# Fileset [kakenhi-1998.xlsx](https://mdr.nims.go.jp/filesets/501d70cf-2bb5-42e4-bc11-ccd5d99b842e/download) ## Creator National Institute for Materials Science ## Rights ## Other metadata [Physics and Chemistry of Functionally Graded Materials 　Research Report 1998 　Grant-in-Aid for Scientific Besearch on PriorityArea, No. 274 　The Ministry of Education, Science, Sports and Culture of Japan](https://mdr.nims.go.jp/datasets/3740f6dc-a19e-4aa7-8a99-eaf8e1c4229c) ## Fulltext Sheet1 BookTitle_j BookTitle_e Volume/Issue Issueddate Page Title_j Title_e AuthorList_j AuthorList_e Abstract Language Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Besearch on PriorityArea, No. 274 The Ministry of Education, Science, Sports and Culture of Japan Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Research on Priority Area, No. 274 5 1999-03-01 1-4 純WCから調整した傾斜機能材料 Functionally Graded Materials prepared from pure WC 大森守、Takeshi Kakita, 大久保昭、平井敏雄東北大学　金属材料研究所980-0812 宮城県仙台市青葉区片平2- 1-1 Mamoru Omori, Takeshi Kakita, Akira Okubo and Toshio HiraiInstitute for Materials Research, Tohoku University 2-1 -1 Katahira, Aoba-ku, Sendai 980-8577, Japan Summary Functionally graded materials (FGMs) were fabricated from WC and Mo powders using. Two layers of WC-Mo powder inserted between WC and Mo layers were sufficient to relax residual stress based on the thermal expansion mismatch between WC (5.4 x 10**-6/K) and Mo (6.9 x 10**-6/K). The toughness of the WC layer was decreased along the periphery of the disk sample near the edge, but increased inside. WC/WC(Co) FGM was prepared from WC plates and WC-10wt%Co powders. There was no residual stress in the WC layer. The toughness of the WC layer was not lowered at the periphery area. English Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Besearch on PriorityArea, No. 274 The Ministry of Education, Science, Sports and Culture of Japan Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Research on Priority Area, No. 274 5 1999-03-01 5-8 組成傾斜多層パッキング配列の浸出コントロールのためのモノサイズ粒子の集合 Assembling of Mono-Sized Particles for the Percolation Control of Composition Graded Multi-Phase Packing Arrangements 渡辺龍三、市来浩一、葉山知徳、 川崎亮東北大学　工学部材料加工学科　980-8579　仙台市青葉区荒巻字青葉１－１ R. Watanabe, K. Ichiki, T. Hayama, and A. KawasakiDept. Materials Processing, School of Eng., Tohoku Univ. Aoba-yama 02, Sendai 980-8579, Japan INTRODUCTION Powder metallurgical process has been widely used for the fabrication of thermal-stress relief type of functionally graded materials, in which the composition profile is designed to develop the aimed performance with respect to thermal and mechanical properties [1- 4] . Admitting its viability for tailoring various graded structures and shape forming freedom for the practical parts fabrication, the minimum size of the microstructural control is limited to several hundreds or thousands of primary particle diameter and the formed microstructure is generally random in a micro scale, which restricts purely artificial control of the materials functions. To overcome this difficulty we have proposed a particle configuration process in which individual single particles will be positioned at the allotted sites according to the theoretical design. The main purpose of this investigation is to establish particle arrangement technique in two and three dimensions and to construct three dimensionally composition-graded compacts. This process will provide a determinate control of the concentration gradient, as well as phase dispersion and connectivity in FGMs. Within the scheme of the whole investigation the following four tasks have been brought up: (1)Preparation of monodisperse particles for controlled particle arrangement. (2)Development of the construction technique of particle arrays of two and three dimension. (3) Sintering of the particle arrays with particular interest in sintering neck formation and the phase reaction at the neck regions (4) Property evaluation of the sintered particle arrays. As to the last item the thermal and electrical properties have been discussed on the basis of percolation theory. In the present paper the development of the construction technique of particle arrays of two and three dimensions will be described with discussions in relation to the other three items. English Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Besearch on PriorityArea, No. 274 The Ministry of Education, Science, Sports and Culture of Japan Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Research on Priority Area, No. 274 5 1999-03-01 9-12 燃焼合成(SHS)/急速緻密化法によるダイヤモンド分散複合体の傾斜材料 Graded Material of Diamond Dispersed Composites by SHS/Rapid Densification methods 大柳満之　辻上哲也1　小泉光恵21 龍谷大学　ハイテクリサーチセンター2 龍谷大学　龍谷エクステンションセンター M.Ohyanagi1, T.Tsujikami1, M.Koizumi21High-tech Research Center, Ryukoku University, Japan 2REC, Ryukoku University, Japan A graded dispersion of diamond in TiB2/Si cermet (90vol% diamond layer / diamond graded dispersed layers / matrix) was achieved by dynamic pseudo isostatic compaction (DPIC) just after self-propagating high temperature synthesis (SHS). And also diamond gradeded WC-Co cermets was fabricated by static pseudo isostatic compaction (SPIC) with induction field activated SHS (IFASHS). The DPIC and SPIC were performed using commercial casting sand as the pressure transmitting medium for the densification of the cermets. The process enabled to simultaneously synthesize and densify the cermet matrix within a few minutes. Diamond (an average particle size, approximately 30 micrometers) mixed with the reactant was fixed in the matrix produced after the SHS. The maximum combustion temperatures were controlled to be approximately 2000 K to prevent the diamond to graphite transformation. The diamond particles were found to be strongly fixed in the matrix even after lapping with a diamond abrasive by SEM. English Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Besearch on PriorityArea, No. 274 The Ministry of Education, Science, Sports and Culture of Japan Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Research on Priority Area, No. 274 5 1999-03-01 13-16 傾斜バンドギャップを伴うTi1-xVxO２固溶体薄膜光電極の調整と光電気化学特性 Preparation and Photoelectrochemical Properties of Ti1-xVxO2 Solid Solution Thin Film Photoelectrodes with Gradient Bandgap 趙高凌、幸塚広光、 H. Lin, M. Takahashi、 横尾俊信京都大学　化学研究所　611-0011　京都府宇治市 G.L. Zhao, H. Kozuka, H. Lin, M. Takahashi and T. YokoInstitute for Chemical Research, Kyoto University, Uji, Kyoto-fu 611-0011, Japan INTRODUCTION Because of the low fabrication cost and the potential ability to convert solar energy into electric and chemical energy simultaneously, a semiconductor-liquid junction solar cell (SLJSC) is believed to be full of promise in the field of solar energy conversion. However, no semiconductor materials have been found to possess all of the requirements [1] necessary for efficient solar energy conversion in SLJSCs. Photoelectrochemically stable semiconductors such as TiO2 and SrTiO3 own wide bandgaps and hence visible light cannot be utilized, whereas narrow bandgap semiconductors such as GaP and GaAs are often photoelectrochemically unstable. On the other hand, mixed semiconductors with gradient composition have been applied to solid state solar batteries [2-4]. Gradient-type heterojunctions have better electron transfer properties than abrupt-type heterojunctions because of the longer carrier lifetime [3]. A gradient bandgap is possible to attain by controlling the composition of solid solutions [2, 3, 5-7]. Our previous work [8] showed that Ti1-xVxO2 solid solution films with x from 0 to 0.1 could be easily prepared by the sol-gel method. Moreover, the optical absorption edge of Ti1-xVxO2 shifted to longer wavelengths with increasing x. Hence, taking into account that TiO2 has high photoelectrochemical stability it is interesting to prepare the gradient bandgap Ti1-xVxO2 semiconductor film electrodes. In the present study, we provide a design for a photoelectrochemically stable semiconductor film electrode with a gradient bandgap. An attempt is made to prepare the gradient bandgap titanium vanadium oxide, Ti1-x VxO2, n- type semiconductor film electrodes by the sol-gel method. The photoelectrochemical properties of the film electrodes are also investigated. English Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Besearch on PriorityArea, No. 274 The Ministry of Education, Science, Sports and Culture of Japan Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Research on Priority Area, No. 274 5 1999-03-01 17-20 MA複合粉末のプラズマ溶射による傾斜機能熱電皮膜の作製 Fabrication of Functionally Graded Thermoelectric Coatings by Plasma Spraying of Mechanically-alloyed Composite Powders 福本昌宏　時本雄次　三河克明　田中康徳豊橋技術科学大学　生産システム工学系　441-8580　愛知県豊橋市天伯町１－１ M. Fukumoto, Y Tokimoto, H. Mikawa and Y.TanakaDepartment of Production Systems Engineering, Toyohashi University of Technology, 1-1, Tempaku-cho, Toyohashi, Aichi 441 -8580 Japan INTRODUCTION Functionally graded structure is regarded as an effective system for thermoelectric conversion(TEC) material[1], as a single element is limited in its generation power. In many configurations of TEC, thick coating may be advantageous in joining[2] . Therefore, thermal spraying is worthy of remark among several processings as the thick coatings of hard-forming materials can be easily made by this process[3] . However, a conventional method, simultaneous spraying of blended elemental metals followed by post heat treatment, is hard to apply because a strict control of elemental composition by delicate heat treatment is required to get the high performance TEC. In this study, homogeneously mixed metal/metal composite powders made by mechanical alloying(MA) were applied to plasma spraying to obtain the thick TEC coatings, and the process conditions for getting the high performance functionally graded TEC coatings were investigated. The great merit of MA prosess is the possibility of controlling the additional dopant fraction and creating the fine and homogeneous structured composite powders. By spraying of several kinds of composite powders, the functionally graded TEC thick coatings are expected to be made as a laminating or joining form. Consequently, optimum conditions of mechanical alloying, plasma spraying and post heat treatment to get the appropriate thermoelectric phases for each material system were empirically decided. As the fundamental research for the FGM processing of TEC coating, the joint type Si-Ge coating with different dopant compositions was fabricated and the thermoelectric property of the joint was evaluated. English Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Besearch on PriorityArea, No. 274 The Ministry of Education, Science, Sports and Culture of Japan Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Research on Priority Area, No. 274 5 1999-03-01 21-24 Mo-Si-C-N-Hポリマーから誘導した非晶質傾斜機能セラミックス Functionally Graded Amorphous Ceramics Derived from Mo-Si-C-N-H Polymers 佐々木眞室蘭工業大学　050-8585　北海道室蘭市水元町２７番１号 Makoto SasakiMuroran Institute of Technology, 27-1 Mizumoto; Muroran; Hokkaido 050-8585, Japan INTRODUCTION Polymer-derived ceramics have been focused on high performance applications of thermoelectric materials and lithium secondary electrode materials1-5). Author and the co-workers have already reported a degradation of carbon contents of Si-C-N amorphous ceramics by introducing of ammonia gas during ceramization of the polymers6). On the other hand, compositional graded coating is of interest to reduce thermal stresses between coated layer and substrate. This work results the effect of ceramization atmosphere on the composition of ceramics derived from molybdenum-containing polysilazanes and their related polymers. Soluble Mo-Si-C-N-H polymers were fabricated by reaction of polysilazane with molybdenum-ammonium complex synthesized from molybdenum chloride and ammonia gas in chloroform. The structural analysis and thermal expansion coefficients measurement were achieved to optimize an FGM fabrication condition. Oxidation resistance of the Mo-Si-N/ Mo-Si-C-N FGM-coated two dimensional (2D)-C/C composite was examined. English Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Besearch on PriorityArea, No. 274 The Ministry of Education, Science, Sports and Culture of Japan Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Research on Priority Area, No. 274 5 1999-03-01 25-28 強-重力場下での原子の沈降を用いた固体中でのナノ－メゾスケール傾斜構造の形成 Formation of Nano-Mezo Scale Graded Structure in Solids