Molybdenum, valued for its high melting point and exceptional physical and chemical properties, is studied in diverse fields such as electronics, petrochemicals, and aviation. Among molybdenum oxides, molybdenum dioxide stands out for its higher electrical conductivity than other transition metal oxides due to its structural characteristics, exhibiting metallic properties. It is applied as pellets to gas sensors, semiconductors, and secondary batteries for its properties. Thus, research on molybdenum dioxide compaction and pressureless sintering is necessary, yet research on pressureless sintering is currently insufficient. This study synthesized MoO₃ powder via solution combustion synthesis and reduced it using the 3% hydrogen/argon gas mixture to investigate the effect of reduction temperature on the powder. Additionally, the reduced powder was compacted and subjected to pressureless sintering with temperature as a variable. The density and the microstructure of brown parts were analyzed and discussed.

As the demand for lithium-ion batteries for electric vehicles is increasing, it is important to recover valuable metals from waste lithium-ion batteries. In this study, the effects of gas flow rate and hydrogen partial pressure on hydrogen reduction of NCM-based lithium-ion battery cathode materials were investigated. As the gas flow rate and hydrogen partial pressure increased, the weight loss rate increased significantly from the beginning of the reaction due to the reduction of NiO and CoO by hydrogen. At 700 °C and hydrogen partial pressure above 0.5 atm, Ni and Li2O were produced by hydrogen reduction. From the reduction product and Li recovery rate, the hydrogen reduction of NCM-based cathode materials was significantly affected by hydrogen partial pressure. The Li compounds recovered from the solution after water leaching of the reduction products were LiOH, LiOH·H2O, and Li2CO3, with about 0.02 wt% Al as an impurity.

This study evaluated the odor mitigation effect of rice husk biochar addition to the bedded pack dairy barn floor using lab-scale reactors for five days. Rice husk biochar mixed with dairy manure and sawdust mixture at different ratios (5%-addition test unit: adding biochar by 5% of the total solid weight of the mixture, 10%-addition test unit: adding biochar by 10% of the total solid weight of the mixture). Cumulative NH3 and H2S emissions of 10%-addition test unit were reduced by 26% (p< 0.05) and 46% (p = 0.0655), respectively, compared with control. However, 5%-addition test unit did not show NH3 and H2S emission reduction. Further research is needed to determine the appropriate level of biochar addition between 5 and 10%, and to evaluate applicability in the field through economic analysis.

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.

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.

We investigate the reduction of SnO2 and the generation of syngas(H2, CO) using methane(CH4) and hydrogen(H2) or a mixed gas of methane and hydrogen as a reducing gas. When methane is used as a reducing gas, carbon is formed by the decomposition of methane on the reduced Sn surface, and the amount of generated carbon increases as the amount and time of the supply of methane increases. However, when hydrogen is used as a reducing gas, carbon is not generated. High purity Sn of 99.8 % and a high recovery rate of Sn of 93 % are obtained under all conditions. The effects of reducing gas species and the gas mixing ratio on the purity and recovery of Sn are not significantly different, but hydrogen is somewhat more effective in increasing the purity and recovery rate of Sn than methane. When 1 mole of methane and 1 mole of hydrogen are mixed, a product gas with an H2/CO value of 2, which is known to be most useful as syngas, is obtained.

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 300oC shows Cu, MoO3, and Cu2MoO5 phases. In contrast, the powder mixture heated at 400oC 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 700oC, shows the dispersion of nano-sized Cu agglomerates on the surface of Mo powders.

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.

