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 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

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.

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.

This study is performed to fabricate a Ti porous body by freeze drying process using titanium hydride (TiH2) powder and camphene. Then, the Ti porous body is employed to synthesize carbon nanotubes (CNTs) using thermal catalytic chemical vapor deposition (CCVD) with Fe catalyst and methane (CH4) gas to increase the specific surface area. The synthesized Ti porous body has 100 μm-sized macropores and 10-30 μm-sized micropores. The synthesized CNTs have random directions and are entangled with adjacent CNTs. The CNTs have a bamboo-like structure, and their average diameter is about 50 nm. The Fe nano-particles observed at the tip of the CNTs indicate that the tip growth model is applicable. The specific surface area of the CNT-coated Ti porous body is about 20 times larger than that of the raw Ti porous body. These CNT-coated Ti porous bodies are expected to be used as filters or catalyst supports.

Microstructural examination of the Nb-Si-B alloys at Nb-rich compositions is performed. The Nb-rich corner of the Nb-Si-B system is favorable in that the constituent phases are Nb (ductile and tough phase with high melting temperature) and T2 phase (very hard intermetallic compound with favorable oxidation resistance) which are good combination for high temperature structural materials. The samples containing compositions near Nb-rich corner of the Nb- Si-B ternary system are prepared by spark plasma sintering (SPS) process using T2 and Nb powders. T2 bulk phase is made in arc furnace by melting the Nb slug and the Si-B powder compact. The T2 bulk phase was subsequently ballmilled to powders. SPS is performed at 1300oC and 1400oC, depending on the composition, under 30 MPa for 600s, to produce disc-shaped specimen with 15 mm in diameter and 3 mm high. Hardness tests (Rockwell A-scale and micro Vickers) are carried out to estimate the mechanical property.

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.

The effect of sublimable vehicle composition in the camphor-naphthalene system on the pore structure ofporous Cu-Ni alloy is investigated. The CuO-NiO mixed slurries with hypoeutectic, eutectic and hypereutectic compo-sitions are frozen into a mold at -25oC. Pores are generated by sublimation of the vehicles at room temperature. Afterhydrogen reduction at 300oC and sintering at 850oC for 1 h, the green body of CuO-NiO is completely converted toporous Cu-Ni alloy with various pore structures. The sintered samples show large pores which are aligned parallel to thesublimable vehicle growth direction. The pore size and porosity decrease with increase in powder content due to thedegree of powder rearrangement in slurry. In the hypoeutectic composition slurry, small pores with dendritic morphologyare observed in the sintered Cu-Ni, whereas the specimen of hypereutectic composition shows pore structure of plateshape. The change of pore structure is explained by growth behavior of primary camphor and naphthalene crystals dur-ing solidification of camphor-naphthalene alloys.

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.

In this study, titanium(Ti) meshes and porous bodies are employed to synthesize carbon nanotubes(CNTs) using methane(CH4) gas and camphene solution, respectively, by chemical vapor deposition. Camphene is impregnated into Ti porous bodies prior to heating in a furnace. Various microscopic and spectroscopic techniques are utilized to analyze CNTs. It is found that CNTs are more densely and homogeneously populated on the camphene impregnated Ti-porous bodies as compared to CNTs synthesized with methane on Ti-porous bodies. It is elucidated that, when synthesized with methane, few CNTs are formed inside of Ti porous bodies due to methane supply limited by internal structures of Ti porous bodies. Ti-meshes and porous bodies are found to be multi-walled with high degree of structural disorders. These CNTs are expected to be utilized as catalyst supports in catalytic filters and purification systems.

In this study, modified catalytic chemical vapor deposition (CCVD) method was applied to control the CNTs (carbon nanotubes) growth. Since titanium (Ti) substrate and iron (Fe) catalysts react one another and form a new phase (Fe2TiO5) above 700℃, the decrease of CNT yield above 800℃ where methane gas decomposes is inevitable under common CCVD method. Therefore, we synthesized CNTs on the Ti substrate by dividing the tube furnace into two sections (left and right) and heating them to different temperatures each. The reactant gas flew through from the end of the right tube furnace while the Ti substrate was placed in the center of the left tube furnace. When the CNT growth temperature was set 700/950℃ (left/right), CNTs with high yield were observed. Also, by examining the micro-structure of CNTs of 700/950℃, it was confirmed that CNTs show the bamboo-like structure.

The present study demonstrates the effect of solidification condition on the pore structure in freeze drying process using the slurries of CuOlimable vehicles. Camphene and Camphor-45 wt% naphthalene based slurries with 14 vol% CuO powder were frozen into a mold at -25℃<, followed by sublimation at room temperature. The green bodies were hydrogen-reduced and sintered at 500℃ for 1 h. The porous Cu specimen, frozen the CuO/camphene slurry into the heated mold of the upper part, showed large pores with unidirectional pore channels and small pores in their internal wall. Also, it was observed that the size of large pores was decreasing near the bottom part of specimen. The change of pore structure depending on the freezing condition was explained by the nucleation behavior of camphene crystals and rearrangement of solid powders during solidification. In case of porous Cu prepared from CuO/Camphor-naphthalene system, the pore structure exhibited plate shape as a replica of the original structure of crystallized vehicles with hypereutectic composition.