Using Sedimentation of Atoms under Strong-Gravity Field Tsutomu MASHIMO and Hirotaka IHARA熊本大学　工学部　〒860　熊本市 Tsutomu MASHIMO and Hirotaka IHARAFaculty of Engineering, Kumamoto University, Kumamoto 860, Japan INTRODUCTION If a graded structures in nano-mezo scale are formed in solids, new functional properties are expected to be appear. On the other hand, the sedimentation of component atoms may realize the formation of graded structures in atomic scale or of nonstoichiometric structures in solids. We have developed an ultracentrifuge apparatus that can generate a strong gravity field of even 1x10**6 g at temperatures of several hundreds of deg. C for several days [1]. We have recently performed the mega-gravity field experiment on a Bi-Sb system alloy [2] and have succeeded in forming composition distributions. On the other hand, colloid particles would move even under not so strong acceleration field due to the large molecular weights. The main purpose of this study is to form a graded structures in nano-mezo scale in solids through the sedimentation of atoms or molecules. We are performing the experiments on some binary-system alloys with low melting temperature and also the sol-gel materials. We also carried out the simulation of the sedimentation process on the basis of the self-consistent theory [3,4]. English Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Besearch on PriorityArea, No. 274 The Ministry of Education, Science, Sports and Culture of Japan Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Research on Priority Area, No. 274 5 1999-03-01 29-31 金属半空間における傾斜機能材料（FGM）層での波動 Waves in a FGM Layer on a Metal HaIf Space 渡辺一美山形大学　機械工学科　992-8510　山形県米沢市 Kazumi WatanabeDepartment of Mechanical Engineering, Yamagata University, Yonezawa, Yamagata 992-8510, Japan Introduction Time-harmonic response of a FGM layer bonded to a metal half space is discussed based on the linear elastodynamic theory. Material parameters, rigidity, poisson ratio and density, are assumed to be varying as Sigmoid functions. Then, all of the material parameters and P and S wave velocities are continuous through out the compound half space. Two cases of a time harmonic load on the surface of FGM layer are considered. Applying the method of high frequency approximation, the leading term for the approximate displacement is derived. Then, it is found that Rayleigh (surface) wave induces a super-sonic leading S-wave (Mach cone) below the some depth where the velocity of S-wave in the FGM layer is lower than that of Rayeigh wave. Acrossing its sonic point, the displacement has a square root singularity at the subsonic side and has no singularity at the super-sonic side. This singular behaviour is one of new wave phenomena in the FGM. English Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Besearch on PriorityArea, No. 274 The Ministry of Education, Science, Sports and Culture of Japan Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Research on Priority Area, No. 274 5 1999-03-01 33-36 ポリマー混合の傾斜機能プラスチックの自己集合と超大表面材料の誘導 Selfassembly of Functionally Graded Plastics of Polymer Blend And Derivation of Super Large Surface Material K.Orihara山形大学　工学部　992-8510　山形県米沢市城南４丁目３－１６ K. OriharaFaculty of Engineering, Yamagata University, 4-3-16 Jonan, Yonezawa, 992-8510 Japan INTRODUCTION In history almost all of the functional materials and the machines have been manufactured artifically. The progress of the manufacture eigineering is considered to be rather a progress of human life itself. However, recently the requests of large scale and super precise process for highly functional products tend to burden the company managements. At one time these were broadcasted as a symbolic phenomon of higher grade technology. But gradually, large energy loss in the complex process and technological limitation in the manufacturing of newly expected products such as super micro machine which will work, for example, in blood vessel. For the breakthrough of above problem in the manufacuturing technology, we had been investigated the possibility of "selfassembly" or "selforganization" processing the functionally materials of polymer or organic-inorganic composite materails. The developement of such selfassemly process is condidered one of most important key-technology in 21 century.[1] Since these new processing of selfassembly is usually found in biological process, we can apply many phenomena in it for forming researching idea. In the present study, selfassembly of functionally graded plastics (FGM) of polymer blend were investigated. Particularly as an application of above structure, the formation of super large surface materials was investigated. Recently functionally garaded structure in engineering plastics, fiber, and film was fabricated by self-assembly [2,3,4] by applying a particular phase separation that had been prebiously found [5,6,7] in the polymer blend. Three basic structures of graded, step, and uniform sea-island structure were observed in the cross-section of the samples as shown in Fig.1. Each structure was formed without any artificial controlling technique during casting process from the solution [2,3] or cooling from the melt [4] of the polymer blend. English Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Besearch on PriorityArea, No. 274 The Ministry of Education, Science, Sports and Culture of Japan Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Research on Priority Area, No. 274 5 1999-03-01 37-40 計算機像解析使用による高い熱伝導率を持つFGM基質材料の開発 Development of FGM Substrate Materials With High Thermal Conductivity by using Computed Image Analysis H.Yokota, 友田陽,太田弘道茨城大学　工学部材料工学科　316-8511　茨城県日立市中成沢町４丁目１２－１ H.Yokota, Y.Tomota and H.OhtaDepartment of Materials Science, Faculty of Engineering, Ibaraki University , 12-1 Nakanarusawa 4chome, Hitachi Ibaraki 316-8511, Japan INTRODUCTION We have studied on the theoretical prediction of thermal conductivity using micromechanical modeling and FEM analysis based on micrographic data [1][2]. Lots of theoretical predictions have been reported for the thermal conductivity of composite materials with the second phase particles dispersed separately in the matrix, showing good agreements with measured data [1]. It is however difficult to predict the properties of a composite material with a percolated microstructure, so that a new method is expected to be developed. Particularly in the case of FGMs with high thermal conductivity, the influence of percolation on their physical properties must be evaluated quantitatively. The present paper describes about two trials of such a purpose, i.e. one is an improvement for FEM calculation procedure and the other is microstructure modeling based on a nucleation and growth kinetics of the second phase formation. English Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Besearch on PriorityArea, No. 274 The Ministry of Education, Science, Sports and Culture of Japan Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Research on Priority Area, No. 274 5 1999-03-01 41-44 無機-有機傾斜複合体の合成と多孔体への応用 Preparation and Application of Porous Inorganic-organic Functionally Graded Complexes 熊田伸弘　木野村陽一山梨大学　工学部　400-0021　甲府市宮前町７ N. Kumada and N. KinomuraFaculty of Engineering, Yamanashi University, Miyamae-7, Kofu 400-8511, Japan INTRODUCTION We had attempted to prepare inorganic-organic functionally graded complexes, zirconium phenylphosphonate phosphates cointercalated with aniline and to convert the complexes to porous materials by removing aniline. Obtained porous materials had high specifc surface area (~200m**2/ g), however, these porous materials decomposed at above 500deg.C. In order to improve thermal stability of the porous materials, it was attempted that silanes were intercalated into the interlayer of(alpha)-zirconium phosphate and the silane derivatives converted to porous materials pillared by silica at elavated temperatures. Silylation of (alpha)-zirconium phosphate was carried out using various silanes in toluene. It was necessary to intercalate organic bases prior to the silylation. Obtained silane derivatives were changed to layered compounds containing silica as a pillar in the interlayer space by heat treatment. Effect of organic base on silylation was also examined. English Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Besearch on PriorityArea, No. 274 The Ministry of Education, Science, Sports and Culture of Japan Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Research on Priority Area, No. 274 5 1999-03-01 45-48 ゴム系傾斜機能複合材料の作製とその物性 Preparation and Properties of Functionally Graded Rubber Materials 池田裕子、掬谷信三京都工芸繊維大学 工芸学部*京都大学化学研究所 Y. Ikeda, S. Kohjiya*Faculty of Engineering and Design, Kyoto Institute of Technology *Institute for Chemical Research, Kyoto University INTRODUCTION Generally, the technology for the homogeneous preparation of rubber vulcanizates has been paid attention in the industrial field. It is because that the homogeneity of mixing and curing much influence the mechanical properties of the vulcanizates. In our study, however, the crosslinking density of vulcanizates were graded and the mechanical properties of vulcanizates were evaluated in order to obtain the fundamental information for the development of new functional materials. Butyl rubber (isobutylene-isoprene copolymer,abbreviated as IIR) was subjected for the preparation of the graded vulcanizates in this report, because IIR shows a high damping property and a strain-induced crystallization. The gradient of the crosslinking densities of IIR vulcanizates is expected to extend the characteristics of IIR vulcanizates. English Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Besearch on PriorityArea, No. 274 The Ministry of Education, Science, Sports and Culture of Japan Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Research on Priority Area, No. 274 5 1999-03-01 49-52 多核錯体の逐次吸着を利用する傾斜機能材料の作成 Preparation of FunctionaIIy-Graded Materials by Means of Stepwise Adsorption of MuItinuclear Complexes 一ノ瀬泉、 T. Yonezawa九州大学　工学部　812-8581　福岡市東区箱崎6-10-1 I. Ichinose and T. YonezawaGraduate School of Engineering, Kyushu University, Hakozaki 6-10-1, Fukuoka 812-8581, Japan The fabrication of functionally graded materials with molecular precision is an essential factor for their chemical applications. Based on this concept, we have developed several preparative techniques for ultrathin nano-graded films by means of stepwise adsorption from solution. First, alternate adsorption technique of oppositely-charged polymers had been extended to a wide range of charged materials such as multinuclear complexes, clay, metal oxide particles, etc. We have also developed a stepwise adsorption of metal alkoxides from solution. This surface sol-gel process is nowadays widely extended to a preparative technique of metal oxide thin films with nanometer precision, organic-inorganic nano-graded composites, and to the molecular imprinting technique for molecular recognition. We also describe here recent development of polymerization-induced adsorption, which is a novel deposition technique of organic polymers at nanometer scale. English Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Besearch on PriorityArea, No. 274 The Ministry of Education, Science, Sports and Culture of Japan Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Research on Priority Area, No. 274 5 1999-03-01 53-56 アルミニウム－金属間物傾斜機能材料への半溶融物形成の応用 Application of Semi-Melt Forming to Aluminum-Intermetallics Functionally Graded Material 福井泰好、岡田裕、熊澤典良鹿児島大学　890-0065　鹿児島市郡元1-21-40 Y. FUKUI, H. OKADA and N. KUMAZAWAKagoshima University, 1-21-40, Korimoto, Kagoshima 890-0065, Japan INTRODUCTION The centrifugal method is one of the techniques to manufacture functionally graded material (FGM). Authors have constructed an FGM manufacturing system and studied the properties of aluminum base FGMs. Considering the aluminum base binary phase diagrams, e.g., Al-Ni and Al-Fe systems, difference between the densities in melt, aluminum and intermetallics, makes a graded composition of intermetallics in one specific direction after solidification. The strength of aluminum base FGM tested heretofore was not very high because of the presence of large intermetallic particles due to a slow cooling rate in a vacuum chamber. If the particles having graded distribution were fine enough to obtain good mechanical properties, aluminum-intermetallics FGM can be used as a structural and/or component material. One