This study analyzed the influence of ball size and process control agents on the refinement and dehydrogenation behavior of TiH2 powder. Powders milled using ZrO2 balls with diameters of 0.1 mm, 0.3 mm, and 0.3+0.5+1 mm exhibited a bimodal particle size distribution, of which the first mode had the smallest size of 0.23 μm for the 0.3 mm balls. Using ethanol and/or stearic acid as process control agents was effective in particle refinement. Thermogravimetric analysis showed that dehydrogenation of the milled powder started at a relatively low temperature compared to the raw powder, which is interpreted to have resulted from a decrease in particle size and an increase in defects. The dehydrogenation kinetics of the TiH2 powder were evaluated by the magnitude of peak shift with heating rates using thermogravimetric analysis. The activation energy of the dehydrogenation reaction, calculated from the slope of the Kissinger plot, was measured to be 228.6 kJ/mol for the raw powder and 194.5 kJ/mol for the milled powder. TEM analysis revealed that both the milled and dehydrogenated powders showed an angular shape with a size of about 200 nm.

This study investigated the effects of revolution speed and ball size in planetary milling on the microstructure and dehydrogenation behavior of TiH2 powder. The particle size analysis showed that the large particles present in the raw powder were effectively refined as the revolution speed increased, and when milled at 500 rpm, the median particle size was 1.47 μm. Milling with a mixture of balls of two or three sizes was more effective in refining the raw powder than milling with balls of a single size. A mixture of 3 mm and 5 mm diameter balls was the optimal condition for particle refinement, and the measured median particle size was 0.71 μm. The dependence of particle size on revolution speed and ball size was explained by changes in input energy and the number of contact points of the balls. In the milled powder, the endothermic peak measured using differential thermal analysis was observed at a relatively low temperature. This finding was interpreted as the activation of a dehydrogenation reaction, mainly due to the increase in the specific surface area and the concentration of lattice defects.

This study demonstrates the effect of the compaction pressure on the microstructure and properties of pressureless-sintered W bodies. W powders are synthesized by ultrasonic spray pyrolysis and hydrogen reduction using ammonium metatungstate hydrate as a precursor. Microstructural investigation reveals that a spherical powder in the form of agglomerated nanosized W particles is successfully synthesized. The W powder synthesized by ultrasonic spray pyrolysis exhibits a relative density of approximately 94% regardless of the compaction pressure, whereas the commercial powder exhibits a relative density of 64% under the same sintering conditions. This change in the relative density of the sintered compact can be explained by the difference in the sizes of the raw powder and the densities of the compacted green body. The grain size increases as the compaction pressure increases, and the sintered compact uniaxially pressed to 50 MPa and then isostatically pressed to 300 MPa exhibits a size of 0.71 m. The Vickers hardness of the sintered W exhibits a high value of 4.7 GPa, mainly due to grain refinement.

The synthesis of porous W by freeze-casting and vacuum drying is investigated. Ball-milled WO3 powders and tert-butyl alcohol were used as the starting materials. The tert-butyl alcohol slurry is frozen at –25oC and dried under vacuum at –25 and –10oC. The dried bodies are hydrogen-reduced at 800oC and sintered at 1000oC. The XRD analysis shows that WO3 is completely reduced to W without any reaction phases. SEM observations reveal that the struts and pores aligned in the tert-butyl alcohol growth direction, and the change in the powder content and drying temperature affects the pore structure. Furthermore, the struts of the porous body fabricated under vacuum are thinner than those fabricated under atmospheric pressure. This behavior is explained by the growth mechanism of tert-butyl alcohol and rearrangement of the powders during solidification. These results suggest that the pore structure of a porous body can be controlled by the powder content, drying temperature, and pressure.

The effects of drying temperature on the microstructure of porous W fabricated by the freeze-casting process of tert-butyl alcohol slurry with WO3 powder was investigated. Green bodies were hydrogen-reduced at 800oC for 1 h and sintered at 1000oC for 6 h. X-ray diffraction analysis revealed that WO3 powders were completely converted to W without any reaction phases by hydrogen reduction. The sintered body showed pores aligned in the direction of tertbutyl alcohol growth, and the porosity and pore size decreased as the amount of WO3 increased from 5 to 10v ol%. As the drying temperature of the frozen body increased from -25oC to -10oC, the pore size and thickness of the struts increased. The change in microstructural characteristics based on the amount of powder added and the drying temperature was explained by the growth behavior of the freezing agent and the degree of rearrangement of the solid powder during the solidification of the slurry.

