Titanium is the ninth most abundant element in the Earth’s crust and is the fourth most abundant structural metal after aluminum, iron, and magnesium. It exhibits a higher specific strength than steel along with an excellent corrosion resistance, highlighting the promising potential of titanium as a structural metal. However, titanium is difficult to extract from its ore and is classified as a rare metal, despite its abundance. Therefore, the production of titanium is exceedingly low compared to that of common metals. Titanium is conventionally produced as a sponge by the Kroll process. For powder metallurgy (PM), hydrogenation-dehydrogenation (HDH) of the titanium sponge or gas atomization of the titanium bulk is required. Therefore, numerous studies have been conducted on smelting, which replaces the Kroll process and produces powder that can be used directly for PM. In this review, the Kroll process and new smelting technologies of titanium for PM, such as metallothermic, electrolytic, and hydrogen reduction of TiCl₄ and TiO₂ are discussed.

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 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.

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• 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

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°C. Freezing of a slurry is performed at -25°C 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°C and then sintered at 800°C and 900°C 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.

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• 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

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°C, and pores in the frozen specimens are generated by sublimation of the camphene crystals. The green bodies are hydrogen-reduced at 750°C and sintered at 1000°C 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.

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• Characteristic Evaluation of WC Hard Materials According to Ni Content Variation by a Pulsed Current Activated Sintering Process
  Hyun-Kuk Park
  Korean Journal of Materials Research.2020; 30(12): 672.     CrossRef
• Effect of α-lath size on the mechanical properties of Ti–6Al–4V using core time hydrogen heat treatment
  Gye-Hoon Cho, Jung-Min Oh, Hanjung Kwon, Jae-Won Lim
  Materials Science and Technology.2020; 36(7): 858.     CrossRef

The hydrogen reduction behavior of MoO₃-CuO powder mixture for the synthesis of homogeneous Mo-20 wt% Cu composite powder is investigated. The reduction behavior of ball-milled powder mixture is analyzed by XRD and temperature programmed reduction method at various heating rates in Ar-10% H₂ atmosphere. The XRD analysis of the heat-treated powder at 300°C shows Cu, MoO₃, and Cu₂MoO₅ phases. In contrast, the powder mixture heated at 400°C is composed of Cu and MoO₂ phases. The hydrogen reduction kinetic is evaluated by the amount of peak shift with heating rates. The activation energies for the reduction, estimated by the slope of the Kissinger plot, are measured as 112.2 kJ/mol and 65.2 kJ/mol, depending on the reduction steps from CuO to Cu and from MoO₃ to MoO₂, respectively. The measured activation energy for the reduction of MoO₃ is explained by the effect of pre-reduced Cu particles. The powder mixture, hydrogen-reduced at 700°C, shows the dispersion of nano-sized Cu agglomerates on the surface of Mo powders.

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• Synthesis of Mo-Cu nanocomposite powder by hydrogen reduction of copper nitrate coated MoO3 powder mixture
  Ji Won Choi, Ji Young Kim, Youngmin Kim, Eui Seon Lee, Sung-Tag Oh
  Materials Letters.2024; 377: 137565.     CrossRef
• Fabrication of Porous Mo-Cu by Freeze Drying and Hydrogen Reduction of Metal Oxide Powders
  Hyunji Kang, Ju-Yeon Han, Sung-Tag Oh
  Journal of Korean Powder Metallurgy Institute.2019; 26(1): 1.     CrossRef
• Hydrogen Reduction Behavior and Microstructure Characteristics of Ball-milled CuO-Co₃O₄ Powder Mixtures
  Ju-Yeon Han, Gyuhwi Lee, Hyunji Kang, Sung-Tag Oh
  Journal of Korean Powder Metallurgy Institute.2019; 26(5): 410.     CrossRef

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 WO_2.9, 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°C, 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°C 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.