possible way to overcome this problem is in the application of hot working and heat treatment refining the sizes of intermetallic particles. However, it was not successful because of the low resistance of intermetallics to the brittle fracture even in the case of hot working temperature. The present FGMs are recycled over and over again. We have experienced that the FGM scraps are initially beaded with molten eutectic aluminum alloy and then melted gradually into an alloy liquid. It took a long time to achieve a full dissolution of intermetallics in a small crucible furnace. If we processed the FGMs under the semi-melt conditions, it may be possible to obtain a near-net shape FGM product with fine intermetallic particles. The aim of the present study is a confirmation of the idea to obtain a FGM product having a graded distribution of fine intermetallics. The semi-solid process considering here is assumed a kind of thixoforming where the operation is done in the solid-liquid coexisting temperature. English Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Besearch on PriorityArea, No. 274 The Ministry of Education, Science, Sports and Culture of Japan Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Research on Priority Area, No. 274 5 1999-03-01 57-60 TiAl合金に対する耐酸化性皮膜の傾斜機能化 Functionally Graded Oxidation-Resistant Coating for TiAl Alloys 間渕博 津田大大阪府立大学　工学部　材料工学科　599-8531　大阪府堺市学園町１－１ Hiroshi Mabuchi and Hiroshi TsudaDepartment of Metallurgy and Materials Science, College of Engineering, Osaka Prefecture University, 1-1 Gakuen-cho, Sakai, Osaka 599-8531, Japan Gamma titanium aluminides ((gamma)-TiAl alloys), having an L10-type structure, are candidate materials for use in future gas turbine aero-engines and automotive engines because of their low density, high specific strength and high stiffness(1)(2). In air, however, it is well known that the titanium aluminide oxidizes at a more rapid rate at temperatures above 1123 K. Therefore, coatings for the TiAl alloy are essential to high temperature oxidation resistance. The purpose of this study is to apply L12 alloy coatings to the TiAl alloy by pack cementation techniques, and to establish the functionally graded layer for oxidation-resistance coatings. To improve the oxidation resistance of (gamma)-TiAl alloys, Ti-43Al-5Cr(L10) alloy substrates were coated with the L12-(Al,Cr)3Ti layer by pack cementation. Coatings were formed by immersing the substrate in a mixture consisting typically of 90%Ti-61Al-14Cr(L12) alloy powders and 10%Al2O3 powders, without activators, e.g., NH4Cl powders, and then heating in an alumina boat under a vacuum of ~l0**-4 Pa for 1~ 96 h at 1423 K. The coating layer for (gamma)-TiAl alloys was effectively formed by surface diffusion and bulk diffusion of aluminum, titanium and chromium from pack alloy powders, and consisted of the two diffusion layers ; outer L12-phase layer and inner L10-phase layer. In these layers, the graded alloy composition for the oxidation resistant coating was successfully established. The coated alloy showed a remarkable improvement in the oxidation over the uncoated TiAl alloys. English Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Besearch on PriorityArea, No. 274 The Ministry of Education, Science, Sports and Culture of Japan Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Research on Priority Area, No. 274 5 1999-03-01 61-65 傾斜機能誘電体基板 A Functionally Graded Substrate for Dielectrics 西田俊彦、Giuseppe PEZZOTTI、塩野剛司京都工芸繊維大学　物質工学科　606-8585　京都府京都市左京区松ケ崎 Toshihiko Nishida, Giuseppe Pezzotti and Takeshi ShionoDepartment of Chemistry and Materials Technology, Kyoto Institute of Technology, Matsugasaki, Sakyo-ku, Kyoto, 606-8585, Japan INTRODUCTION In the previous report1), we showed the dielectric substrate with functionally graded dielectric constant allows the minimization of the signal loss at high frequency. In Table 1, typical processes for the preparation of functionally graded material and the correspondent thickness of the graded layers are summarized2), which were followed in this project supported by Ministry of Education Grants. When using usual powder metallurgy methods, the thickness of the graded layers ranges from 1 mm up to a few cm order. Approaches involving molecular or atomic scale processes may allow to reduce the thickness of graded phase to a nm order. In materials for electronic substrates, a suitable process for producing graded structures with individual thickness in the range from a few hundreds micrometer up to 1 mm are not easily available. In this research project, a typical barium titanate dielectric body is attentioned. The dielectric constant can be controlled by adding same aids as a depresser or sifter. From the surface of the porous body of barium titanate, an alkoxide solution as additive is infiltrated. By heat-treatment after such an infiltration processing, densification is achieved of a body with a functionally graded dielectric constant. SUMMARY A barium titanate dielectric material, with a dielectric constant graded structure exploited within the range between a few hundreds micron and one millimeter, has been successfully produced by using a liquid infiltration method into the porous body. The initial porosity of the body can be varied to act on the amount of additive infiltrated. Exploiting the stability of the infiltrated additive, it is also possible to control the gradient function within the barium titanate body. In this research it is shown that the preparation on mass production of dielectric substrates can be pursued according to a simple and low cost process. The infiltration method in a porous body is used as an intermediate step between basic sintering steps of ceramics (powder preparation, molding and sintering) to obtain a simple process for producing functionally graded structures of electronic ceramics. English Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Besearch on PriorityArea, No. 274 The Ministry of Education, Science, Sports and Culture of Japan Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Research on Priority Area, No. 274 5 1999-03-01 65-68 改良型Bi4Ti3O12セラミックスの調整と焦電特性 Preparation and Pyroelectric Properties of Modified Bi4Ti3012 Ceramics 一ノ瀬昇, Y. Takahashi早稲田大学　理工学部　169-8555　東京都新宿区大久保３丁目４－１ N. Ichinose and Y. TakahashiSchool of Science and Enginnering, Waseda University, 3-4-1, Ohokubo, Shinjyuku-ku Tokyo 169-8555, Japan INTRODUCTION Bithumuth layer-structured ferroelectrics such as Bi4Ti3O12 (BIT), PbBi2Nb2O9 (PBN) and Na0.5Bi4.5Ti4O15 (NBT) are characterized1) 2) by (1) lower (epsilon)(gamma) (100-200), (2) lower tan (delta) ( < 0.005 ) and higher Curie temperature Tc (300-900deg.C). These properties are useful for piezoelectric and pyroelectric materials. In this paper, the pyroelectric properties of Bi4Ti3O12 based ceramics have been investigated from the viewpoint of their application to pyro-sensor materials. Here, BIT ceramics are added with Nb2O5 for improving the electrical properties. Futhermore, lanthanum modified BIT ceramics with compositions of (Bi4-xLax)Ti3O12 + 1.0 mol% of Nb2O5 (x = 0 ~ 1.10) are also studied for obtaining higher pyroelectric coefficient in the wide temperature range because Tc of this system is decreasing with increase of the La2O3. The compositionally graded materials in the (Bi4-xLax)Ti3O12 + 1.0 mol% Nb2O5 system are expected to improve pyroelectric properties. English Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Besearch on PriorityArea, No. 274 The Ministry of Education, Science, Sports and Culture of Japan Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Research on Priority Area, No. 274 5 1999-03-01 69-72 傾斜機能圧電アクチュエーター Functionally Graded Piezoelectric Actuators 谷順二、T.Morita、菱進浩東北大学　流体科学研究所 　980-8577　宮城県仙台市青葉区片平２丁目１－１ J.Tani,T.Morita,J.QiuInstitute of Fluid Science,Tohoku University, 2- 1- 1,Katahira, Aoba-ku,Sendai,Miyagi 980-8577, Japan Many studies have been carried out on the development and application of piezoelectric/electrostritive actuators. The typical piezoelectric actuators with large displacement include unimorph actuators and bimorph actuators. These actuators are manufactured by bonding a piezoelectric layer and a metal shim layer or two piezoelectric layers together. Due to the stress concentration and physical weakness on the bonding interface of the two layers, cracks and delamination can easily be induced during actuation. Hence, these actuators are not suitable for applications requiring high reliability. To solve this problem, a new type of actuator called RAINBOW has been proposed2). RAINBOW actuators have the same structure as unimorph actuators except that the shim layer is obtained by chemically reducing the piezoelectric material on one side of an actuator instead of bonding a metal layer. Since the reduced layer and the unreduced piezoelectric layer are chemically integrated, the interface has higher strength and delamination on the interface can be avoided. However, the chemical reduction process is performed at high temperature, and the reduced layer and unreduced layer have different heat expansion factors. Therefore thermal stress are induced in the actuator after cooling down. The thermal stress becomes the main factor of fracture of RAINBOW actuators since in some region of the piezoelectric layer the thermal stress is extensional. A new type of bending actuator with functionally graded composition of a piezoelectric material and a dielectric material in the thickness direction was proposed and numerical simulation was performed on the performance analysis of the actuators in the preceding academic year. In this academic year three types of functionally graded piezoelectric actuators were manufactured and were measured in the properties. The high performance of FGM piezoelectric actuators has been confirmed from the result of this study. English Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Besearch on PriorityArea, No. 274 The Ministry of Education, Science, Sports and Culture of Japan Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Research on Priority Area, No. 274 5 1999-03-01 73-76 傾斜機能磁性薄膜 Functionally Graded Magnetic Thin Films 本間敬之、Y.Kita, 逢坂哲彌早稲田大学　理工学部　応用化学科　169-8555　東京都新宿区大久保３丁目４－１ T. Homma, Y. Kita, and T. OsakaDepartment of Applied Chemistry, School of Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku-ku, Tokyo 169-8555, Japan The areal density of information stored in magnetic disk drives has been advanced rapidly and the recording media which can achieve further higher density are required. We have developed various media suitable for high-density magnetic recording using electroless deposition techniques. The results of our previous studies revealed that "double-layered" media consisting of the films with different magnetic properties exhibited excellent recording characteristics, suggesting that it is significant to control the properties precisely toward the direction of film thickness, in accordance with the head field distribution. Thus, it is expected that the film with graded magnetic properties in accordance with the head field gradient could achieve further higher performance. Recently we have achieved such a gradient control of magnetic properties by using electroless CoNiP films [5,6]. Based on this result, we further investigated the gradient control of the magnetic properties, such as coercivity, Hc, in electroless-deposited thin films. In the present work, cross-sectional microstructure of the films was examined, and film deposition process was electrochemically analyzed in order to clarify the origin of graded properties. Moreover, magnetic distribution of the head field gradient was theoretically calculated for designing the gradient-controlled magnetic recording media. Cross-sectional TEM and RHEED analyses clarified that graded control of magnetic properties is due to the graded conditions in crystalline properties. The analysis of the film deposition process revealed that the rotational speed of substrates effects mainly on the Co deposition and oxidation of the reducing agent. In addition, the calculation of the magnetic distribution carried out the magnetic force of the recording head along the medium thickness, and the magnetic properties of the recording media could design from the results. It was clarified that could make the functionally graded magnetic recording media suitable for the design. English Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Besearch