A black nickel oxide powder, one of the commercial nickel oxide ores, was reduced by hydrogen gas in a batchtype fluidized-bed reactor in a temperature range of 350 to 500 oC and in a residence time range of 5 to 120 min. The hydrogen reduction behavior of the black nickel oxide was found to be somewhat different from that of green nickel oxide ore. For the black nickel oxide, the maximum temperature (below which nickel oxide particles can be reduced without any agglomeration) was significantly lower than that observed for the green nickel oxide. In addition, the best curve fittings of the Avrami model were obtained at higher values of the overall rate constant “k” and at lower values of the exponent “m”, compared to those values for the green nickel oxide. It may be inferred from these results that the hydrogen reduction rate of the black nickel oxide is faster than that of the green nickel oxide in the early stages, but the situation reverses in the later stages. For the black nickel oxide ore, in spite of the low temperature sintering, it was possible to achieve a high degree fluidized-bed reduction at lower temperatures and at lower gas consumption rates than was possible for the green nickel oxide. In this regard, the use of black nickel oxide is expected to yield a benefit if its ore price is sufficiently lower than that of the green nickel oxide.

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 Bi2Te2.7Se0.3 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.

A commercial NiO (green nickel oxide, 86 wt% Ni) powder was reduced using a batch-type fluidized-bed reactor in a temperature range of 500 to 600 oC and in a residence time range of 5 to 90 min. The reduction rate increased with increases in temperature; however, agglomeration and sintering (sticking) of Ni particles noticeably took place at high temperatures above 600 oC. An increasing tendency toward sticking was also observed at long residence times. In order to reduce the oxygen content in the powder to a level below 1 % without any sticking problems, which can lead to defluidization, proper temperature and residence time for a stable fluidized-bed operation should be established. In this study, these values were found to be 550 oC and 60 min, respectively. Another important condition is the specific gas consumption rate, i.e. the volume amount (Nm3) of hydrogen gas used to reduce 1 ton of Green NiO ore. The optimum gas consumption rate was found to be 5,000 Nm3/ton-NiO for the complete reduction. The Avrami model was applied to this study; experimental data are most closely fitted with an exponent (m) of 0.6 ± 0.01 and with an overall rate constant (k) in the range of 0.35~0.45, depending on the temperature.

In this study, the reduction kinetics and behaviors of oxides in the water-atomized iron powder have been evaluated as a function of temperature ranging 850-1000˚C in hydrogen environment, and compared to the reduction behaviors of individual iron oxides including Fe2O3, Fe3O4 and FeO. The water-atomized iron powder contained a significant amount of iron oxides, mainly Fe3O4 and FeO, which were formed as a partially-continuous surface layer and an inner inclusion. During hydrogen reduction, a significant weight loss in the iron powder occurred in the initial stage of 10 min by the reduction of surface oxides, and then further reduction underwent slowly with increasing time. A higher temperature in the hydrogen reduction promoted a high purity of iron powder, but no significant change in the reduction occurred above 950˚C. Sequence reduction process by an alternating environment of hydrogen and inert gases effectively removed the oxide scale in the iron powder, which lowered reduction temperature and/or shortened reduction time.

In this study, nano-scale copper powders were reduction treated in a hydrogen atmosphere at the relativelyhigh temperature of 350℃ in order to eliminate surface oxide layers, which are the main obstacles for fabricating anano/ultrafine grained bulk parts from the nano-scale powders. The changes in composition and microstructure beforeand after the hydrogen reduction treatment were evaluated by analyzing X-ray diffraction (XRD) line profile patternsusing the convolutional multiple whole profile (CMWP) procedure. In order to confirm the result from the XRD lineprofile analysis, transmitted electron microscope observations were performed on the specimen of the hydrogen reduc-tion treated powders fabricated using a focused ion beam process. A quasi-statically compacted specimen from the nano-scale powders was produced and Vickers micro-hardness was measured to verify the potential of the powders as thebasis for a bulk nano/ultrafine grained material. Although the bonding between particles and the growth in size of theparticles occurred, crystallites retained their nano-scale size evaluated using the XRD results. The hardness results dem-onstrate the usefulness of the powders for a nano/ultrafine grained material, once a good consolidation of powders isachieved.