The effect of the mixing method on the characteristics of hybrid-structure W powder with nano and micro sizes is investigated. Fine WO₃ powders with sizes of ~0.6 μm, prepared by ball milling for 10 h, are mixed with pure W powder with sizes of 12 μm by various mixing process. In the case of simple mixing with ball-milled WO₃ and micro sized W powders, WO₃ particles are locally present in the form of agglomerates in the surface of large W powders, but in the case of ball milling, a relatively uniform distribution of WO₃ particles is exhibited. The microstructural observation reveals that the ball milled WO₃ powder, heat-treated at 750°C for 1 h in a hydrogen atmosphere, is fine W particles of ~200 nm or less. The powder mixture prepared by simple mixing and hydrogen reduction exhibits the formation of coarse W particles with agglomeration of the micro sized W powder on the surface. Conversely, in the powder mixture fabricated by ball milling and hydrogen reduction, a uniform distribution of fine W particles forming nano-micro sized hybrid structure is observed.

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  Hosang Jeon, Won Chul Shin, Hee Yun Seol, Yongkan Ki, Kyeong Baek Kim, Ki Seok Choo, Sang Don Lee, Suk-Woong Kang
  Journal of the Korean Fracture Society.2023; 36(4): 111.     CrossRef
• Facile phosphorus-embedding into SnS2 using a high-energy ball mill to improve the surface kinetics of P-SnS2 anodes for a Li-ion battery
  Hongsuk Choi, Seungmin Lee, KwangSup Eom
  Applied Surface Science.2019; 466: 578.     CrossRef
• Hydrogen reduction behavior and microstructural characteristics of WO3 and WO3-NiO powders
  Hyunji Kang, Young-Keun Jeong, Sung-Tag Oh
  International Journal of Refractory Metals and Hard Materials.2019; 80: 69.     CrossRef
• Fabrication of Densified W-Ti by Reaction Treatment and Spark Plasma Sintering of WO3-TiH2 Powder Mixtures
  Hyunji Kang, Heun Joo Kim, Ju-Yeon Han, Yunju Lee, Young-Keun Jeong, Sung-Tag Oh
  Korean Journal of Materials Research.2018; 28(9): 511.     CrossRef

The effects of the heat treatment temperature and of the atmosphere on the dehydrogenation and hydrogen reduction of ball-milled TiH₂-WO₃ powder mixtures are investigated for the synthesis of Ti-W powders with controlled microstructure. Homogeneously mixed powders with refined TiH₂ particles are successfully prepared by ball milling for 24 h. X-ray diffraction (XRD) analyses show that the powder mixture heat-treated in Ar atmosphere is composed of Ti, Ti₂O, and W phases, regardless of the heat treatment temperature. However, XRD results for the powder mixture, heat-treated at 600°C in a hydrogen atmosphere, show TiH₂ and TiH peaks as well as reaction phase peaks of Ti oxides and W, while the powder mixture heat-treated at 900°C exhibits only XRD peaks attributed to Ti oxides and W. The formation behavior of the reaction phases that are dependent on the heat treatment temperature and on the atmosphere is explained by thermodynamic considerations for the dehydrogenation reaction of TiH₂, the hydrogen reduction of WO₃ and the partial oxidation of dehydrogenated Ti.

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• Fabrication of Porous W-Ti by Freeze-Drying and Hydrogen Reduction of WO3-TiH2 Powder Mixtures
  Hyunji Kang, Sung Hyun Park, Sung-Tag Oh
  Journal of Korean Powder Metallurgy Institute.2017; 24(6): 472.     CrossRef

An optimum route to synthesize Ti-Mo system powders is investigated by analyzing the effect of the heat treatment atmosphere on the formation of the reaction phase by dehydrogenation and hydrogen reduction of ball-milled TiH₂-MoO₃ powder mixtures. Homogeneous powder mixtures with refined particles are prepared by ball milling for 24 h. XRD analysis of the heat-treated powder in a hydrogen atmosphere shows TiH₂ and MoO₃ peaks in the initial powders as well as the peaks corresponding to the reaction phase species, such as TiH_0.7, TiO, MoO₂, Mo. In contrast, powder mixtures heated in an argon atmosphere are composed of Ti, TiO, Mo and MoO₃ phases. The formation of reaction phases dependent on the atmosphere is explained by the partial pressure of H2 and the reaction temperature, based on thermodynamic considerations for the dehydrogenation reaction of TiH₂ and the reduction behavior of MoO₃.