on PriorityArea, No. 274 The Ministry of Education, Science, Sports and Culture of Japan Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Research on Priority Area, No. 274 5 1999-03-01 77-80 高周波応用のための傾斜機能磁気材料 Functionally Graded Magnetic Materials for High Frequency Applications 平塚信之、山崎武志、小林秀彦、柿崎浩一埼玉大学　大学院理工学研究科　338-8570　浦和市下大久保255 N. Hiratsuka, T. Yamazaki, H. Kobayashi, K. KakizakiGraduate School of Science and Engineering, Saitama University, 255 Shimo-Ohkubo,Urawa,Saitama 338-8570, Japan INTRODUCTION Core materials for actuators and magnetic heads need to have high saturation magnetic flux density (Bs) and initial permeability ((mu)i) for minutuarizing apparatus and high speed informative communication. Moreover magnetic materials require higher (mu)i in high frequency of giga hertz order in high-grade informative society of late years. However relation between resonance frequency (fr) and initial permeability ((mu)i) can be represented as follows : equation(1)where (mu)0 = permeability of vacuum (12.566 x 10**-7[H/m]), (gamma)= gyro-magnetic constant (1.1051 x 10**5[m/Asec]), and Is = saturation magnetization. It is well-known that the product of fr and (mu)i is constant from the equation. Thus single metal or oxide magnetic material cannot satisfy these requirements simultaneously. Metal magnetic materials have merits of high Bs and high (mu)i. Oxide magnetic materials (ferrite) have a merit of high resistance (R) . A magnetic material which has the above-mentioned merits is expected as new high frequency applications, when multi-layered structure of magnetic metal and oxide materials is realized. When metal and oxide magnetic materials were simply laminated, they had cracked and spalled at molding or sintering process. We therefore designed to have the magnetic characteristics of metal (Fe-Ni alloy) and oxide (ferrite) by assorting both of them. "Ferrite/Metal functionally graded materials" with compositional gradient was fabricated for preventing cracks and spalling of the bulk. Besides frequency dependence of initial permeability of the samples were investigated. English Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Besearch on PriorityArea, No. 274 The Ministry of Education, Science, Sports and Culture of Japan Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Research on Priority Area, No. 274 5 1999-03-01 81-84 固体酸化物燃料電池のための傾斜機能電極の製造と特性評価 Fabrication and Characterization of Functionally Graded Electrode for Solid Oxide Fuel Cells 湯上浩雄　内藤均東北大学　大学院工学研究科　980-8579　宮城県仙台市青葉区荒巻字青葉１－１ Hiroo Yugami, Hitoshi Naito*Graduate School of Engineering, Tohoku University, Aoba O1, Aramaki, Aoba-ku, Sendai, Miyagi 980-8579, Japan INTRODUCTION A mixed electronic and ionic conductor is preferred for an electrode material for Solid Oxide Fuel Cells (SOFCs). Since YSZ is used as electrolyte for SOFC, good adherence can be achieved by using a zirconia-based mixed conductor as an electrode. From this point, Worrell et al. investigated a single component solid oxide fuel cell, which is composed of YSZ electrolyte and Ti-and Tb-doped YSZ electrodes [1]. To improve electronic conductivity in zirconia-based mixed conductor, higher concentration of dopant, which promotes electronic conduction, is required. However, when a dopant concentration increases, a large difference in mechanical properties, such as thermal expansion and lattice parameter, between electrolyte and electrode occurs. To overcome this problem, we applied functionally graded materials (FGMs) to the electrode. The dopant concentration in the electrode is gradually changed from gas/electrode interface (high dopant concentration) to electrode/electrolyte interface (low concentration) . The concept of single component SOFC is shown in Fig. 1. Grading the dopant concentration, ionic and electronic transference numbers are expected to be graded and exhibit good mixed conduction at the former interface and good electrochemical compatibility and adherence at the latter interface . Nagata et al. demonstrated NiO-YSZ FGM and showed long-term stability of the cell [2]. The problems of homogeneous dispersion and coagulation of Ni,however, still remain. Sasaki et al. proposed several graded configurations and demonstrated some cathode materials [3]. We investigated CeO2 doped YSZ (Ce-YSZ) mixed conducting films, in which Ce concentration was varied, fabricated by laser ablation method. Ce-YSZ shows high electronic conductivity at low oxygen partial pressure, and the crystal structure is the same as YSZ. In this paper, the electrochemical properties of Ce-YSZ and performances of a single cell with FGM mixed conducting anode are reported. English Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Besearch on PriorityArea, No. 274 The Ministry of Education, Science, Sports and Culture of Japan Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Research on Priority Area, No. 274 5 1999-03-01 85-88 フェロ・フェリ分子磁性体の傾斜組成で構成される革新的磁気薄膜 The novel types of magnetic thin films composed of a gradient composition between ferromagnetic and ferrimagnetic components: 大越慎一東京大学　先端科学技術研究センター　153-8904　東京都目黒区駒場４丁目６－１ Shin-ichi OhkoshiResearch Center for Advanced Science and Technology, The University of Tokyo, 4-6-1 Komaba, Meguro-ku,Tokyo153-8904, Japan INTRODUCTION In general, materials which exhibit strong bulk magnetization can be roughly divided into two categories, ferromagnets (parallel spin ordering) and ferrimagnets (antiparallel ordering of unlike spins). Our objective in the present work is to gain understanding of a new type of magnet, the graded magnetic thin film, which has both ferromagnetic and ferrimagnetic character. For this attempt, we have chosen Prussian blue analogs as target materials. These materials comprise one of the more attractive classes of molecule-based magnets,1-3 some with high critical temperatures (Tc). Recently, we have prepared the new classes of magnetic thin films composed of (FeIIxCrII1-x)1.5[CrIII(CN)6]zH2O. Their colors could be controlled by controlling the compositional factor x ( =FeII / (FeII+CrII) ), e.g., colorless (x= 0), violet (x= 0.20), red (x= 0.42) and orange (x= 1). Moreover, their magnetic properties were also rich in variety depending on x, e.g., disappearance of saturation magnetization, compensation temperatures, and anomalous coercive fields. Using this system, we designed the novel types of magnetic thin films composed of a gradient composition between ferromagnetic and ferrimagnetic components. English Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Besearch on PriorityArea, No. 274 The Ministry of Education, Science, Sports and Culture of Japan Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Research on Priority Area, No. 274 5 1999-03-01 89-92 レーザーMBE法による強誘電体／強磁性体傾斜機能材料の創成 Creation of Functionally Graded Ferromagnetic/Ferroelectric Materials by Laser MBE Technique 田畑仁、川合知二大阪大学　産業科学研究所　567-0047　大阪府茨木市美穂が丘8－1 Hitoshi Tabata and Tomoji KawaiInstitute of Scientific and Industrial Research, Osaka University 8-1 Mihogaoka, Ibaraki, Osaka 567-0047, Japan INTRODUCTION Transition metal oxides have a lot of interesting potential for the functional electric devices. Early transition metal oxides, such as PZT and BaTiO3, show ferroelectric and dielectric properties corresponding to their band insulative characters. They are also expected to large piezoelectric and electro-strictive effect. Magnetic character is interesting on the middle transition metal oxide group (Mn, Fe, Co etc.) with increasing the number of spins. Until now, the materials researches tend to be performed independently on magnetic and ferroelectric field. We have constructed hetero-structures with combination of ferroelectric- ferromagnetic materials by a laser MBE technique. An ideal hetero-epitaxy can be obtained owing to the similar lattice parameter of ferroelectric BaTiO3, PZT and antiferro- or ferro-magnetic (La, Sr)MnO3, LaMnO3, LaCrO3 and LaFeO3. New spin order and spin frustration are expected competing with ferromagnetism of self-doped LaMnO3 and anti-ferromagnetism of LaFeO3 on SrTiO3(111) and (100) surface. Spin glass phase transition (casp shape in magnetization vs. temperature measurements) is observed actually at around 50K in the 1/1 - 3/3 FGMs. In case of LaMnO3/LaFeO3 FGMs on (111) surface, on the other hand, spin glass does not occur. Furthermore, Curie temperatures maintain almost same value from 1/1 to 9/9 periodic sequences. This behavior is quite different from non-doped LaFeO3/LaCrO3 FGMs. English Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Besearch on PriorityArea, No. 274 The Ministry of Education, Science, Sports and Culture of Japan Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Research on Priority Area, No. 274 5 1999-03-01 93-96 組成傾斜K(Nb,Ta)O3結晶中の誘電特性の相間活動と分布 Phase Boundary Movement and Distribution of Dielectric Properties in Composition-Graded K(Nb,Ta)O3 Crystals 山根久典、島田昌彦東北大学　素材工学研究所 　980-8577　宮城県仙台市青葉区片平２丁目１－１ H. Yamane and M. ShimadaInstitute for Advanced Materials Processing, Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577, Japan INTRODUCTION Curie temperatures of some perovskite-type ferroelectrics forming continuous solid solutions can be shifted by composition of the elements in the substitutional site [1]. High dielectric constants are usually obtained around the Curie temperatures. We have attempted to fabricate high-dielectric materials with temperature dependence of the dielectric constant being controlled by changing the composition of solid solutions gradually. In the previous studies, we have prepared composition graded crystals of KNbO3 - KTaO3 perovskite-type ferroelectric solid solutions by non-equilibrium cooling of the melts [2-4]. Ta content analyzed was rich in the core of all crystals. The composition of Nb increased gradually in the regions from the core to the outer part of the crystals. The dielectric properties reflected the composition gradient which depended on the cooling process of the crysal growth. The crystals obtained with a higher cooling rate exhibited smaller temperature dependence of the dielectric constant. Zonal structures, in which a cubic phase was surrounded by a tetragonal phase and the tetragonal phase was surrounded by an orthorhombic phase, were observed in the crystals with a polarized optical microscope. Because of the composition gradient, the boundarys between the phases should move in the crystals with temperature increase or decrease. The dielectric constant should be higher in the boundary area where the cubic to tetragonal phase transition occurs. However, the movement of the phase boundary and the distribution of dielectric properties have not been clarified before. In the present paper, we report the results of high-temperature microscope observation on the movement of the phase boundary in the crystals. The distribution of dielectric properties were characterized by scanning nonlinear dielectric microscopy. English Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Besearch on PriorityArea, No. 274 The Ministry of Education, Science, Sports and Culture of Japan Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Research on Priority Area, No. 274 5 1999-03-01 97-100 固溶体の１直列とそれらの誘電特性の形成による傾斜機能BaTiO3セラミックスの調整 Preparation of Functionally Gradient BaTiO3-Based Ceramics by Forming a Series of Solid Solutions and Its Dielectric Property T. Ota名古屋工業大学　セラミック研究施設　507-0071　岐阜県多治見市 T. OtaCRL, Nagoya Institute of Technology, Tajimi 507-0071, Japan BaTiO3 (BT) is characterized by a high electric permittivity which assumes maximum at a Curie temperature (Tc) of 120 deg.C. However, a sharp peak in the profile of (epsilon) vs T at Tc is undesirable for application as a capacitor material. Practically, the peak is shifted to lower temperatures by additives such as SrTiO3 (ST) or BaZrO3, and depressed by additives such as MgTiO3 or CaTiO3. Besides, the peak is also depressed and broadened by mixing two phases with different Tc. The two-phase mixture gives a lower variation of permittivity with temperature than single-phase materials. This is due to the paraelectric/ferroelectric phase transition occuring at different temperatures for different regions of the sample. Consequently, a distribution of different transition temperatures in the polyphase mixture should yield an overall broadened peak in the profile of (epsilon) vs T. Mixtures of ideal dielectrics can be most simply considered on the basis of layer materials with the layers either horizontal or vertical to the applied field.When layers are horizontal to the electrodes, the structure corresponds to capacitive elements in series, and the inverse capacitances are additive. In contrast, when layers are arranged vertical to the electrodes, the structure corresponds to capacitive elements in parallel, and the capacitances are additive. In this study, the polyphase mixtures with the layered stucture were prepared by laminating Ba1-xSrxTiO3(BST) ceramics with different compositions. That is to say, gradient BST ceramics, which had a continuously varying composition from one surface to the other in a single body, were prepared. It is expected that the gradient BST ceramics would exhibit a linear characteristics of permittivity with temperature . However, functionally gradient materials (FGM) have hardly been investigated with respect to dielectric property. English Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Besearch on PriorityArea, No. 274 The Ministry of Education, Science, Sports and Culture of Japan Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Research on Priority Area, No. 274 5 1999-03-01 101-104 窒素濃縮傾斜金属窒化物多層中の混成機能 Hybridized Functionality in Nitrogen Concentration Graded Metal Nitride Multilayer 吉川信一大阪大学　産業科学研究所　567-0047　大阪府茨木市美穂が丘8－1 S. KikkawaISIR, Osaka University, Mihogaoka 8-1, Ibaraki, Osaka 567-0047, Japan INTRODUCTION We have been investigated the structure and properties of both multilayered and granular magnetic thin films in either Fe-Al (or Si)-N ternary system prepared using rf-sputter deposition in the present FGM project [1-3 etc.]