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.

Ni–Cr–Al metal-foam-supported catalysts for steam methane reforming (SMR) are manufactured by applying a catalytic Ni/Al2O3 sol–gel coating to powder alloyed metallic foam. The structure, microstructure, mechanical stability, and hydrogen yield efficiency of the obtained catalysts are evaluated. The structural and microstructural characteristics show that the catalyst is well coated on the open-pore Ni–Cr–Al foam without cracks or spallation. The measured compressive yield strengths are 2–3 MPa at room temperature and 1.5–2.2 MPa at 750oC regardless of sample size. The specimens exhibit a weight loss of up to 9–10% at elevated temperature owing to the spallation of the Ni/Al2O3 catalyst. However, the metal-foam-supported catalyst appears to have higher mechanical stability than ceramic pellet catalysts. In SMR simulations tests, a methane conversion ratio of up to 96% is obtained with a high hydrogen yield efficiency of 82%.

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 Fe-22wt.%Cr-6wt.%Al foams were fabricated via the powder alloying process in this study. The structural characteristics, microstructure, and mechanical properties of Fe-Cr-Al foams with different average pore sizes were investigated. Result of the structural analysis shows that the average pore sizes were measured as 474 μm (450 foam) and 1220 μm (1200 foam). Regardless of the pore size, Fe-Cr-Al foams had a Weaire-Phelan bubble structure, and α-ferrite was the major constituent phase. Tensile and compressive tests were conducted with an initial strain rate of 10−3 /s. Tensile yield strengths were 3.4 MPa (450 foam) and 1.4 MPa (1200 foam). Note that the total elongation of 1200 foam was higher than that of 450 foam. Furthermore, their compressive yield strengths were 2.5 MPa (450 foam) and 1.1 MPa (1200 foam), respectively. Different compressive deformation behaviors according to the pore sizes of the Fe-Cr-Al foams were characterized: strain hardening for the 450 foam and constant flow stress after a slight stress drop for the 1200 foam. The effect of structural characteristics on the mechanical properties was also discussed.

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.

Porous metals demonstrate not only excessively low densities, but also novel physical, thermal, mechanical, electrical, and acoustic properties. Thus, porous metals exhibit exceptional performance, which are useful for diesel particulate filters, heat exchangers, and noise absorbers. In this study, SUS316L foam with 90% porosity and 3,000 μm pore size is successfully manufactured using the electrostatic powder coating (ESPC) process. The mean size of SUS316L powders is approximately 12.33 μm. The pore properties are evaluated using SEM and Archimedes. As the quantity of powder coating increases, pore size decreases from 2,881 to 1,356 μm. Moreover, the strut thickness and apparent density increase from 423.7 to 898.3 μm and from 0.278 to 0.840 g/cm3, respectively. It demonstrates that pore properties of SUS316L powder porous metal are controllable by template type and quantity of powder coating.

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.

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.

With the matters of climate change, energy security and resource depletion, a growing pressure exists to search for replacements for fossil fuels. Among various sustainable energy sources, hydrogen is thought of as a clean energy, and thus efficient hydrogen storage is a major issue. In order to realize efficient and safe hydrogen storage, various porous materials are being explored as solid-states materials for hydrogen storage. For those purposes, it is a prerequisite to characterize a material’s textural properties to evaluate its hydrogen storage performance. In general, the textural properties of porous materials are analyzed by the Brunauer-Emmett-Teller (BET) measurement using nitrogen gas as a probe molecule. However, nitrogen BET analysis is sometimes not suitable for materials possessing small pores and surfaces with high curvatures like MOFs because the nitrogen molecule may sometimes be too large to reach the entire porous framework, resulting in an erroneous value. Hence, a smaller probe molecule for BET measurements (such as hydrogen) may be required. In this study, we describe a cost-effective novel cryostat for BET measurement that can reach temperatures below the liquefaction of hydrogen gas. Temperature and cold volume of the cryostat are corrected, and all measurements are validated using a commercial device. In this way, direct observation of the hydrogen adsorption properties is possible, which can translate directly into the determination of textural properties.

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.

Porous SiC beads were prepared by freeze-drying a polycarbosilane (PCS) emulsion. The water-in-oil (w/o) emulsion, which was composed of water, PCS dissolved p-xylene, and sodium xylenesulfonate (SXS) as an emulsifier, was frozen by dropping it onto a liquid N2 bath; this process resulted in 1~2 mm sized beads. Beads were cured at 200 oC for 1 h in air and heat-treated at 800 oC and 1400 oC for 1 h in an Ar gas flow. Two types of pores, lamella-shaped and spherical pores, were observed. Lamellar-shaped pores were found to develop during the freezing of the xylene solvent. Water droplets in the w/o emulsion were changed into spherical pores under freeze-drying. At 1400 oC of heat-treatment, porous SiC was synthesized with a low level of impurities.

The present study demonstrates the effect of freezing conditions on the pore structure of porous Cu-10 wt.% Sn prepared by freeze drying of CuO-SnO2/camphene slurry. Mixtures of CuO and SnO2 powders are prepared by ball milling for 10 h. Camphene slurries with 10 vol.% of CuO-SnO2 are unidirectionally frozen in a mold maintained at a temperature of -30oC for 1 and 24 h, respectively. Pores are generated by the sublimation of camphene at room temperature. After hydrogen reduction and sintering at 650oC for 2 h, the green body of the CuO-SnO2 is completely converted into porous Cu-Sn alloy. Microstructural observation reveals that the sintered samples have large pores which are aligned parallel to the camphene growth direction. The size of the large pores increases from 150 to 300 μm with an increase in the holding time. Also, the internal walls of the large pores contain relatively small pores whose size increases with the holding time. The change in pore structure is explained by the growth behavior of the camphene crystals and rearrangement of the solid particles during the freezing process.

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 metallic glass compact (PMGC) are developed by electro-discharge sintering (EDS) process of gas atomized Zr41.2Ti13.8Cu12.5Ni10Be22.5 metallic glass powder under of 0.2 kJ generated by a 450 μF capacitor being charged to 0.94 kV. Functional iron-oxides are formed and growth on the surface of PMGCs via hydrothermal synthesis. It is carried out at 150oC for 48hr with distilled water of 100 mL containing Fe ions of 0.18 g/L. Consequently, two types of iron oxides with different morphology which are disc-shaped Fe2O3 and needle-shaped Fe3O4 are successfully formed on the surface of the PMGCs. This finding suggests that PMGC witih hydrothermal technique can be attractive for the practical technology as a new area of structural and functional materials. And they provide a promising road map for using the metallic glasses as a potential functional application.