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• Effect of titanium addition on mechanical properties of Mo-Si-B alloys
  Won June Choi, Seung Yeong Lee, Chun Woong Park, Jung Hyo Park, Jong Min Byun, Young Do Kim
  International Journal of Refractory Metals and Hard Materials.2019; 80: 238.     CrossRef

The recent rise in applications of thermoelectric materials has attracted interest in studies toward the fabrication of thermoelectric materials using mass production techniques. In this study, we successfully fabricate n-type Bi₂Te_2.7Se_0.3 material by a combination of mass production powder metallurgy techniques, gas atomization, and spark plasma sintering. In addition, to examine the effects of hydrogen reduction in the microstructure, the thermoelectric and mechanical properties are measured and analyzed. Here, almost 60% of the oxygen content of the powder are eliminated after hydrogen reduction for 4 h at 360°C. Micrographs of the powder show that the reduced powder had a comparatively clean surface and larger grain sizes than unreduced powder. The density of the consolidated bulk using as-atomized powder and reduced atomized powder exceeds 99%. The thermoelectric power factor of the sample prepared by reduction of powder is 20% better than that of the sample prepared using unreduced powder.

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  Applied Physics A.2024;[Epub]     CrossRef
• Enhancing thermoelectric performance of K-doped polycrystalline SnSe through band engineering tuning and hydrogen reduction
  Nan Xin, Yifei Li, Guihua Tang, Longyun Shen
  Journal of Alloys and Compounds.2022; 899: 163358.     CrossRef
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  Journal of Korean Powder Metallurgy Institute.2017; 24(2): 115.     CrossRef
• The Preparation and Growth Mechanism of the Recovered Bi2Te3 Particles with Respect to Surfactants
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  Seung Tek Han, Pradip Rimal, Chul Hee Lee, Hyo-Seob Kim, Yongho Sohn, Soon-Jik Hong
  Intermetallics.2016; 78: 42.     CrossRef

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.

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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 synthesis of NiTi alloy powders by hydrogen reduction and dehydrogenation process of NiO and TiH₂ powder mixtures is investigated. Mixtures of NiO and TiH₂ powders are prepared by simple mixing for 1 h or ball milling for 24 h. Simple-mixed mixture shows that fine NiO particles are homogeneously coated on the surface of TiH₂ powders, whereas ball milled one exhibits the morphology with mixing of fine NiO and TiH₂ particles. Thermogravimetric analysis in hydrogen atmosphere reveals that the NiO and TiH₂ phase are changed to metallic Ni and Ti in the temperature range of 260 to 290°C and 553 to 639°C, respectively. In the simple-mixed powders by heat-up to 700°C, agglomerates with solid particles and solidified liquid phase are observed, and the size of agglomerates is increased at 1000°C. From the XRD analysis, the presence of liquid phase is explained by the formation and melting of NiTi₂ intermetallic compound due to an exothermic reaction between Ni and Ti. The simple-mixed powders, heated to 1000°C, lead to the formation of NiTi phase but additional Ni-, Ti-rich and Ti-oxide phases. In contrast, the microstructure of ball-milled powders is characterized by the neck-grown particles, forming Ni3Ti, Ti-oxide and unreacted Ni phase.

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• Effect of Heat Treatment Atmosphere on the Microstructure of TiH2-MoO3 Powder Mixtures
  Ki Cheol Jeon, Sung Hyun Park, Na-Yeon Kwon, Sung-Tag Oh
  Journal of Korean Powder Metallurgy Institute.2016; 23(4): 303.     CrossRef

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 1200°C in hydrogen atmosphere. TGA analysis revealed that the PMMA was decomposed at about 400°C and WO₃ was reduced to metallic W at 800°C. 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.

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