This paper describes the surface modification effect of a Ti substrate for improved dispersibility of the cat-alytic metal. Etching of a pure titanium substrate was conducted in 50% H₂SO₄, 50˚C for 1h-12h to observe the sur-face roughness as a function of the etching time. At 1h, the grain boundaries were obvious and the crystal grains weredistinguishable. The grain surface showed micro-porosities owing to the formation of micro-pits less than 1 µm in diam-eter. The depths of the grain boundary and micro-pits appear to increase with etching time. After synthesizing the cat-alytic metal and growing the carbon nano tube (CNT) on Ti substrate with varying surface roughness, the distributiontrends of the catalytic metal and grown CNT on Ti substrate are discussed from a micro-structural perspective.

Freeze drying for porous Mo was accomplished by using MoO3 powder as the source and camphor-naph- thalene eutectic system as the sublimable material. Eutectic composition of camphor-naphthalene slurries with the initial MoO3 content of 5 vol%, prepared by milling at 55o C with a small amount of oligomeric dispersant, was frozen at -25o C. The addition of dispersant showed improvement of dispersion stability in slurries. Pores were generated subse- quently by sublimation of the camphor-naphthalene during drying in air for 48 h. To convert the MoO3 to metallic Mo, the green body was hydrogen-reduced at 750o C, and sintered at 1100o C for 2 h. The sintered samples, frozen by heated Teflon cylinder, showed large pores with the size of about 40 µm which were aligned parallel to the sublimable vehicles growth direction. The formation of unidirectionally aligned pores is explained by the rejection and accumulation of solid particles in the serrated solid-liquid interface.

Porous Ti-systems with unidirectionally aligned channels were synthesized by freeze-drying and a heat treatment process. TiH2 powder and camphene were used as the source materials of Ti and sublimable vehicles, respectively. Camphene slurries with TiH2 content of 10 and 15 vol% were prepared by milling at 50˚C with a small amount of oligomeric polyester dispersant. Freezing of the slurry was done in a Teflon cylinder attached to a copper bottom plate cooled at -25˚C while unidirectionally controlling the growth direction of the camphene. Pores were generated subsequently by sublimation of the camphene during drying in air for 48 h. The green body was heat-treated at 1100˚C for 1 h in a nitrogen and air atmosphere. XRD analysis revealed that the samples composed of TiN and TiO2 phase were dependent on the heat-treatment atmosphere. The sintered samples showed large pores of about 120 mm which were aligned parallel to the camphene growth direction. The internal wall of the large pores had relatively small pores with a dendritic structure due to the growth of camphene dendrite depending on the degree of nucleation and powder rearrangement in the slurry. These results suggest that a porous body with an appropriate microstructure can be successfully fabricated by freeze-drying and a controlled sintering process of a camphene/TiH2 slurry.

In order to fabricate the porous metal with controlled pore characteristics, unique processing by using metal oxide powder as the source and camphene as the sublimable material is introduced. CuO powder was selected as the source for the formation of Cu metal via hydrogen reduction. Camphene-based CuO slurry, prepared by milling at with a small amount of dispersant, was frozen at . Pores were generated subsequently by sublimation of the camphene. The green body was hydrogen-reduced at for 30 min, and sintered at for 1 h. Microstructural analysis revealed that the sintered Cu showed aligned large pore channels parallel to the camphene growth direction, and fine pores are formed around the large pore. Also, it showed that the pore size was controllable by the slurry concentration.

Mo nanopowder was synthesized by ball-milling and subsequent hydrogen-reduction of powder. To fabricate ultra fine grained molybdenum, two-step sintering and spark plasma sintering process were employed. The grain size of specimen by two-step sintering and spark plasma sintering was around and , respectively. Mechanical properties of ultra fine grained Mo with relative density of above 90% were significantly improved at room and high temperatures comparing to commercial bulk Mo of 99% relative density. This result was mainly explained by the grain size refinement due to diffusion-controlled sintering.

3-D shape soft magnetic composite parts can be formed by general compaction method of powder metallurgy. In this study, the results on the high density nanostructured Fe-Si/Fe composite prepared by a warm compaction method were presented. Ball-milled Fe-25 wt.%Si powder, pure Fe powder and Si-polymer were mixed and then the powder mixture was compacted at various temperatures and pressures. Pore free density of samples up to 95% theoretical value has been obtained. The warm compacted sample prepared at 650 MPa and 240℃ had highest compaction properties in comparison with other compacts prepared at 300, 400 MPa and room temperature and 120℃. The magnetic properties such as core loss, magnetization saturation and coercivity were measured by B-H curve analyzer and vibration sample magnetometer.

The sintering behavior and mechanical property of Mo nanopowder was investigated as a function of various sintering condition. Mo oxide nanopowders were milled using a high energy ball-milling process. After the ball milling for 20h, the crystalline size of was about 20 nm. The nanopowders were reduced at the temperature of without holding time in atmosphere. The sinterability of Mo nanopowder and commercial Mo powder was investigated by dilatometric analysis. Mo nanopowder and commercial Mo powder were sintered at for 1 hand for 3 h, respectively. In both specimens the measured relative density was about 95%. But the measured hardness values were 2.34 GPa for nanopowder and 1.87 GPa for commercial powder. Probably due to finer grain size of the sintered body prepared from Mo nanopowder than that prepared using commercial Mo powder. The mean grain sizes were measured to be about 1.4 mm and 6.2 mm, respectively.