. Giant magnetization component was present in the Fe/AlN multilayered thin films [3 etc.]. A new research project has been started in this academic year to hybridize the giant magnetism with electrical conductivity or with superconductivity. It is still in a preliminary stage in sample preparation. This manuscript describes very interesting experimental results on the Fe/AlN multilayers obtained in this year. The reaction mechanism to obtain the interface iron nitrides with the giant magnetization could be clearly estimated from both their temperature dependence of magnetization in high temperature and Al K-XAFS. English Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Besearch on PriorityArea, No. 274 The Ministry of Education, Science, Sports and Culture of Japan Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Research on Priority Area, No. 274 5 1999-03-01 105-108 傾斜磁気材料のための2次元磁気特性の局在化測定 Localized Measurement of Two-dimensional Magnetic Properties for Gradient Magnetic Materials M. Enokizono, T. Todaka and Y. Tsuchida大分大学　工学部電気電子工学科　870-1192　大分県大分市大字旦野原７００ M. Enokizono, T. Todaka and Y. TsuchidaDepartment of Electrical and Electronic Engineering, Faculty of Engineering, Oita University, 700 Dannoharu, Oita 87-1 192, Japan INTRODUCTION It was found that the local distributions of magnetic field strength H-vector and magnetic flux density B-vector are not uniform and pararell in grain-oriented silicon steel sheet [1][2]. These phenomena are closely related to not only the magnetic properties, but also the local loss distributions. Thus it is necessary to measure the local B and H as vector valuables with those vector relations in constructed cores. We have measured the two-dimensional magnetic properties in a grain-oriented sheet by using a small sensor which can be applied to the local measurement [3]. The result shows the relationship between the magnetic properties, the grain structure and magnetic domain structure in the specimen. English Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Besearch on PriorityArea, No. 274 The Ministry of Education, Science, Sports and Culture of Japan Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Research on Priority Area, No. 274 5 1999-03-01 109-112 低次元蛍光体の傾斜機能の研究 Study on graded function of low-dimensional phosphor 遠藤忠東北大学　大学院工学研究科　980-8579　宮城県仙台市青葉区荒巻字青葉 Tadashi EndoGraduate school of Engineering, Tohoku University, Aoba, Aoba-ku, Sendai, Miyagi 980-8579, Japan INTRODUCTION Recently, we have found that the substitutional solid solution was introduced into self-activated phosphor ZnGa2O4 to make changes in the bandgap Eg and the peak position of luminescent spectra over the whole composition range, so that the origin of the luminescence could be fully explained by the donor-acceptor recombination in a conventional band model. Accordingly, when the incident beams reached and penetrated enough the solid solution, especially designed "graded-composition", the white-luminescence was generated. Practically, the "rainbow-coloured emission" should be observed according to the profile of beam trajectorie within a very short interval. On the other hand, the white-luminescence was made basically with the overlapping of the phosphors emitted in blue, green and red colours. To achieve the proper combination of colours, it was necessary enough understand the color mixture theory of colourimetry. Accordingly, a single phosphor with various activator was required to realize such colour blend, because the excitation of phosphor was effectively performed at the same wavelength. In this present work, we try to obtain some of the information to prepare new phophors with better luminescence quantum yield in the system Ln-Zn-Ga-O (Ln; rare earth metals). With the rare earth-activated phosphors which gave the intense and narrow emission under a 254nm excitation (low pressure mercury vaper lamps), the generation of white-luminescence was systematically examined. Succesively, it was expected that the white colour was uniformly distributed throughout the phosphor (display) plate. It was clear that the formation of thin films was much convenient to improve the exciattion and emission efficiencies of phosphors. Some functions of films such as graded-reflective-index fiber were demonstrated. English Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Besearch on PriorityArea, No. 274 The Ministry of Education, Science, Sports and Culture of Japan Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Research on Priority Area, No. 274 5 1999-03-01 113-116 多機能傾斜熱電材料の熱電特性制御メカニズム Thermoelectric Properties Control Mechanism For Multi - Functionally Graded Thermoelectric Material 梶川武信湘南工科大学　電気工学科　神奈川県藤沢市辻堂西海岸1-1-25 T. Kajikawa Shonan lhstitute of Technology, Department of Electrical Engineering 1-1-25 Tsujido-nishikaigan Fujisawa. Kanagawa, Japan Introduction Thermoelectric energy conversion is the simplest way to convert heat to electricity. It is recognized that thermoelectrics can play an important role to the efficient utilization of many dispersed energy sources such as rejected thermal energy sources from the automobiles and combustion heat of municipal solid waste [1]. It is urged to develop an efficient thermoelectric element, for which energy conversion efficiency is determined with the temperatures Th,Tc at the top and the bottom of the thermoelectric element and thermoelectric performance such as the thermoelectric Figure of Merit averaged along the overall temperature range. The performance of the conventional thermoelectric elements is sensitive to the temperature. In general the peculiar temperature range is narrow [2]. In order to obtain the broad thermoelectric characteristics on temperature the concept of Functionally Graded Material for thermoelectric materials has been developed [3,4]. The characteristics of the sintered thermoelectric materials are determined with the structural factors such as material composition,their solid solutions,grain size and grain boundary condition , and crystalline factors such as crystalline structure,band structure and phase condition These factors affect the Seeback coefficient, electrical resistivity and thermal conductivity in complexity. Moreover, for the sintered and impurity doped thermoelectric element the dependence of these factors on the performance is different from that for a single crystal and melt-grown element. The research objectives are to investigate the dependence of the sintering and doping conditions on the thermoelectric properties and to clarify the possibility of continuously, functionally graded thermoelectric bulk element due to the zone traveling sintering method. English Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Besearch on PriorityArea, No. 274 The Ministry of Education, Science, Sports and Culture of Japan Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Research on Priority Area, No. 274 5 1999-03-01 117-120 プラズマ処理粉末を用いて調整したミクロ傾斜機能構造を有する熱電気セラミックス Thermoelectric Ceramics with Functionally Graded Microstructures Prepared by Using Plasma-Treated Powder 小柳剛、岸本堅剛山口大学　大学院理工学研究科　755-8611　山口県宇部市常盤台２５５７＊山口大学　工学部　755-8611　山口県宇部市常盤台２５５７ T. Koyanagi and K. Kishimoto*Graduate School of Science and Engineering, Yamaguchi University, 2557, Tokiwadai, Ube 755, Japan *Faculty of Engineering, Yamaguchi University, 2557, Tokiwadai, Ube 755, Japan INTRODUCTION There is a possibility of improvement of the thermoelectric performance in the thermoelectric sintered materials of which microstructures are controlled since not only a decrease in the electric resistivity but also a decrease in the thermal conductivity and an increase in the Seebeck coefficient can be expected In this study, we have investigated the control of microstructures in thermoelectric sintered materials by the plasma powder treatment technique1,2) in order to improve their thermoelectric performance. Functionally graded structures can be formed at grain boundaries of sintered materials by sintering their raw powders of which surfaces are modified in reactive plasmas. These sintered materials are regarded as a kind of the functionally graded materials (micro-FGM). In this year, we have studied the CoSb3 thermoelectric sintered materials. CoSb3 is known as a promising thermoelectric material since its hole mobility is extremely high (~2000cm2/Vs at room temperature) for p-type and its electron mass is considerably heavy (~3m0) for n-type3,4). However, CoSb3 has too large values of the thermal conductivity to be applied to thermoelectric devices. We have tried to lower the thermal conductivity of CoSb3 by forming oxide layers at grain boundaries of its sintered materials, at which phonons are effectively scattered. Further, we can expect the CoSb3 sintered materials, in which a potential barrier due to the oxide layers is present at the grain boundaries, to exhibit large Seebeck coefficients by the energy filtering effect5-8). In order to obtain the CoSb3 sintered materials with such a structure, we have treated the CoSb3 raw powder in an O2- plasma9-12). It is difficult to reveal the energy filtering effect on the Seebeck coefficient in sintered materials since carriers are randomly transported over grain boundaries. In films, the columnar structure can be obtained on substrates and is suitable for study on the energy filtering effect. We have also investigated the thermoelectric properties of PbTe films, which were prepared by the rf sputtering, in order to clarify the energy filtering effect on the thermoelectric properties13-16). English Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Besearch on PriorityArea, No. 274 The Ministry of Education, Science, Sports and Culture of Japan Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Research on Priority Area, No. 274 5 1999-03-01 121-124 傾斜機能CuInSe2薄膜太陽電池 Functionally Graded CuInSe2 Thin Film Solar Cells 伊藤太一郎、小見崇、伊崎昌伸＊、芦田淳大阪府立大学　工学部　599-8531　大阪府堺市＊大阪市立工業研究所　536-8553　大阪府大阪市城東区森之宮 Taichiro Ito, Takashi Omi, Masanobu lzaki* and Atsushi AshidaCollege of Engineering, Osaka Prefecture University, Sakai, Osaka 599-8531, Japan * Osaka Municipal Tech. Research Institute, Morinomiya, Osaka 536-8553, Japan CuInSe2 has attracted keen attention to apply to advanced high efficiency polycrystalline thin film solar cells. It is the most desirable that CuInSe2 thin film as an optical absorption layer in a solar cell has (112) preferred orientation. Because, it is very remunerative terms for fabricating heterojunction with a wide band gap semiconductor thin film as window layer. Furthermore, a smooth surface of CuInSe2 thin film is also convenient to fabricate the heterojunction. On the other hand, transparent and conductive zinc oxide (ZnO) film has recently attracted increasing attention as components in a CuInSe2 