This study investigated the effects of revolution speed and ball size in planetary milling on the microstructure and dehydrogenation behavior of TiH2 powder. The particle size analysis showed that the large particles present in the raw powder were effectively refined as the revolution speed increased, and when milled at 500 rpm, the median particle size was 1.47 μm. Milling with a mixture of balls of two or three sizes was more effective in refining the raw powder than milling with balls of a single size. A mixture of 3 mm and 5 mm diameter balls was the optimal condition for particle refinement, and the measured median particle size was 0.71 μm. The dependence of particle size on revolution speed and ball size was explained by changes in input energy and the number of contact points of the balls. In the milled powder, the endothermic peak measured using differential thermal analysis was observed at a relatively low temperature. This finding was interpreted as the activation of a dehydrogenation reaction, mainly due to the increase in the specific surface area and the concentration of lattice defects.

W-10 wt% Ti alloys that have a homogeneous microstructure are prepared by thermal decomposition of WO3-TiH2 powder mixtures and spark plasma sintering. The reduction and dehydrogenation behavior of WO3 and TiH2 are analyzed by temperature programmed reduction and a thermogravimetric method, respectively. The X-ray diffraction analysis of the powder mixture, heat-treated in an argon atmosphere, shows W- oxides and TiO2 peaks. Conversely, the powder mixtures heated in a hydrogen atmosphere are composed of W, WO2 and TiO2 phases at 600 ℃ and W and W-rich β phases at 800 ℃. The densified specimen by spark plasma sintering at 1500 ℃ in a vacuum using hydrogen-reduced WO3-TiH2 powder mixtures shows a Vickers hardness value of 4.6 GPa and a homogeneous microstructure with pure W, β and Ti phases. The phase evolution dependent on the atmosphere and temperature is explained by the thermal decomposition and reaction behavior of WO3 and TiH2.

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.

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 600oC 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 900oC 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.

Titanium carbide (TiC) powders are successfully synthesized by carburization of titanium hydride (TiH2) powders. The TiH2 powders with size lower than 45 μm (-325 Mesh) are optimally produced by the hydrogenation process, and are mixed with graphite powder by ball milling. The mixtures are then heat-treated in an Ar atmosphere at 800-1200oC for carburization to occur. It has been experimentally and thermodynamically determined that the dehydrogenation, “TiH2 = Ti + H2”, and carburization, “Ti + C = TiC”, occur simultaneously over the reaction temperature range. The unreacted graphite content (free carbon) in each product is precisely measured by acid dissolution and by the filtering method, and it is possible to conclude that the maximal carbon stoichiometry of TiC0.94 is accomplished at 1200oC.

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 TiH0.7, 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.

A sintered body of TiB2-reinforced iron matrix composite (Fe-TiB2) is fabricated by pressureless-sintering of a mixture of titanium hydride (TiH2) and iron boride (FeB) powders. The powder mixture is prepared in a planetary ball-mill at 700 rpm for 3 h and then pressurelessly sintered at 1300, 1350 and 1400oC for 0-2 h. The optimal sintering temperature for high densities (above 95% relative density) is between 1350 and 1400oC, where the holding time can be varied from 0.25 to 2 h. A maximum relative density of 96.0% is obtained from the (FeB+TiH2) powder compacts sintered at 1400oC for 2 h. Sintered compacts have two main phases of Fe and TiB2 along with traces of TiB, which seems to be formed through the reaction of TiB2 formed at lower temperatures during the heating stage with the excess Ti that is intentionally added to complete the reaction for TiB2 formation. Nearly fully densified sintered compacts show a homogeneous microstructure composed of fine TiB2 particulates with submicron sizes and an Fe-matrix. A maximum hardness of 71.2 HRC is obtained from the specimen sintered at 1400oC for 0.5 h, which is nearly equivalent to the HRC of conventional WC-Co hardmetals containing 20 wt% Co.

Fe-30 wt% TiC composite powders are fabricated by in situ reaction synthesis after planetary ball millingof (Fe, TiH2, Carbon) powder mixture. Two sintering methods of a pressureless sintering and a spark-plasma sinteringare tested to densify the Fe-30 wt% TiC composite powder compacts. Pressureless sintering is performed at 1100, 1200and 1300oC for 1-3 hours in a tube furnace under flowing argon gas atmosphere. Spark-plasma sintering is carried outunder the following condition: sintering temperature of 1050oC, soaking time of 10 min, sintering pressure of 50 MPa,heating rate of 50oC/min, and in a vacuum of 0.1 Pa. The curves of shrinkage and its derivative (shrinkage rate) areobtained from the data stored automatically during sintering process. The densification behaviors are investigated fromthe observation of fracture surface and cross-section of the sintered compacts. The pressureless-sintered powder com-pacts are not densified even after sintering at 1300oC for 3 h, which shows a relative denstiy of 66.9%. Spark-plasmasintering at 1050oC for 10 min exhibits nearly full densification of 99.6% relative density under the sintering pressure of50 MPa.

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 290oC and 553 to 639oC, respectively. In the simple-mixed powders by heat-up to 700oC, agglomerates with solid particles and solidified liquid phase are observed, and the size of agglomerates is increased at 1000oC. 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 1000oC, 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.

