Cr-doped higher manganese silicides (HMSs) (Mn1-xCrx)Si1.75 (x = 0–0.35) have been prepared by repeated sintering from raw elemental powder using spark plasma sintering. The a- and cMn-axis length increases with increasing Cr content x. The results of powder X-ray diffraction and microstructural observation suggest that impurity phases, e.g. (Mn, Cr)Si and CrSi2, exist in the samples with x = 0.20 or above. The electrical resistivities and Seebeck coefficient decrease with increasing Cr content x. The Cr content x of 0.10 indicated the largest power factor at 850 K (1.39×10-3W/mK), followed in order by x of 0.25, 0, 0.05, 0.15, 0.20. To confirm the effect of Cr-doping on outputs of modules, two paired p-n modules consisting of n-type purchased Mg2Si and p-type Cr-doped HMS with x = 0, 0.05, 0.10, and 0.20 elements were prepared. The module consisting of (Mn0.9Cr0.1)Si1.75 showed the highest output, that is, 845 mW at 873 K on the hot side. There was approximately 8% improvement compared with that of the module consisting of Cr-free elements.

We applied NiSi2 as an electrode for thermoelectric modules because NiSi2 has high electric conductivity and is expected to suppress the inter-diffusion of Si from MgSi2 and higher manganese silicide (HMS). The thermal expansion coefficient of NiSi2 is close to that of Mg2Si but differs from that of HMS. Therefore, to reduce thermal stress, we tried to insert a buffer layer consisting of HMS and NiSi2 for the interface between the HMS sintered body and the NiSi2 electrode. The NiSi2 was prepared by using spark plasma sintering (SPS) equipment. NiSi2 electrodes and gradients were formed and connected with the HMS by SPS treatment. Crack-free bonding was achieved by inserting gradients consisting of HMS and NiSi2. The inserted composite buffer layer reduced interface stress and interface resistance between HMS and NiSi2.

The magnesium compound Mg2Si and its solid solutions are expected as n-type thermoelectric (TE) material because they are non-toxic, have a large Clarke number, and are light weight. In this study, we improved TE performance by doping Ge into Sb-doped Mg2Si to cause phonon scattering and increase carrier concentration. A bulk of Sb-doped Si-Ge alloy as the raw material was fabricated using an arc-melting method. A high-purity Mg2Si was synthesized from metal Mg and Sb-doped Si-Ge alloy using spark plasma sintering equipment. For the samples with the same Sb concentration, the electrical conductivity was equivalent. On the other hand, the Seebeck coefficient was dependent on Ge concentration. Due to phonon scattering, thermal conductivity decreased by a small amount of Ge doping and κph dominated for thermal conduction. The minimum thermal conductivity of Mg2Si0.90Ge0.10 was 2.25 W/mK (κph: 2.06 W/mK, κel: 0.19 W/mK). The dimensionless figure of merit (ZT) for the Mg2Si0.945Ge0.05Sb0.005 sample was higher than that of the others due to reducing thermal conductivity and increasing carrier concentration. The maximum ZT was 0.47 at 713 K.

We established a Ca1-xBixMn1-yNiyO3 (0 ≤ x, y ≤ 0.1) powder library using a combinatorial system based on the electrostatic spray deposition method. Single phase perovskite-type structures were identified in all of the powders. To measure electrical conductivity, the powder library was subjected to high-pressure (200 MPa) and heat-treated at 950°C for 1 hour in an oxygen atmosphere. As a representative example, the electrical conductivity of 5%-Bi-substituted CaMnO3-δ showed a higher value (63 S·cm-1) than an unsubstituted powder (13 S·cm-1). The improved electrical conductivity, on the other hand, was still very far from the ideal result (167 S·cm-1).

In this study, we fabricated Mg2Si from metal Mg and Si with different particle sizes (425 - 300, 300 - 180, and 75 μm or less) using spark plasma sintering (SPS) equipment. Additionally, the Mg2Si formation was investigated. A sieved Si powder was mixed with metal Mg powder in an inert gas (Ar) atmosphere. The mixture was placed in a graphite die while still in an Ar atmosphere and subjected to SPS at 923 K and 1113 K. The obtained sintering bodies were Mg2Si particles with a size of about 5 μm. Then, the sintered bodies were evaluated by X-ray diffraction (XRD). As a result, it was confirmed that generation of Mg2Si increased with decreasing Si particle size.