photovoltaic device. ZnO films are prepared by several techniques, such as magnetron sputtering, chemical vapor deposition, and molecular beam epitaxy. We have devised new preparation technique, that is electrochemical preparation, which presents several advantages over above mentioned techniques; (i) the thickness and morphology of films can be controlled by electrochemical parameters, (ii) relatively uniform film can be obtained on substrates of complex shape, (iii) the deposition rate is high, and (iv) the equipment is not expensive. We have prepared a 1-micrometer-thick ZnO film with changing electrical resistivity from 1x10**6 to 7.8x10**-3(ohm)cm in the thickness direction by a chemical deposition of thin ZnO film on a non-conductive substrate in a simple aqueous solution and by the electrochemical growth in the same solution. The ZnO film, however, showed poor transparency, because of the large surface irregularity and the existence of defects such as pore. Peulon pointed out that the high density nucleation on a substrate was indispensable to obtain a dense and defect-free ZnO film. This paper deals a preparation of transparent and conductive ZnO film by an enhancement of nucleation density on a non-conductive substrate. English Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Besearch on PriorityArea, No. 274 The Ministry of Education, Science, Sports and Culture of Japan Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Research on Priority Area, No. 274 5 1999-03-01 125-128 光学的傾斜機能ポリマーの分子設計と特性評価 Design and Characterization of Functionally Graded Photonics Polymer Materials 小池康博・二瓶栄輔・石榑崇明慶應義塾大学　理工学部物理情報工学科　223-8522　神奈川県横浜市港北区日吉3-14-1　／神奈川科学技術アカデミー　236　横浜市金沢区福浦 1-1-1 Yasuhiro Koike, Eisuke Nihei, and Takaaki IshigureFaculty of Science and Technology, Keio University, 3-14-1, Hiyoshi, Kohoku-ku, Yokohama 223 Japan / Kanagawa Academy of Science and Technology, 1-1-1, Fukuura, Kanazawa-ku, Yokohama 236 Japan Considerable research activity lately has been focused on the development of the optical component and devices that have the capability to support the high-speed telecommunication. Silica base single mode optical fiber has been widely utilized in the long distance trunk area for the order of giga bit per second transmission because of its high bandwidth and transparency. However, realization of all optical networks by the single mode fiber requires many breakthroughs in the total system cost. Because of the small core size such as 5 to 10 micrometers, accurate alignment is necessary in the light coupling to the fiber and the connection of fibers, which increases the total system cost including fiber connectors, transceiver, packaging, and installation, etc. On the other hand, use of the silica base multimode fiber is a recent trend in the field of local area network (LAN) and interconnection, because the large core diameter of the multimode fiber such as 50 micrometers increases the tolerance of misalignment in the fiber connection compared to that of single mode fiber. However, in the case of the multimode fiber, the accurate connection by using ferrule is required if a coherent light source such as vertical cavity surface emitting laser is used because of the serious modal noise problem. We have proposed a large-core, high-bandwidth, and low-loss GI POF1,2. Large core of the GI POF enables the use of inexpensive plastic connector which is prepared by the injection molding, eliminating the problem of the modal noise. In this paper, recent result of the modal analysis in the GI POF and the design of the refractive index gradient based on the analysis are described. English Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Besearch on PriorityArea, No. 274 The Ministry of Education, Science, Sports and Culture of Japan Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Research on Priority Area, No. 274 5 1999-03-01 129-132 光学的線形・非線形傾斜機能型ガラスセラミックスの研究 Study of Optically Linear/Nonlinear Functional Graded Glass-Ceramics 小松高行、紅野安彦、 and Y.Takahashi長岡技術科学大学　化学系　940-2188　新潟県長岡市上富岡町1603-1 T. Komatsu, Y Benino and Y.TakahashiDepartment of Chemistry, Nagaoka University of Technology, 1603-1 Kamitomioka-cho, Nagaoka 940-2188, Japan Recently, we succeeded in fabricating transparent TeO2-based glass-ceramics showing a second harmonic generation (SHG) such as 15K2O-15Nb2O5-70TeO2 and proposed optically linear/nonlinear functional graded glass-ceramics. In materials with a gradient in optical nonlinearity, it is possible to convert light energy and confine light, and it is also considered that a graded structure itself is just like a device. We, further, found that the intensity of SHG at the surface of transparent glass-ceramics is much stronger than that in the interior. This means that the physical state of the surface crystalline layer is different compared with that in the interior and is graded in the direction from the surface into the interior. It is known that the surface dominant crystallization occurs frequently in glasses, and one might apply positively the surface crystallization to optical functional graded materials. In this study, we focus our attention on the optical nonlinearity (i.e. SHG) at the surface crystallization layer in transparent TeO2-based glass-ceramics. We also tried to fabricate transparent La2O3-B2O3-GeO2 glass-ceramics which generate more intense second harmonicity compared with TeO2-based glass-ceramics and at which the surface crystallization is dominant. To our best knowledge, there has been no report on the transparent La2O3-B2O3-GeO2 glass-ceramics. English Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Besearch on PriorityArea, No. 274 The Ministry of Education, Science, Sports and Culture of Japan Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Research on Priority Area, No. 274 5 1999-03-01 133-136 バンドポテンシャルのデザインによるA‐Si1‐xGex:H(F)合金のキャリヤー輸送特性のコントロール Control of Carrier Transport Properties of A-Si1-xGex:H(F) Alloy by Designing Band Potential 白井肇埼玉大学　工学部　338-8570　浦和市下大久保255 Hajime ShiraiDepartment of Functional Materials Science. Faculty of Engineering. Saitama University. 255 Shimo-Okubo. Urawa. Saitama 338-8570. Japan For further improvement of the performance of optoelectrical devices such as solar cell and sensors, it is required to design the highly photoconductive Si related films with low defect density as well as the precise control of the internal band potential. Uniformed and high rate deposition of the film has been required for large area devices. The band potential is formed by homo- and heterojunctions of semiconductors and dielectric materials to control the carrier transport properties. We have designed highly photoconductive Si based thin films by various kinds of PE-CVD techniques. The distribution of space charge was designed to control the carrier transport properties later . In order to introduce the material designs such as a compositional gradient or multilayered structures, conditions are needed as follows. First is the development of the deposition technique to fabricate highly photoconductive a-Si:H, (mu)c-Si:H and thier based materials (a-SiGe). Second is the no interuption of palsma by sequential or gradual supply of guest gases. And the third is no additional defects by changing the flow of guest molecules such as GeF4 or SiH4 in this study. The development of a novel fabrication technique using plasma technologies is required to overcome these difficulties. This report describes (a) the design and fabrication of compositional gradients using a-Si 1-xGex:H(F)(0-0.5) alloys and (b) of the Si films with the phase gradients from a-Si:H to (mu)c-Si:H toward the depth to enhance the optical absorption efficiencies of infrared region above 800nm. The carrier transport properties were systematically studied in the a-Si 1-xGex:H(F)(0-0.5) gradient structure with different potential slope (dV/dX). In addition, highly photoconductive a-Si:H(Cl) and (mu)c-Si:H(Cl) films have been designed at high deposition rate from SiH2Cl2/SiH4/H2 for application to large area electronic device such as solar cell. English Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Besearch on PriorityArea, No. 274 The Ministry of Education, Science, Sports and Culture of Japan Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Research on Priority Area, No. 274 5 1999-03-01 137-140 分子性傾斜配向を有する光伝導性液晶材料の光電特性 Photo-electric Properties of Photoconductive Liquid Crystals With Graded Molecular Alignment 半那純一　舟橋正治東京工業大学　像情報工学研究施設　226-8503　横浜市緑区長津田町 4259 Jun-ichi Hanna and Masahiro FunahashiImaging Science and Engineering Laboratory, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama, 226-8503, Japan Liquid crystals, which exhibit self-organizing behavior based on weak intermolecular interactions, are utilized for display devices owing to the optical anisotropy induced by the molecular alignment sensitive to the surface properties of the substrate and to applied electric field. Recently, we have created new functionality liquid crystals, photoconductive liquid crystals and characterized their photo-electrical properties, in which the carrier transport is significantly enhanced and mobility goes up to 10**-3-10**-2 cm2/Vs due to their closely packed molecular alignment. We have investigated to find out new photo-electric properties in molecularly graded alignment cells of these photoconductive liquid crystals. In the first phase, we concentrated ourselves on the establishing the graded molecular alignment with the photoconductive liquid crystal. The serious problem came out. That is difficulty in establishment of the graded molecular alignment. As is known that it is not feasible in smectic liquid crystals to control the graded alignment because of their viscus nature. Thus, in second phase, we created photoconductive nematic liquid crystals such as 2-(4'-cyanophenyl)-6-octylnaphthalene. This liquid crystal, however, exhibited no clear difference in terms of photoconductive behavior in various molecular alignment including the graded one. We suspected that this results was attributed to the ionic conduction in the photoconductive nematic liquid crystals. In the present study, we have clarified the conduction mechanism in the photoconductive nematic liquid crystals to find out the exit to the new results with the graded molecular alignment. Then, we tried to establish the electronic conduction in the graded molecular alignment cell with photoconductive nematic liquid crystals by polymerization of photoconductive nematic liquid crystal, in which the graded alignment is expected to be achieved because of the low viscosity of nematic phase before polymerization and the electronic conduction because of the high viscosity of polymerized nematic liquid crystal after polymerization. Photo-electrical properties of the polymerized liquid crystal cells were characterized by steady and transient photo-current measurements. English Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Besearch on PriorityArea, No. 274 The Ministry of Education, Science, Sports and Culture of Japan Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Research on Priority Area, No. 274 5 1999-03-01 141-144 傾斜機能超格子膜構造を用いたアバランシェ増幅型光導電膜 Avalanche Multiplication Photodiode Films using Functionally Graded Super lattice Structure Kazuaki Sawada and Makoto Ishida豊橋技術科学大学　工学部電子・電気工学科　441-8580　愛知県豊橋市天伯町字雲雀ケ丘１－１ Kazuaki Sawada and Makoto IshidaDepartment of Electrical and Electronic Engineering, Toyohashi University of Technology. 