Freeze drying of a porous Cu-Sn alloy with unidirectionally aligned pore channels was accomplished by using a composite powder of CuO-SnO2 and camphene. Camphene slurries with CuO-SnO2 content of 3, 5 and 10 vol% were prepared by mixing with a small amount of dispersant at 50˚C. Freezing of a slurry was done at -25˚C while the growth direction of the camphene was unidirectionally controlled. Pores were generated subsequently by sublimation of the camphene during drying in air for 48 h. The green bodies were hydrogen-reduced at 650˚C and then were sintered at 650˚C and 750˚C for 1 h. XRD analysis revealed that the CuO-SnO2 powder was completely converted to Cu-Sn alloy without any reaction phases. The sintered samples showed large pores with an average size of above 100μm which were aligned parallel to the camphene growth direction. Also, the internal walls of the large pores had relatively small pores. The size of the large pores decreased with increasing CuO-SnO2 content due to the change of the degree of powder rearrangement in the slurry. The size of the small pores decreased with increase of the sintering temperature from 650˚C to 750˚C, while that of the large pores was unchanged. These results suggest that a porous alloy body with aligned large pores can be fabricated by a freeze-drying and hydrogen reduction process using oxide powders.

The study on the fabrication of iron powder from forging scales using hydrogen gas has been conducted on the effect of hydrogen partial pressure, temperature, and reactive time. The mechanism for the reduction of iron oxides was proposed with various steps, and it was found that reduction pattern might be different depending on tem- perature. The iron content in the scale and reduction ratio of oxygen were both increased with increasing reactive time at 0.1atm of hydrogen partial pressure. On the other hand, for over 30 minutes at 0.5 atm of hydrogen partial pressure, the values were found to be almost same. In the long run, iron metallic powder was obtained with over 90% of iron content and an average size of its powder was observed to be about 100 µm.

In order to fabricate the porous Mo with controlled pore characteristics, unique processing by using powder as the source and camphene as the sublimable material is introduced. Camphene-based 15 vol% slurries, prepared by milling at with a small amount of dispersant, were frozen at . Pores were generated subsequently by sublimation of the camphene during drying in air for 48 h. The green body was hydrogen-reduced at , and sintered at for 1 h. After heat treatment in hydrogen atmosphere, powders were completely converted to metallic W without any reaction phases. The sintered samples showed large pores with the size of about which were aligned parallel to the camphene growth direction. Also, the internal wall of large pores and near bottom part of specimen had relatively small pores due to the difference in the camphene growth rate during freezing process. The size of small pores was decreased with increase in sintering temperature, while that of large pores was unchanged. The results are strongly suggested that the porous metal with required pore characteristics can be successfully fabricated by freeze-drying process using metal oxide powders.

Bismuth-telluride based thermoelectric powders were fabricated by two-step planetary milling process which produces bimodal size distribution ranging . The powders were reduced in hydrogen atmosphere to minimize oxygen contents which cause degradation of thermoelectric performance by decreasing electrical conductivity. Oxygen contents were decreased from 0.48% to 0.25% by the reduction process. In this study, both the as-synthesized and the reduced powders were consolidated by the spark plasma sintering process at for 10 min at the heating rate of and then their thermoelectric properties were investigated. The sintered samples using the reduced p-type thermoelectric powders show 15% lower specific electrical resistivity () than those of the as-synthesized powders while Seebeck coefficient and thermal conductivity do not change a lot. The results confirmed that ZT value of thermoelectric performance at room temperature was improved by 15% due to high electric conductivity caused by the controlled oxygen contents present at bismuth telluride materials.

The present investigation has attemped to optimize hydrogen reduction process for the mass production of Fe-8wt%Ni nanoalloy powder from ball milled powder. In-situ hygrometry study was performed to monitor the reduction behavior in real time through measurement of water vapor outflowing rate. It was found that the reduction process can be optimized by taking into account the apparent influence of water vapor trap in the reactor on reduction kinetics which strongly depends on gas flow rate, reactor volume and reduction.