The (Ga1-xZnx)(N1-xOx) solid solution is attracting extensive attention for photocatalytic water splitting and wastewater treatment owing to its narrow and controllable band gap. To optimize the photocatalytic performance of the solid solution, the key points are to decrease its band gap and recombination rate. In this study, (Ga1-xZnx)(N1-xOx) nanofibers with various Zn fractions are prepared by electrospinning followed by calcination and nitridation. The effect of the composition and crystallinity of electrospun oxide nanofibers on the morphology and optical properties of the obtained solid-solution nanofibers are systematically investigated. The results show that the final shape of the (Ga1-xZnx) (N1-xOx) material is greatly affected by the crystallinity of the oxide nanofibers before nitridation. The photocatalytic properties of (Ga1-xZnx)(N1-xOx) with different Ga:Zn atomic ratios are investigated by studying the degradation of rhodamine B under visible light irradiation.

The effect of tert-butyl alcohol (TBA) as a freezing solvent on the pore structure of a porous tungsten body prepared by freeze-drying is analyzed. TBA slurries with a WO3 content of 10 vol% are prepared by mixing with a small amount of dispersant and binder at 30oC. The slurries are frozen at -25oC, and pores are formed in the frozen specimens by the sublimation of TBA during drying in air. After hydrogen reduction at 800oC and sintering at 1000oC, the green body of WO3 is completely converted to porous W with various pore structures. Directional pores from the center of the specimen to the outside are observed in the sintered bodies because of the columnar growth of TBA. A decrease in pore directionality and porosity is observed in the specimens prepared by long-duration drying and sintering. The change in pore structure is explained by the growth of the freezing solvent and densification.

The present study demonstrates the effect of magnetic pulse compaction and spark plasma sintering on the microstructure and mechanical property of a sintered W body. The relative density of green specimens prepared by magnetic pulse compaction increases with increase in applied pressure, but when the applied pressure is 3.4 GPa or more, some cracks in the specimen are observed. The pressureless-sintered W shows neck growth between W particles, but there are still many pores. The sintered body fabricated by spark plasma sintering exhibits a relative density of above 90 %, and the specimen sintered at 1,600 oC after magnetic pulse compaction shows the highest density, with a relative density of 93.6 %. Compared to the specimen for which the W powder is directly sintered, the specimen sintered after magnetic pulse compaction shows a smaller crystal grain size, which is explained by the reduced W particle size and microstructure homogenization during the magnetic pulse compaction process. Sintering at 1,600 oC led to the largest Vickers hardness value, but the value is slightly lower than that of the conventional W sintered body, which is attributed mainly to the increased grain size and low sintering density.

The effect of sublimable vehicles on the pore structure of Cu fabricated by freeze drying is investigated. The 5 vol% CuO-dispersed slurries with camphene and various camphor-naphthalene compositions are frozen in a Teflon mold at -25oC, followed by sublimation at room temperature. After hydrogen reduction at 300oC and sintering at 600 °C, the green bodies of CuO are completely converted to Cu with various pore structures. The sintered samples prepared using CuO/camphene slurries show large pores that are aligned parallel to the sublimable vehicle growth direction. In addition, a dense microstructure is observed in the bottom section of the specimen where the solidification heat was released, owing to the difference in the solidification behavior of the camphene crystals. The porous Cu shows different pore structures, such as dendritic, rod-like, and plate shaped, depending on the composition of the camphornaphthalene system. The change in pore structure is explained by the crystal growth behavior of primary camphor and eutectic and primary naphthalene. Keywords: Porous Cu, Pore structure

Porous Cu-14 wt% Co with aligned pores is produced by a freeze drying and sintering process. Unidirectional freezing of camphene slurry with CuO-Co3O4 powders is conducted, and pores in the frozen specimens are generated by sublimation of the camphene crystals. The dried bodies are hydrogen-reduced at 500oC and sintered at 800oC for 1 h. The reduction behavior of the CuO-Co3O4 powder mixture is analyzed using a temperature-programmed reduction method in an Ar-10% H2 atmosphere. The sintered bodies show large and aligned parallel pores in the camphene growth direction. In addition, small pores are distributed around the internal walls of the large pores. The size and fraction of the pores decrease as the amount of solid powder added to the slurry increases. The change in pore characteristics according to the amount of the mixed powder is interpreted to be due to the rearrangement and accumulation behavior of the solid particles in the freezing process of the slurry.