TiH2 nanopowder was made by high energy ball milling. The milled TiH2 and CNT powders were then simultaneously synthesized and consolidated using pulsed current activated sintering (PCAS) within one minute under an applied pressure of 80 MPa. The milling did not induce any reaction between the constituent powders. Meanwhile, PCAS of the TiH2-CNT mixture produced a Ti-TiC composite according to the reaction (0.92TiH2 + 0.08CNT→0.84Ti + 0.08TiC + 0.92H2, 0.84TiH2 + 0.16CNT→0.68Ti + 0.16TiC + 0.84H2). Highly dense nanocrystalline Ti-TiC composites with a relative density of up to 99.7% were obtained. The hardness and fracture toughness of the dense Ti-8 mole% TiC and Ti-16 mole% TiC produced by PCAS were also investigated. The hardness of the Ti-8 mole% TiC and Ti-16 mole% TiC composites was higher than that of Ti. The hardness value of the Ti-16 mole% TiC composite was higher than that of the Ti-8 mole% TiC composite without a decrease in fracture toughness.

Porous Ti-systems with unidirectionally aligned channels were synthesized by freeze-drying and a heat treatment process. TiH2 powder and camphene were used as the source materials of Ti and sublimable vehicles, respectively. Camphene slurries with TiH2 content of 10 and 15 vol% were prepared by milling at 50˚C with a small amount of oligomeric polyester dispersant. Freezing of the slurry was done in a Teflon cylinder attached to a copper bottom plate cooled at -25˚C while unidirectionally controlling the growth direction of the camphene. Pores were generated subsequently by sublimation of the camphene during drying in air for 48 h. The green body was heat-treated at 1100˚C for 1 h in a nitrogen and air atmosphere. XRD analysis revealed that the samples composed of TiN and TiO2 phase were dependent on the heat-treatment atmosphere. The sintered samples showed large pores of about 120 mm which were aligned parallel to the camphene growth direction. The internal wall of the large pores had relatively small pores with a dendritic structure due to the growth of camphene dendrite depending on the degree of nucleation and powder rearrangement in the slurry. These results suggest that a porous body with an appropriate microstructure can be successfully fabricated by freeze-drying and a controlled sintering process of a camphene/TiH2 slurry.

In present work, manufacturing technologies of titanium hydride powder were studied for recycling of titanium tuning chip and for this, attrition ball milling was carried out under H2 pressure of 0.5 MPa. Ti chips were completely transformed into TiH2 within several hundred seconds. Dehydrogenation process TiH2 powders is consist of two reactions: one is reaction of TiH2 to TiHx and the other decomposition of TiHx to Ti and H2. The former reaction shows relatively low activation energy and it is suggested that the reaction is caused by introduction of defects due to milling.

We manufactured the metal hydrides of using a very easy and cheap way that Ti-12%Mg blending powder was mechanically milled with liquid milling media such as isopropyl alcohol (, containing oxygen) and hexane (, no oxygen) as hydrogen source. The synthesized in isopropyl alcohol contained the high oxygen of 11.2%, while one in hexane had the low oxygen content of 0.7%. Such a difference of oxygen content affected the dehydriding behavior, phase transformation, and microstructural evolution at high temperature, which was investigated through X-ray diffraction and DSC measurements, and electron microscope observations

티타늄 수소화물(TiH2) 분말을 원료로 사용하여 Ti 소결체를 제조하였다. 원료분말은 수소화-탈수소화법(HDH법)에 의해 제조한 상용분말이었으며 비교를 위해 동일한 입도를 갖는 Ti 분말도 함께 소결하였다. TiH2는 소결체의 밀도를 현저하게 촉진하였으며 TiH2→Ti+H2의 탈수소반응에 의해 생성되 청정한 Ti분말이 소결을 촉진하기 때문인 것으로 판단된다. 같은 이유로 TiH2소결체의 산소농도는 Ti 소결체보다 낮게 나타났다. 소결체의 잔류수소는 소결온도가 증가함에 따라 감소하였으며 1200˚C 이상에서는 5 ppm 이하의 낮은 값을 나타냈다. 소결체의 경도는 소결밀도 및 산소량에 비례하는 것으로 나타났다. TiH2분말의 cubic→tetragonal 변태온도는 X-선 회절분석 결과 16~20˚C 구간으로 밝혀졌다.

지구외핵은 순수한 철원소 이외에, 철보다 원자량이 낮은 원소가 상당량 포함되어 있다. 수소도 외핵내에 존재할 가능성이 있는 성분 중의 하나로 인식되고 있다. 따라서, 철수화물에 대한 압력에 따른 수소의 용해도에 대한 연구와 병행하여, 기타 금속수화물에 대한 연구의 확대 또한 중요하다. 수소는 또한 석유의 대체물질로써 그 가능성이 매우 높으며, 금속수화물상태로 수소를 보다 효율적으로 저장할 수 있는 설정구조에 대한 연구 역시 요구된다. 이러한 두가지 이류로, TiH2를 철수화물의 결정구조적 유사물로 선택하여, 고온-고압하에서 특성화 현상을 연구하였다. 결정질 TiH2 분말시료에 대하여 두가지 다른 온도-압력 조건하에서 고온-고압실험이 시해되었다. 이러한 실험 중 하나는 소형 고온 발생장치가 부착된 피스톤-실린더 다이아몬드 앤질기기를 이용하여 압력은 최고 15 GPa 까지, 온도는 500˚에 고정시킨 상태에서 처리한 시료를 상온-상압상태로 변환시켜 X-선 회절실험을 하였다. 이러한 실험에서, 11.3 GPa 압력 이상에서 고온-고압처리한 시료로 부터 사방정계 결정구조를 보이는 비가역성의 새로운 광물상을 발견하였는데 이는 Ti수화물이 고압하에서 안정한 결정 격자구조를 보이는 새로운 것이다. 이 상변이에 따른 몰부피의 변화는 약 10%이다.