperature. In the longitudinal direction, however, there was no temperature gradient. The temperature gradient of the die in the radial direction strongly depended on a ratio of die volume to punch area