The hydrogen reduction behavior of the CuO-Co3O4 powder mixture for the synthesis of the homogeneous Cu-15at%Co composite powder has been investigated. The composite powder is prepared by ball milling the oxide powders, followed by a hydrogen reduction process. The reduction behavior of the ball-milled powder mixture is analyzed by X-ray diffraction (XRD) and temperature-programmed reduction at different heating rates in an Ar-10%H2 atmosphere. The scanning electron microscopy and XRD results reveal that the hydrogen-reduced powder mixture is composed of fine agglomerates of nanosized Cu and Co particles. The hydrogen reduction kinetics is studied by determining the degree of peak shift as a function of the heating rate. The activation energies for the reduction of the oxide powders estimated from the slopes of the Kissinger plots are 58.1 kJ/mol and 65.8 kJ/mol, depending on the reduction reaction: CuO to Cu and Co3O4 to Co, respectively. The measured temperature and activation energy for the reduction of Co3O4 are explained on the basis of the effect of pre-reduced Cu particles.

Nb-Si-B alloys with Nb-rich compositions are fabricated by spark plasma sintering for high-temperature structural applications. Three compositions are selected: 75 at% Nb (Nb0.7), 82 at% Nb (Nb1.5), and 88 at% Nb (Nb3), the atomic ratio of Si to B being 2. The microstructures of the prepared alloys are composed of Nb and T2 phases. The T2 phase is an intermetallic compound with a stoichiometry of Nb5Si3-xBx (0 ≤ x ≤ 2). In some previous studies, Nb-Si- B alloys have been prepared by spark plasma sintering (SPS) using Nb and T2 powders (SPS 1). In the present work, the same alloys are prepared by the SPS process (SPS 2) using Nb powders and hypereutectic alloy powders with composition 67at%Nb-22at%Si-11at%B (Nb67). The Nb67 alloy powders comprise T2 and eutectic (T2 + Nb) phases. The microstructures and hardness of the samples prepared in the present work have been compared with those previously reported; the samples prepared in this study exhibit finer and more uniform microstructures and higher hardness.

In this study, freeze drying of a porous Ni with unidirectionally aligned pore channels is accomplished by using a NiO powder and camphene. Camphene slurries with NiO content of 5 and 10 vol% are prepared by mixing them with a small amount of dispersant at 50℃. Freezing of a slurry is performed at -25℃ while the growth direction of the camphene is unidirectionally controlled. Pores are generated subsequently by sublimation of the camphene during drying in air for 48 h. The green bodies are hydrogen-reduced at 400℃ and then sintered at 800℃ and 900℃ for 1 h. X-ray diffraction analysis reveals that the NiO powder is completely converted to the Ni phase without any reaction phases. The sintered samples show large pores that align parallel pores in the camphene growth direction as well as small pores in the internal walls of large pores. The size of large and small pores decreases with increasing powder content from 5 to 10 vol%. The influence of powder content on the pore structure is explained by the degree of powder rearrangement in slurry and the accumulation behavior of powders in the interdendritic spaces of solidified camphene.

In this study, porous Mo-5 wt% Cu with unidirectionally aligned pores is prepared by freeze drying of camphene slurry with MoO3-CuO powders. Unidirectional freezing of camphene slurry with dispersion stability is conducted at -25℃, and pores in the frozen specimens are generated by sublimation of the camphene crystals. The green bodies are hydrogen-reduced at 750℃ and sintered at 1000℃ for 1 h. X-ray diffraction analysis reveals that MoO3- CuO composite powders are completely converted to a Mo-and-Cu phase without any reaction phases by hydrogen reduction. The sintered bodies with the Mo-Cu phase show large and aligned parallel pores to the camphene growth direction as well as small pores in the internal walls of large pores. The pore size and porosity decrease with increasing composite powder content from 5 to 10 vol%. The change of pore characteristics is explained by the degree of powder rearrangement in slurry and the accumulation behavior of powders in the interdendritic spaces of solidified camphene.