1-1 Hibarigaoka, Tempaku-cho, Toyohashi, Aichi 441 -8580, Japan High resolution and high sensitive image sensors have been desirable. However, as the resolution is increased, the size of the pixels will be reduced. Then, photons introduced in the photodiode area decrease. This leads a degradation of a signal to noise ratio of the image sensor. So it is necessary to realize a photo-conversion device for a next generation imaging sensor that amplify photo-signals larger than 100% quantum efficiency with noise free. The a-Si:H film can be absorbed the visible light efficiently, and it is compatible with the conventional CCD (Charge Coupled Device) process. It seems that an a-Si:H photodiode film is suitable for a photo-conversion film of the stacked type image sensor. The avalanche process is intrinsically statistical in nature so that individual carriers have different avalanche gains characterized by a distribution with an average. This causes the excess noise. To realize an avalanche photodiode with excess noise free, the concept of the staircase avalanche photodiode with linearly graded multilayer structure is accepted. On the staircase APD, the avalanche process is much less random than in a conventional APD, because each electrons are impact-ionized once at after each conduction band step and then the multiplication occurs only at a well-defined position in space. Previously, we report the characteristics of an a-Si:H/a-SiC:H staircase photodiode with linearly graded-gap multiplication regions. Fig.1 shows the energy band diagram of an a-Si: H/a-SiC: H staircase photodiode film with three band discontinuity under an extra-reverse bias. In this paper, we report a noise characteristics of the a-Si: H/a-SiC: H staircase photodiode films with one and three linearly graded-gap region. English Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Besearch on PriorityArea, No. 274 The Ministry of Education, Science, Sports and Culture of Japan Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Research on Priority Area, No. 274 5 1999-03-01 145-148 無機―有機傾斜組成複合光学マトリックスの設計と創製 Design and Preparation for Optical Matrices with the Graded Composition between Inorganic and Organic Components 町田憲一大阪大学　大学院工学研究科　565-0871　大阪府吹田市山田丘 Ken-ichi MachidaDepartment of Applied Chemistry, Faculty of Engineering, Osaka University, Yamadaoka 2-1, Suita, Osaka 565-0871, Japan INTRODUCTION The composite materials consisting of inorganic glass forming units such as silica and various organosilanes possess a possibility to form optical matrices with excellent thermal or mechanical resistivity and good molding or shaping characteristics. Furthermore, physical properties of the matrices, e.g. refractive index, are continuously changed by controlling the composition of inorganic and organic components and, as a result, a grading function is expected to be revealed by this treatment. In this study, aiming to establish the design principle and fabrication technique for the excellent optically functional materials with high transparency as well as good thermal or mechanical resistivity and good molding characteristics from the above view points, a series of ORMOSIL (organically modified silicates) composite glasses consisting of silica and organosilane units are synthesized at various compositions of the inorganic and organic components, and their glass forming regions as films are studied. In addition, waveguided luminescent solar collector (LSC) panels were prepared from quartz plates by coating them with the ORMOSIL composite glass phosphor films incorporated with [Eu(phen)2]Cl3 and the photovoltaic characteristics of silicon solar cells using such LSC panels were studied. English Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Besearch on PriorityArea, No. 274 The Ministry of Education, Science, Sports and Culture of Japan Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Research on Priority Area, No. 274 5 1999-03-01 149-152 植物の階層的傾斜構造 Hierarchical and Functionally Graded Structure of Plants 天田重庚*、深尾守昭*、K.Kurabayashi* and 小野勝道**群馬大学　376-8515　群馬県桐生市天神町1-5-1茨城大学　316-8511　茨城県日立市中成沢町４丁目１２－１ S. Amada*, M.Fukao*, K.Kurabayashi* and K.Ono***Gunma University, 1-5-1, Tenjin, Kiryu, Gunma 376-8515, Japan**Ibaraki University, 4-12-1, Naka-Narusawa, Hitachi, Ibaraki 316-8511, Japan INTRODUCTION To develop a new functional material we should learn from the natural materials, for example, plants and animals. Because those have acquired various intelligent properties for a long time to adapt to their natural environments. The typical those properties are hierarchical and functionally graded structures, which can generate a far superior function. Bamboo must be a typical one of those, which has a fiber-reinforcedand composite material. Fig.1 shows the hierarchy of bamboo based on the mechanical structure1). The 1st scale level on the bamboo shape, 2nd scale level on the fiber distribution and the 3rd scale level on the fiber-wall structure have a functionally graded structure2)3)4). This report presents a graded distribution of torsional rigidity and viscoelastic property of bamboo, which belong to the 2nd scale level, and the bamboo fiber property in the 3rd scale level. English Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Besearch on PriorityArea, No. 274 The Ministry of Education, Science, Sports and Culture of Japan Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Research on Priority Area, No. 274 5 1999-03-01 153-156 生体活性傾斜機能材料の設計 Design of Bioactive Functionally Graded Materials 小久保正、H.-M. Kim京都大学　工学研究科　京都府京都市左京区吉田 T. Kokubo and H.- M. KimFaculty of Engineering, Kyoto University, Yoshida, Sakyo-ku, Kyoto 606-8501, Japan Bioactive ceramics, that spontaneously bond to living bone, are now widely available for bone-repairing materials [1]. They bond to and integrate with living bone through a biologically active bonelike apatite layer which is formed on their surfaces in the body. None of the bioactive ceramics, however, has fracture toughness as high as that of human cortical bone. On the other hand, Ti and its alloys have been widely used as load-bearable implants, but not bioactive. Coating of bioactive ceramics onto the metals are therefore performed to provide bone-bonding ability. However, thus-coated bioactive ceramics typically contain resorbable molten phases that degrade after implantation to decrease its adhesion to surrounding bone. Recently, the present authors showed that pure Ti and Ti-6Al-4V alloy form a bioactive functionally graded structure of sodium titanate on their surfaces by a simple NaOH and subsequent heat treatments to be possessed of a bioactive functionally graded structure of sodium titanate on its surface [4]. The metals spontaneously and tightly bond to bone via the formation of bonelike apatite layer on their surfaces in the body as the bioactive ceramics do [5]. Thus-formed apatite layer has a graded interface structure against the metal to give a tight bonding between the metals and bone. In the present study, Ti-15Mo-5Zr-3Al alloy metal, the composition of which is very different from those of Ti and Ti-6Al-4V alloy, was subjected to the NaOH and heat treatments. This alloy is recently attracting much attention as an implant material, because it has not only superior mechanical strength to Ti and Ti-6Al-4V alloy but also compositional merit of being free of toxic alloying species such as V. Surface structure of the alloy after the NaOH and heat treatments and exposure to a simulated body fluid were investigated to clarify what bioactive graded surface structure forms on the alloy and how it changes in body environment. English Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Besearch on PriorityArea, No. 274 The Ministry of Education, Science, Sports and Culture of Japan Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Research on Priority Area, No. 274 5 1999-03-01 157-160 チタン素地傾斜機能インプラントとレーザ－溶接チタンの生体反応/耐火金属生体インプラント Bioresponse of Titanium-Based Functionally Graded Implants and Laser - Welded Titanium | Refractory Metal Biimplants 亘理文夫, 横山敦郎,　松野浩宣、佐相史徳、宇尾基弘、R. MIYAO、川崎貴生北海道大学　歯学部　060-8586　北海道札幌市 F.WATARI, A.YOKOYAMA, H.MATSUNO, F.SASO,M.UO, R.MIYAO, T.KAWASAKIHokkaido University School of Dentistry, Sapporo 060- 8586, JAPAN INTRODUCTION The implants are used as artificial bone in reconstruction of femur, jaw bone, teeth. The materials need to satisfy the all -round properties of biocompatibility, strength, corrosion resistance. The importance of functions necessary for each part of implant may differ from part to part. For example a dental implant lies through from the inside of jaw bone where bone affinity is important to the outside (in oral cavity) where enough strength is necessary. Implant may equip further functions in future to control various bioresponse. FGM structure would be ideal for these applications. In this study the animal implantation test was done with (1) pure metal implants of Ti, Hf, Nb, Ta, Re, Ni, (2) laser-welded Ti|Zr, Ti|Hf, Ti|V biimplants and (3) Ti/20HAP FGM implants to evaluate the biocompatibility and capability of osteogenesis of materials. The emphasis was made on the investigation of the tissue response to the gradient composition and structure of FGM. In the followings the biimplant and FGM implant are expressed, for example, as Ti|V and Ti/20HAP(20%hydroxyapatite), respectively, depending on their components and concentration. English Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Besearch on PriorityArea, No. 274 The Ministry of Education, Science, Sports and Culture of Japan Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Research on Priority Area, No. 274 5 1999-03-01 161-164 植物中のFGMsのモデリングメカニズムとデザインコンセプト(配位子ゲートチャンネルをコントロールすることによる人工モデリング) Modelling Mechanisms and Design Concepts of FGMs in Plants (Man-made modelling by controlling a ligand-gated channel) 野方文雄岐阜大学　工学部機械システム工学科　501-1193　岐阜県岐阜市柳戸１－１ Fumio NogataDepartment of Mechanical and Systems Engineering, Gifu University, 1-1 Yanagido, Gifu 501-1193, Japan Examining some biological load carriers such as plant and tree stems, animal bones and other biological hard tissues, reveals that their geometry changes under loading to match mainly stress- or strain-dependent requirements. For example, the interior structure (architecture) of a bone exhibits an optimized shape with respect to the principal stress directions and the shear stress magnitude in the body [Koch,1917]. This indicates that the bone is managed by a self-optimizing system with sensing mechanisms (e.g., piezoelectric and/or streaming potential effect of bone) that detect external mechanical stimuli to control the modelling/remodelling of the skeletal system.This has been explained to be due to an optimized mechanical design that is characterized by uniform stress distribution with no localized stress peaks [Mattech,1990]. Thus, it can be inferred that the shape and ingenious construction of biological hard tissues are the result of a continuous process of intelligent optimization. Biological structures are complicated and nonuniform, which suggests that a judicious combination of elements, materials and components of differing strength in the same structure can lead to acceptable and adequate hybrid systems whose properties are managed for specific purposes. The goals of this work are to gain an understanding of the principles of design and processes found in biological materials and to apply these findings toward developing new, intelligent, superior material/structure concepts. In the present report, we focus adaptive growth mechanisms of design architecture of FGMs in plants from the viewpoint of biologic chemical signals (Fig.1). Especially we will mention that how do plants manage to develop optimum architectrues, as well as can we create man-made architectures by controlling the cell-base mechanosensor. English Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Besearch on PriorityArea, No. 274 The Ministry of Education, Science, Sports and Culture of Japan Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Research on Priority Area, No. 274 5 1999-03-01 165-168 耐候性鋼上で後期安定保護さび積層を構成するCr置換針鉄鋼中での組成傾斜とイオン選択性 Compositional Gradient and Ion Selectivity in Cr-Substituted Goethite Consisting the Final Stable Protective Rust Layer on Weathering Steel 三澤俊平室蘭工業大学　材料物性工学科　050-8585　北海道室蘭市水元町２７番１号 Toshihei MisawaDepartment of Materials Science and Engineering, Muroran Institute of Technology, 27-1 Mizumoto-cho, Muroran, Hokkaido 050-8585, Japan INTRODUCTION Weathering steel possesses high corrosion resistance, approxixmately twice of that of carbon steels, and therefore has been widely used as a structural material in an atmospheric corrosion environment. However, it has been a problem on applying the weathering steels for using as a structural material, that the protective rust layer is usually formed spontaneously only after over 10 years exposure. Most recently, we have elucidated that the inner stable and protective rust layer which covered the surface of a weathering steel exposed for more than a quarter of a century mainly consists of nano-particles of Cr-substituted goethite, i.e. (alpha)-(Fe1-x, Crx)OOH. In this paper, effect of graded content of Cr on the ion selective properties of (alpha)-(Fe1-x, Crx)OOH has been examined. On the basis of the results, a newly acceleration method of final protective