Magnesium silicide (Mg2Si) has attracted much interest as an n-type thermoelectric material because it is eco-friendly, non-toxic, light, and relatively abundant compared with other thermoelectric materials. In this study, we tried to improve the thermoelectric performance by doping Sb and Ge in the Mg2Si, as well as further optimizing x in the carrier concentration to cause phonon scattering. A high purity Mg2Si was synthesized from metal Mg and Sb doped Si-Ge alloy by using spark plasma sintering (SPS) equipment. The sintered samples were cut and polished. They were evaluated by using X-ray diffraction (XRD) and X-ray fluorescence (XRF) analyses. The carrier concentration of the samples was measured by using Hall measurement equipment. The electrical conductivity and Seebeck coefficient were measured by using a standard four-probe method in a He atmosphere. The thermal conductivity was measured by using a laser-flash system. We succeeded in obtaining a Sb doped Mg2Si0.95Ge0.05 sintered body easily without any impurities with the SPS equipment. The electrical conductivity of the sample was increased, and thermal conductivity was decreased by increasing the amount of doped Sb. The dimensionless figure of merit ZT became 0.74 at 733 K in the Mg2Si0.95-xGe0.05Sbx sample with x = 0.0022.

NaxCoO2 has a particularly high contact resistance because it forms an insulated layer of NaHCO3 and Na2CO3, which are produced in a chemical reaction with carbon dioxide and water in air on the surface. In this study, we tried to improve the interface resistance between NaxCoO2 and Ag sheet electrodes by connecting these materials with the spark plasma sintering (SPS) technique. The interface resistance between NaxCoO2 and Ag sheet electrodes connected by SPS is compared with that connected with Ag paste. In an experiment, the interface resistance of a sample treated by decrease to less than 1/600 of the former value. It is thought that the NaHCO3 and Na2CO3 insulated layer is decomposed through the application of a large value of applied DC current by using the SPS technique.

In order to decrease the use of cobalt element as in LiCoO2,which is mainly used for cathode materials in lithium ion secondary batteries, a newly pseudo-quintenary layered-type Fe-doped Li-Ni-Co-Ti oxides library was created using the combinatorial technology "M-ist Combi system" based on the electrostatic spray deposition method.

The starting materials used were LiNO3, Ni(NO3)2·6H2O, Co(NO3)2·6H2O, Fe(NO3)3·9H2O and TiO2 nano-slurry. These materials were dissolved or dispersed in a mixture of ethanol and butyl carbitol and mixed in a predefined ratio, respectively. Subsequently, each of the mixtures was sprayed and dried on a grounded reaction plate that was heated to 400˚C. The deposited powder was sintered at 700˚C for 5 hours in air atmosphere. Phase identification of the obtained powder library was evaluated by a combinatorial powder x-ray diffractometer. A reaction phase diagram was established from the structure information and chemical composition by ICP-AES measurement.

From all results, single-phase layered-type compounds showed the composition region that included many Co and Ni elements. On the other hand, single phase spinel-type compounds existed in the Ti-rich composition region.

Layered-type LiNi0.4Co0.6-xTixO2 (0≤x≤0.2) were prepared by conventional electrostatic spray deposition method for studying the correlation of crystal structure and electrode property. Starting materials used were LiNO3, Ni(NO3)2·6H2O, Co(NO3)2·6H2O and TiO2 nano-slurry. These materials were dissolved or dispersed in a mixture of ethanol and butyl carbitol and mixed by predefined ratio, respectively. Then, each of mixtures was sprayed and dried on the grounded reaction plate which was heated at 400 °C. Deposited powder was sintered at 700˚C for 10 hours in air atmosphere. Library of LiNi0.4Co0.6-xTixO2 (0≤x≤0.2) was indexed R-3m by powder X-ray diffraction patterns and its chemical compositions from ICP emission spectroscopy method corresponded to the initial composition conditions. From the diffracted intensity ratio of I(003)/I(104) and the structure refinement by Rietveld method, it was found that the proportion of cation mixing effect increased with increasing amount of Ti among of transition metals. And, from the observation by scanning electron microscope and the calculation by Scherrer’s method, the crystallite size decreased with increasing amount of Ti element. From the charge-discharge property of LiNi0.4Co0.6-xTixO2 (0≤x≤0.2) library, LiNi0.4Co0.5Ti0.1O2 showed better cycle behavior among the library.

