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 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 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 W-10 wt% Ti alloys are prepared by freeze-drying a WO3-TiH2/camphene slurry, using a sintering process. X-ray diffraction analysis of the heat-treated powder in an argon atmosphere shows the WO3 peak of the starting powder and reaction-phase peaks such as WO2.9, WO2, and TiO2 peaks. In contrast, a powder mixture heated in a hydrogen atmosphere is composed of the W and TiW phases. The formation of reaction phases that are dependent on the atmosphere is explained by a thermodynamic consideration of the reduction behavior of WO3 and the dehydrogenation reaction of TiH2. To fabricate a porous W-Ti alloy, the camphene slurry is frozen at -30℃, and pores are generated in the frozen specimens by the sublimation of camphene while drying in air. The green body is hydrogen-reduced and sintered at 1000℃ for 1 h. The sintered sample prepared by freeze-drying the camphene slurry shows large and aligned parallel pores in the camphene growth direction, and small pores in the internal walls of the large pores. The strut between large pores consists of very fine particles with partial necking between them.

Porous W with spherical and directionally aligned pores was fabricated by the combination of sacrificial fugitives and a freeze-drying process. Camphene slurries with powder mixtures of WO3 and spherical PMMA of 20 vol% were frozen at −25 oC and dried for the sublimation of the camphene. The green bodies were heat-treated at 400 oC for 2 h to decompose the PMMA; then, sintering was carried out at 1200 oC in a hydrogen atmosphere for 2 h. TGA and XRD analysis showed that the PMMA decomposed at about 400 oC, and WO3 was reduced to metallic W at 800 oC without any reaction phases. The sintered bodies with WO3-PMMA contents of 15 and 20 vol% showed large pores with aligned direction and small pores in the internal walls of the large pores. The pore formation was discussed in terms of the solidication behavior of liquid camphene with solid particles. Spherical pores, formed by decomposition of PMMA, were observed in the sintered specimens. Also, microstructural observation revealed that struts between the small pores consisted of very fine particles with size of about 300 nm.

Porous W with controlled pore structure was fabricated by thermal decomposition and hydrogen reduction process of PMMA beads and WO3 powder compacts. The PMMA sizes of 8 and 50 μm were used as pore forming agent for fabricating the porous W. The WO3 powder compacts with 20 and 70 vol% PMMA were prepared by uniaxial pressing and sintered for 2 h at 1200oC in hydrogen atmosphere. TGA analysis revealed that the PMMA was decomposed at about 400oC and WO3 was reduced to metallic W at 800oC. Large pores in the sintered specimens were formed by thermal decomposition of spherical PMMA, and their size was increased with increase in PMMA size and the amount of PMMA addition. Also the pore shape was changed from spherical to irregular form with increasing PMMA contents due to the agglomeration of PMMA in the powder mixing process.

Dependence of the freeze-drying process condition on microstructure of porous W and pore formation mechanism were studied. Camphene slurries with contents of 10 vol% were prepared by milling at with a small amount of dispersant. Freezing of a slurry was done in Teflon cylinder attached to a copper bottom plate cooled at . Pores were generated subsequently by sublimation of the camphene during drying in air for 48 h. The green body was hydrogen-reduced at for 30 min, and sintered in the furnace at for 1 h. After heat treatment in hydrogen atmosphere, powders were completely converted to metallic W without any reaction phases. The sintered samples showed large pores with the size of about which were aligned parallel to the camphene growth direction. Also, the internal wall of large pores and near bottom part of specimen had relatively small pores with dendritic structure due to the growth of camphene dendrite depending on the degree of nucleation and powder rearrangement in the slurry.

Electro-Discharge Sintering (EDS) employs a high-voltage/high-current-density pulse of electrical energy, discharged from a capacitor bank, to instantaneously consolidate powders. In the present study, a single pulse of 0.57-1.1 kJ/0.45 g-atomized spherical powders in size range of 10~30 and consisting of -(Ti, Zr) and icosahedral phases were applied to examine the structural evolution of icosahedral phase during EDS. Structural investigation reveals that high electrical input energy facilitates complete decomposition of icosahedral phase into C14 laves and -(Ti, Zr) phases. Moreover, critical input energy inducing decomposition of the icosahedral phase during EDS depends on the size of the powder. Porous Ti and W compacts have been fabricated by EDS using rectangular and spherical powders upon various input energy at a constant capacitance of in order to verify influence of powder shape on microstructure of porous compacts. Besides, generated heat () during EDS, which is measured by an oscilloscope, is closely correlated with powder size.