W-10 wt% Ti alloys that have a homogeneous microstructure are prepared by thermal decomposition of WO3-TiH2 powder mixtures and spark plasma sintering. The reduction and dehydrogenation behavior of WO3 and TiH2 are analyzed by temperature programmed reduction and a thermogravimetric method, respectively. The X-ray diffraction analysis of the powder mixture, heat-treated in an argon atmosphere, shows W- oxides and TiO2 peaks. Conversely, the powder mixtures heated in a hydrogen atmosphere are composed of W, WO2 and TiO2 phases at 600 ℃ and W and W-rich β phases at 800 ℃. The densified specimen by spark plasma sintering at 1500 ℃ in a vacuum using hydrogen-reduced WO3-TiH2 powder mixtures shows a Vickers hardness value of 4.6 GPa and a homogeneous microstructure with pure W, β and Ti phases. The phase evolution dependent on the atmosphere and temperature is explained by the thermal decomposition and reaction behavior of WO3 and TiH2.

A unique porous material with controlled pore characteristics can be fabricated by the freeze-drying process, which uses the slurry of organic material as the sublimable vehicle mixed with powders. The essential feature in this process is that during the solidification of the slurry, the dendrites of the organic material should repel the dispersed particles into the interdendritic region. In the present work, a model experiment is attempted using some transparent organic materials mixed with glass powders, which enable in-situ observation. The organic materials used are camphor-naphthalene mixture (hypo- and hypereutectic composition), salol, camphene, and pivalic acid. Among these materials, the constituent phases in camphor-naphthalene system, i.e. naphthalene plate, camphor dendrite, and camphornaphthalene eutectic exclusively repel the glass powders. This result suggests that the control of organic material composition in the binary system is useful for producing a porous body with the required pore structure.

The hydrogen reduction behavior of MoO3-CuO powder mixture for the synthesis of homogeneous Mo-20 wt% Cu composite powder is investigated. The reduction behavior of ball-milled powder mixture is analyzed by XRD and temperature programmed reduction method at various heating rates in Ar-10% H2 atmosphere. The XRD analysis of the heat-treated powder at 300oC shows Cu, MoO3, and Cu2MoO5 phases. In contrast, the powder mixture heated at 400oC is composed of Cu and MoO2 phases. The hydrogen reduction kinetic is evaluated by the amount of peak shift with heating rates. The activation energies for the reduction, estimated by the slope of the Kissinger plot, are measured as 112.2 kJ/mol and 65.2 kJ/mol, depending on the reduction steps from CuO to Cu and from MoO3 to MoO2, respectively. The measured activation energy for the reduction of MoO3 is explained by the effect of pre-reduced Cu particles. The powder mixture, hydrogen-reduced at 700oC, shows the dispersion of nano-sized Cu agglomerates on the surface of Mo powders.

The present study demonstrates the effect of raw powder on the pore structure of porous W-Ni prepared by freeze drying of camphene-based slurries and sintering process. The reduction behavior of WO3 and WO3-NiO powders is analyzed by a temperature programmed reduction method in Ar-10% H2 atmosphere. After heat treatment in hydrogen atmosphere, WO3- NiO powder mixture is completely converted to metallic W without any reaction phases. Camphene slurries with oxide powders are frozen at −30 oC, and pores in the frozen specimens are generated by sublimation of the camphene during drying in air. The green bodies are hydrogen-reduced at 800 oC and sintered at 1000 oC for 1 h. The sintered samples show large and aligned parallel pores to the camphene growth direction, and small pores in the internal wall of large pores. The strut between large pores, prepared from pure WO3 powder, consists of very fine particles with partially necking between the particles. In contrast, the strut densification is clearly observed in the Ni-added W sample due to the enhanced mass transport in activation sintering.

Porous Cu with a dispersion of nanoscale Al2O3 particles is fabricated by freeze-drying CuO-Al2O3/camphene slurry and sintering. Camphene slurries with CuO-Al2O3 contents of 5 and 10 vol% are unidirectionally frozen at -30oC, and pores are generated in the frozen specimens by camphene sublimation during air drying. The green bodies are sintered for 1 h at 700oC and 800oC in H2 atmosphere. The sintered samples show large pores of 100 μm in average size aligned parallel to the camphene growth direction. The internal walls of the large pores feature relatively small pores of ~10 μm in size. The size of the large pores decreases with increasing CuO-Al2O3 content by the changing degree of powder rearrangement in the slurry. The size of the small pores decreases with increasing sintering temperature. Microstructural analysis reveals that 100-nm Al2O3 particles are homogeneously dispersed in the Cu matrix. These results suggest that a porous composite body with aligned large pores could be fabricated by a freeze-drying and H2 reducing process.