Reaction phase diagram of pseudo four-components Li-Ni-Co-Ti oxides was established for finding new chemical composition and functional materials by the combinatorial high-throughput preparation system “M-ist Combi,” based on electrostatic spray deposition process and the combinatorial x-ray powder diffraction apparatus. The new layered-type compounds were found wider composition region than the previous reported composition region of LiNi0.8-yCo0.2TiyO2 (0≤y≤0.1). Furthermore, the new composition regions of single phase for spinel-type and rock salt-type compounds in pseudo four-components Li-Ni-Co-Ti oxides system were also found in a short time.

A newly developed high-throughput exploration system “M-ist Combi” can control mixing ration of five-component compounds. Furthermore, the M-ist Combi system can also be obtained not only thin film but also powder and liquid libraries by controlling applied voltage and used flexibly in either a normal atmosphere or controlled atmosphere. By combining the M-ist Combi system with combinatorial XRD apparatus, we successfully completed the high-throughput powder preparation and phase identification of over 150 samples in one day.

Surface properties and photocatalytic oxidation reactions on the hollandite-type compound K2Ga2Sn6O16 (KGSO) were examined for photoinduced hydrophilicity and oxidative decomposition of an endocrine-disrupting chemical, pentachlorophenol (C6Cl5OH, PCP), under ultraviolet (UV) illumination. The thin films and mesoporous powders of hollandite were used for examination of surface properties and photocatalysis, respectively. The photoinduced surface property was examined by measurement of the contact angle of water, ortho-chlorophenol (o-C6H4ClOH), and toluene on the surface of KGSO. The contact angle of H2O and o-C6H4ClOH decreased to 0° under UV illumination. The toluene showed little change in contact angle under UV irradiation. It is concluded that the surface of KGSO shows photoinduced hydrophilicity for H2O and aromatic compounds with hydroxyl groups (−OH). In addition, KGSO clearly showed a photo-oxidative decomposition of PCP under weak UV illumination at room temperature. The decomposition speed of C6Cl5OH on KGSO was much faster than that on previous reported nano-sized SnO2 photocatalysts. It is expected that photo-oxidative decomposition of aromatic compound will be controlled by a combination of optimum composition of the hollandite phase and control of the morphology of the hollandite particles. This suggests that hollandite would be a promising photocatalyst for decomposition of aromatic compounds in endocrine-disrupting chemicals.

Scanning Nonlinear Dielectric Microscopy (SNDM) is the method for observing ferroelectric polarization distribution, and now, its resolution has become to the sub-nanometer order, which is much higher than other scanning probe microscopy (SPM) methods for the same purpose. Up to now, we have studied high-density ferroelectric data storage using this microscopy. In this study, we have conducted fundamental experiments of nano-sized inverted domain formation in LiTaO3 single, and successfully formed inverted dot array with the density of 1.5 Tbit/inch2.

We developed a combinatorial robot system as the first step of combinatorial approach to wet and dry synthesis of ceramics. In this study, nanoparticles mixtures having maghemite and a small amount of Y2O3 were prepared successively by using the combinatorial robot system. maghemite and Y2O3 slurries were volumetrically and automatically measured and mixed by repetition of sucking and injecting with a micro-pipette attached to the robot arm. The structural phase transition temperature of maghemite to hematite, which was investigated from the exothermic peak in the DTA curve, increased from ca.813K to ca.1093K by 2atom%Y2O3 addition. It was considered that Y2O3 dissolution into the crystal structure of maghemite had an important role on increasing the temperature of the structural phase transition for stabilizing maghemite phase. (Combinatorial, Slurries, Maghemite, Nanoparticles, Phase transition)

KxGaxSn8−xO16 (x ≤ 2) powders with hollandite structure were prepared by the sol-gel method using metal alkoxides. Dried gels, when being annealed at 973 K, changed to well-crystallized hollandite powders with about 22 m2/g in BET value which consisted of needle-like crystallites 25 nm wide and 65 nm long in average. The specific surface area was nearly 100 times larger than that of the hollandite produced at 1648 K by the conventional method, and the preparation temperature was lowered by 500 to 700 K. The powders obtained at 973 K were characterized as an attractive porous material showing a pore size distribution profile sharply monodispersed at 10.7 nm in the mesopore range.