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 -25°C, followed by sublimation at room temperature. After hydrogen reduction at 300°C 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.

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 500°C and sintered at 800°C 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.

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 -30°C, and pores are generated in the frozen specimens by camphene sublimation during air drying. The green bodies are sintered for 1 h at 700°C and 800°C 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.

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 -30°C for 1 and 24 h, respectively. Pores are generated by the sublimation of camphene at room temperature. After hydrogen reduction and sintering at 650°C 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.

Citations

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• Fabrication of Porous Ni by Freeze Drying and Hydrogen Reduction of NiO/Camphene Slurry
  Jae-Hun Jeong, Sung-Tag Oh, Chang-Yong Hyun
  Journal of Korean Powder Metallurgy Institute.2019; 26(1): 6.     CrossRef
• Fabrication of Al2O3 Dispersed Porous Cu by Freeze Drying of CuO-Al2O3/Camphene Slurry
  Hyunji Kang, Doh-Hyung Riu, Sung-Tag Oh
  journal of Korean Powder Metallurgy Institute.2018; 25(1): 25.     CrossRef
• Porous W-Ni Alloys Synthesized from Camphene/WO3-NiO Slurry by Freeze Drying and Heat Treatment in Hydrogen Atmosphere
  Sung Hyun Park, Seong-Min Park, So-Jeong Park, Bo-Yeong Park, Sung-Tag Oh
  Korean Journal of Materials Research.2018; 28(2): 108.     CrossRef

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

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• Freeze Drying Process and Pore Structure Characteristics of Porous Cu with Various Sublimable Vehicles
  Gyuhwi Lee, Sung-Tag Oh, Myung-Jin Suk, Young-Keun Jeong
  Journal of Korean Powder Metallurgy Institute.2020; 27(3): 198.     CrossRef
• Interaction of Solid Particles with the Solidifying Front in the Liquid-Particle Mixture
  Ho-Suk Lee, Kyu-Hee Lee, Sung-Tag Oh, Young Do Kim, Myung-Jin Suk
  Journal of Korean Powder Metallurgy Institute.2018; 25(4): 336.     CrossRef

This study reports a simple way of fabricating the porous Cu with unidirectional pore channels by freeze drying camphene slurry with Cu oxide coated Cu powders. The coated powders were prepared by calcination of ballmilled powder mixture of Cu and Cu-nitrate. Improved dispersion stability of camphene slurry could be achieved using the Cu oxide coated Cu powders instead of pure Cu powders. Pores in the frozen specimen at -25°C were generated by sublimation of the camphene during drying in air, and the green bodies were sintered at 750°C for 1 h in H₂ atmosphere. XRD analysis revealed that the coated layer of Cu oxide was completely converted to Cu phase without any reaction phases by hydrogen heat treatment. The porous Cu specimen prepared from pure Cu powders showed partly large pores with unidirectional pore channels, but most of pores were randomly distributed. In contrast, large and aligned parallel pores to the camphene growth direction were clearly observed in the sample using Cu oxide coated Cu powders. Pore formation behavior depending on the initial powders was discussed based on the degree of powder rearrangement and dispersion stability in slurry.

Citations

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• Effect of Freezing and Sintering Condition of CuO-SnO2/Camphene Slurries on the Pore Structure of Porous Cu-Sn
  Joo-Hyung Kim, Sung-Tag Oh, Chang-Yong Hyun
  Journal of Korean Powder Metallurgy Institute.2016; 23(1): 49.     CrossRef
• Fabrication of Cu-30 vol% SiC Composites by Pressureless Sintering of Polycarbosilane Coated SiC and Cu Powder Mixtures
  Yeon Su Kim, Na-Yeon Kwon, Young-Keun Jeong, Sung-Tag Oh
  Korean Journal of Materials Research.2016; 26(6): 337.     CrossRef
• Synthesis of Aligned Porous Sn by Freeze-Drying of Tin Chloride/camphene Slurry
  수룡 방, 승탁 오
  Korean Journal of Materials Research.2015; 25(1): 27~31.     CrossRef

Cu-Ni alloys with unidirectionally aligned pores were prepared by freeze-drying process of CuO-NiO/camphene slurry. Camphene slurries with dispersion stability by the addition of oligomeric polyester were frozen at -25°C, and pores in the frozen specimens were generated by sublimation of the camphene during drying in air. The green bodies were hydrogen-reduced at 300°C and sintered at 850°C for 1 h. X-ray diffraction analysis revealed that CuO-NiO composite powders were completely converted to Cu-Ni alloy without any reaction phases by hydrogen reduction. The sintered samples showed large and aligned parallel pores to the camphene growth direction, and small pores in the internal wall of large pores. The pore size and porosity decreased with increase in CuO-NiO content from 5 to 10 vol%. The change of pore characteristics was explained by the degree of powder rearrangement in slurry and the accumulation behavior of powders in the interdendritic spaces of solidified camphene.

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• Enhancement in electrical conductivity of pastes containing submicron Ag-coated Cu filler with palmitic acid surface modification
  Eun Byeol Choi, Jong-Hyun Lee
  Applied Surface Science.2017; 415: 67.     CrossRef
• Investigation for Microstructure and Hardness of Welded Zone of Cu-Ni Alloy using W92-Ni-Fe Sintering Tool
  Tae-Jin Yoon, Sang-Won Park, Myung-Chang Kang, Joong-Suk Noh, Sung-Wook Chung, Chung-Yun Kang
  Journal of Korean Powder Metallurgy Institute.2015; 22(3): 181.     CrossRef
• Controlling Structural and Electrical Properties of Pt Nanopowder-Dispersed SiO2Film
  Jae Ho Lee, In Joo Shin, Sung Woo Lee, Hyeong Cheol Kim, Byung Joon Choi
  Journal of Korean Powder Metallurgy Institute.2014; 21(5): 355.     CrossRef