rust formation has been proposed in practice. English Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Besearch on PriorityArea, No. 274 The Ministry of Education, Science, Sports and Culture of Japan Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Research on Priority Area, No. 274 5 1999-03-01 169-172 金（Au）濃度勾配表面上での化学波の伝播プロセスのコントロール Control of the propagation process of chemical wave on the Au concentration-graded surface 朝倉清高東京大学　理学部スペクトル化学研究センター 113-0033　東京都文京区本郷 K.AsakuraResearch Center for Spectrochemistry, Graduate School of Science, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo, 113-0033, Japan Introduction When chemical reactions take place on the surface, a large amount of free energy is released which can be utilized to create a self-organized structure or dissipative structure. The self-organized structure can be described by non-linear wave function and the self-organized structure can propagates on the surface like a wave. Thus it is called as chemical wave. Pt(110) and Pt(100) surfaces are typical ones which produce chemical waves during CO oxidation reaction. [1,2] Because the chemical wave can propagate macroscopic level such as a few cm or more, it can convey information about surface state from one side and control the reaction on the whole surface. The purpose of this work is to establish the way to control chemical wave and regulate the surface reaction. English Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Besearch on PriorityArea, No. 274 The Ministry of Education, Science, Sports and Culture of Japan Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Research on Priority Area, No. 274 5 1999-03-01 173-176 コラーゲン会合体の傾斜構造の生体における意義 Biological Significance of Graded Structure of Collagen Supramolecular Aggregates 林利彦　広瀬志弘　水野一乗　中里浩一　小杉浩章　吉川究　　E.Adachi東京大学　大学院総合文化研究科生命環境科学系　153-8902　東京都目黒区駒場３丁目８－１ T. Hayashi, M. Hirose, K. Mizuno, K. Nakazato, H. Kosugi, K. Yoshikawa, E. AdachiDept. of Life Sciences, Graduate School of Arts & Sciences, The University of Tokyo, 3-8-1 Komaba. Meguro-ku, Tokyo, 153-8902, Japan Animal tissues have a graded distribution of filamentous and/or meshwork aggregates that are reminiscent of the reconstituted aggregates from isolated type I collagen, type V collagen, and type IV collagen (Fig.1)(1,2). We have proposed that the major four collagen types may comprise the scaffoldings of various tissues in a graded manner as shown in Fig. 2. We then further incorporate the different type of cells in the graded distribution of the supramolecular structures of collagen. The order of cell types lining from endothelial cells, smooth muscle cells and fibroblasts may correspond to the graded collagen aggregates from type IV collagen, type V collagen, and type I collagen. It would be intriguing to think that whether the graded distribution of cells with different functions in accord with the graded distribution of collagen supramolecular aggregates has any biological significance. It was already known that proliferation, shape, migration, gene expression, and responses to growth factors of the cultured fibroblasts were greatly affected by the type I collagen fibrils. In the present report, the hypothesis was tested by asking whether dfferentiated cells have preferences for aggregates reconstituted from different types of collagen. Thus endothelial cells and smooth muscle cells that are surrounded by type IV collagen and/or type V collagen more closely were cultured on the reconstituted type IV collagen aggregates in a gel form. English Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Besearch on PriorityArea, No. 274 The Ministry of Education, Science, Sports and Culture of Japan Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Research on Priority Area, No. 274 5 1999-03-01 177-180 細胞機能を調節するためのホスホリピド傾斜表面の調整 Preparation of Phospholipid Gradient Surfaces to Regulate Cell Function Y.Iwasaki*1, K.Ishihara*2*1　東京医科歯科大学　101-0062　東京都千代田区神田駿河台2-3-10*2　東京大学　工学部大学院　113-8656　東京都文京区本郷7-3-1 Y.Iwasaki*1, K.Ishihara*2*1Institute for Medical and Dentinal University, Tokyo Medical and Dental University, 2 -3-10, Kanda-surugadai, Chiyoda-ku, Tokyo, 101-0062, Japan *2 Department of Materials Science, Graduate School of Engineering, The University of Tokyo, 7-3-1, Hongo, Bunkyo-ku, Tokyo, 1 13-8656, Japan INTRODUCTION It is very important to recognize the surface characterization for development of new biomedical materials. Graft polymerization is one of the most familiar methods to improve the biocompatibility of polymer materials. Many studies have recently been focused on the preparation of surfaces whose properties are gradually changed along the material length. Such gradient surfaces are particular interest for basic studies of the interactions between biological species and surface, because the effect of a selected property can be examined in a single experiment on one surface. We have synthesized 2-metahcryloyloxyethyl phosphorylcholine (MPC) polymer as a new blood compatible material with attention to the surface structure of biomembrane and investigated its blood compatibility. It was reported that the MPC polymer could effectively reduce plasma protein adsorption and platelet adhesion when the MPC polymer was contacted with the blood. With attention to the hydrophobicity of the phospholipid moiety, (omega)-methacryloyloxyalkyl phosphorylcholine (MAPC) polymers which have various methylene chain lengths between the phospholipid polar group and the backbone, were synthesized. In this study, we prepared the poly (MAPC)-gradient surface on the low density polyethylene (PE) sheet by corona discharge treatment method with gradually increasing power and graft polymerization of MAPC to clarify the effect of the chemical structure of MAPC unit on the cell adhesion. English Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Besearch on PriorityArea, No. 274 The Ministry of Education, Science, Sports and Culture of Japan Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Research on Priority Area, No. 274 5 1999-03-01 181-184 DNA二重鎖が配向する傾斜機能フィルム Functionally Graded Films in Which DNA Double Strands are aligned 岡畑恵雄東京工業大学　生命理工学部　226　横浜市緑区長津田町 Yoshio OkahataDepartment of Biomolecular Engineering, Tokyo Institute of Technology, Nagatsuda, Midori-ku, Yokohama, 226 Japan INTRODUCTION DNA is important as a source of biological information depending on base sequences. DNA is also interesting as a molecular material that shows a long double helical structure with base-pair stacking: the base separation is 3.4A while the diameter of the helix is about 20A. It therefore is a good candidate for gradually graded electron conduction materials. In this report, we describe two methods to prepare organic thin films in which DNA strands aligned in one direction by i) uniaxial stretching of a cast film of DNA-lipid complex and ii) vertical dipping LB method of anionic DNA strands with cationic lipid monolayers. English Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Besearch on PriorityArea, No. 274 The Ministry of Education, Science, Sports and Culture of Japan Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Research on Priority Area, No. 274 5 1999-03-01 185-188 傾斜高分子膜の調整と膜透過‐分離機能 Preparation and Permeation-separation Function of Graded Polymeric Membranes 辻田義治, H. Yoshimizu, T. Suzuki名古屋工業大学　工学部　466-8555　愛知県名古屋市昭和区御器所町 Y. Tsujita, H. Yoshimizu, T. SuzukiDepartment of Materials Science and Engineering, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya 466-8555, Japan INTRODUCTION In this study, we try to prepare the graded polymeric membrane which the composition of two components are linearly changed by utilizing the miscible polymer blend system, and estimate its gas permeation properties. It had been reported that the graded membrane composed with polymethyl methacrylate and poly (styrene-co-acrylonitrile) (PMMA, SAN) could be prepared by the two-step solution-cast method i.e., a SAN solution drops on a PMMA cast film1). By this simple method the competition of the interdiffusion in PMMA and SAN and the solvent evaporation during the 2nd cast-step occurred, as a result, it can be expected that the membrane having a graded composition of PMMA and SAN along the thickness direction is formed. This graded structure was suggested by comparing the observed permeability coefficient and the calculated one using some simple assumption (the series model). In here, we try to estimate such a graded structure by 129Xe NMR spectroscopy using polyphenyleneoxide/polystyrene (PPO/PS) blend system as an another method. Since the Xe atom has a very large polarizability, it is expected that 129Xe NMR signals (the chemical shift, peak width etc.) are sensitively influenced by its environment. Especially, the induced 129Xe NMR chemical shifts are strongly correlated the size and nature of the microvoids in glassy polymers, because the interactions with host system perturb the Xe electron density. English Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Besearch on PriorityArea, No. 274 The Ministry of Education, Science, Sports and Culture of Japan Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Research on Priority Area, No. 274 5 1999-03-01 189-192 不均質系アパタイトの合成設計と生体材料への応用 Synthesis Design of Heterogeneous Apatites and Their Application to Biomaterials 岡崎正之　高橋純造　荘村泰治　寺岡文雄　平雅之　前田芳信大阪大学　歯学部　565-0871　大阪府吹田市山田丘1-8 M. Okazaki, J. Takahashi, T. Sohmura, F. Teraoka, M. Taira and Y. MaedaOsaka University Faculty of Dentistry, 1-8 Yamadaoka, Suita, Osaka 5659 Japan INTRODUCTION Apatites have been exclusively synthesized in aqueous systems[1-3] from the view point of biodegradable materials. Biological apatites contain several % carbonate ions CO3**2- and other trace elements[4]. We synthesized CO3apatite with a chemical composition and crystallinity[5] similar to those of bone. Then, a composite of this CO3apatite and collagen was made. This composite showed good biocompatibility for both soft and hard tissues in rats. The composite was successfully replaced by new bone. However, bone density and mechanical strength did not seem to recover completely. Stable hydroxyapatite covered with metabolic apatite is expected to yield a relatively tough biomaterial. Recently, functionally graded materials (FGM) have been developed for use in engineering fields[6]. We speculate that each apatite crystal can have an ionic distribution even in the crystal structure. We first generated a two-step fluoride supply system to solve the complicated heterogeneous phenomena of apatite formation[7]. In this study, we designed a continuous gradient carbonate supply system by developing this system, and then carbonate-containing apatite with a relatively soluble surface and stable core was investigated. English Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Besearch on PriorityArea, No. 274 The Ministry of Education, Science, Sports and Culture of Japan Physics and Chemistry of Functionally Graded Materials Research Report 1998 Grant-in-Aid for Scientific Research on Priority Area, No. 274 5 1999-03-01 193-196 電気泳動法による傾斜機能ポリウレタンの合成と応用 Synthesis and Application of Functionally Graded Polyurethanes by Electrophoresis 椎葉哲朗 古川睦久長崎大学　工学部材料工学科　852-8521　長崎県長崎市文教町１－１４ Tetsuro Shiiba and Mutsuhisa FurukawaDepartment of Materials Science and Engineering, Faculty of Engineering, Nagasaki University, 1-14 Bunkyo-machi, Nagasaki 852-8521, Japan INTRODUCTION Among the wide variety of polymeric composite materials that have been developed recently, compositions with a gradient of physical or chemical properties have attracted interest. These materials include the gradient interpenetrating polymer networks (GIPNs), which have been investigated by the swelling method since 1970s. In this paper, we proposed a novel preparation method of the functionally graded interpenetrating networks. The ionic vinyl monomer (N, N-dimethyl-aminoethylacrylate-Quaternary)(DMAEA) was introduced to the polyurethane elastomers (PUEs) by a method of electrophoresis, and polymerized to produce the networks. The concentration of PDMAEA through the thickness of PUEs was determined by elemental analysis. Water and benzene were used to determine the degree of swelling by means of a measuring microscope. Glass transition temperature, storage modulus of the modified PUEs were measured by DSC and dynamic mechanical tester. Chemomechanical responsibility by the electric-stimulus was also explored. English