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.

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.

The hydrogen reduction behavior of the CuO-Co₃O₄ powder mixture for the synthesis of the homogeneous Cu-15at%Co composite powder has been investigated. The composite powder is prepared by ball milling the oxide powders, followed by a hydrogen reduction process. The reduction behavior of the ball-milled powder mixture is analyzed by X-ray diffraction (XRD) and temperature-programmed reduction at different heating rates in an Ar-10%H2 atmosphere. The scanning electron microscopy and XRD results reveal that the hydrogen-reduced powder mixture is composed of fine agglomerates of nanosized Cu and Co particles. The hydrogen reduction kinetics is studied by determining the degree of peak shift as a function of the heating rate. The activation energies for the reduction of the oxide powders estimated from the slopes of the Kissinger plots are 58.1 kJ/mol and 65.8 kJ/mol, depending on the reduction reaction: CuO to Cu and Co₃O₄ to Co, respectively. The measured temperature and activation energy for the reduction of Co₃O₄ are explained on the basis of the effect of pre-reduced Cu particles.

Citations

Citations to this article as recorded by  

• Synthesis of Porous Cu-Co using Freeze Drying Process of Camphene Slurry with Oxide Composite Powders
  Gyuhwi Lee, Ju-Yeon Han, Sung-Tag Oh
  Journal of Korean Powder Metallurgy Institute.2020; 27(3): 193.     CrossRef