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.

Porous W with controlled pore characteristics was fabricated by a freeze-drying process. WO3 powder and camphene were used as the source materials of W and sublimable vehicles, respectively. Camphene slurries with WO3 contents of 10 and 15 vol% were prepared by milling at 50˚C with a small amount of oligomeric polyester dispersant. Freezing of a slurry was done in a Teflon cylinder attached to a copper bottom plate cooled at -25˚C while the growth direction of the camphene was unidirectionally controlled. Pores were generated subsequently by sublimation of the camphene during drying in air for 48 h. The green body was hydrogen-reduced at 800˚C for 30 min and sintered in a furnace at 900˚C for 1 h under a hydrogen atmosphere. Microstructural observation revealed that all of the sintered samples were composed of only W phase and showed large pores which were aligned parallel to the camphene growth direction. The porosity and pore size increased with increasing camphene content. The difference in the pore characteristics depending on the slurry concentration may be explained by the degree of powder rearrangement in the slurry. The results strongly suggest that a porous metal with the required pore characteristics can be successfully fabricated by a freeze-drying process using metal oxide powders.

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.