Updated on 2024/03/30

写真a

 
UCHIYAMA,Hiroaki
 
Organization
Faculty of Chemistry, Materials and Bioengineering Professor
Title
Professor
Contact information
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Degree

  • 博士(工学) ( 2008.9 )

Research Areas

  • Nanotechnology/Materials / Inorganic compounds and inorganic materials chemistry

Education

  • Keio University   Graduate School, Division of Science and Engineering

    2008

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  • Keio University   Graduate School, Division of Science and Engineering

    2005

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  • Keio University   Faculty of Science and Engineering

    - 2004

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Research History

  • Kansai University   Faculty of Chemistry , Materials and Bioengineering Department of Chemistry and Materials Engineering   Professor

    2021.4

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  • Swedish University of Agricultural Sciences

    2015.3 - 2016.3

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  • Kansai University   Faculty of Chemistry , Materials and Bioengineering Department of Chemistry and Materials Engineering   Associate Professor

    2014.4 - 2021.3

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  • Kansai University   Faculty of Chemistry , Materials and Bioengineering Department of Chemistry and Materials Engineering   Assistant Professor

    2009.4 - 2014.3

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  • 日本学術振興会特別研究員 PD

    2008.9 - 2009.3

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  • 日本学術振興会特別研究員 DC2

    2008.4 - 2008.9

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Papers

  • Hydrothermal synthesis of dittmarite-group NH4(Co1−xMnx)PO4·H2O particles as inorganic violet pigments Reviewed

    H. Uchiyama, S. Tachibana

    RSC Adv.   14, 1939   2024.1

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  • Effect of the heating rate on crystallization and densification of TiO2 films prepared from alkoxide solutions containing various organic additives Reviewed

    H. Uchiyama, Y. Tanaka, S. Mizuguchi

    J Asian Ceram Soc.   11, 480   2023.11

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  • Nature-inspired compositional control of transition-metal-doped ammoniotinsleyite and spheniscidite particles for design of color hue Reviewed

    H. Uchiyama, D. Nagoshi, Y. Nagasu

    CrystEngComm   25, 1556   2023.3

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  • Viscoelastic behavior of alkali and alkaline earth aluminophosphate glasses Reviewed

    N. Kitamura, T. Hayashido, N. Matsushita, K. Fukumi, H. Uchiyama, H. Kozuka

    J. Non-Cryst. Solids   591, 12044   2022.9

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  • Water-assisted crystallization and densification of sol–gel-derived TiO<sub>2</sub> films during low-temperature heating Reviewed

    Hiroaki Uchiyama, Takahiro Bando

    Journal of Asian Ceramic Societies   10 ( 1 )   253 - 261   2022.1

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    Authorship:Lead author, Corresponding author   Language:English   Publishing type:Research paper (scientific journal)   Publisher:Informa UK Limited  

    DOI: 10.1080/21870764.2022.2039347

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  • Aqueous Synthesis of Manganese Phosphate Hydrate Crystals for Creating Inorganic Pigment Materials Reviewed

    Hiroaki Uchiyama, Itta Okumura, Sho Inoue, Masanori Kato, Masashi Wakahara

    Inorganic Chemistry   60 ( 19 )   14779 - 14785   2021.10

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    Authorship:Lead author, Corresponding author   Language:English   Publishing type:Research paper (scientific journal)   Publisher:American Chemical Society (ACS)  

    DOI: 10.1021/acs.inorgchem.1c02008

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  • Single-Source Alkoxide Precursor Approach to Titanium Molybdate, TiMoO<sub>5</sub>, and Its Structure, Electrochemical Properties, and Potential as an Anode Material for Alkali Metal Ion Batteries Reviewed

    Hiroaki Uchiyama, Dhanya Puthusseri, Jekabs Grins, Daniel Gribble, Gulaim A. Seisenbaeva, Vilas G. Pol, Vadim G. Kessler

    Inorganic Chemistry   60 ( 6 )   3593 - 3603   2021.3

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    Authorship:Lead author   Language:English   Publishing type:Research paper (scientific journal)   Publisher:American Chemical Society (ACS)  

    DOI: 10.1021/acs.inorgchem.0c03087

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  • Aqueous synthesis of tin- and indium-doped WO<sub>3</sub> films <i>via</i> evaporation-driven deposition and their electrochromic properties Reviewed

    Hiroaki Uchiyama, Yoshiki Nakamura, Seishirou Igarashi

    RSC Advances   11 ( 13 )   7442 - 7449   2021.2

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    Authorship:Lead author, Corresponding author   Language:English   Publishing type:Research paper (scientific journal)   Publisher:Royal Society of Chemistry (RSC)  

    <p>WO<sub>3</sub> and M-doped WO<sub>3</sub> (M = Sn or In) electrochromic films were obtained from aqueous solutions via evaporation-driven deposition. The In–WO<sub>3</sub> films showed a faster electrochromic response than WO<sub>3</sub> and Sn–WO<sub>3</sub> films, and a good cycle stability.</p>

    DOI: 10.1039/d1ra00125f

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  • Nano- and micro-structural control of WO3 photoelectrode films through aqueous synthesis of WO3·H2O and (NH4)0.33WO3 precursors

    H. Uchiyama, Y. Nagayasu

    RSC Adv.   10, 11444   2020.3

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  • Biomimetic synthesis of nanostructured WO3·H2O particles and subsequent thermal conversion to WO3

    H. Uchiyama, S. Mizuguchi, S. Hirano, H. Kozuka

    R. Soc. Open Sci.   6, 181237   2019.6

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  • Effect of the amount of H2O and HNO3 in Ti(OC3H7i)4 solutions on the crystallization of sol-gel-derived TiO2 films

    H. Uchiyama, T. Bando, H. Kozuka

    Thin solid films   669, 157-161   2019.1

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  • Additive-free alkoxide–water–alcohol solutions as precursors for crystalline titania thin films

    Shinnosuke Yamazaki, Hiroaki Uchiyama, Hiromitsu Kozuka

    Journal of Sol-Gel Science and Technology   87, 537-543   1 - 7   2018.6

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:Springer New York LLC  

    Abstract: When titanium alkoxides are hydrolyzed for preparing coating solutions for titania thin film deposition, chelating and peptizing agents such as acetylacetone and hydrochloric acid, respectively, are employed in order to suppress the formation of precipitates and obtain homogeneous sols. The present work demonstrates that precipitation can be avoided when 2-methoxyethanol is used as solvent for hydrolyzing titanium isopropoxide even without using chelating or peptizing agents. A sol obtained from a simple solution of molar compositions, Ti(OC3H7 i)4:H2O:CH3OC2H4OH = 1:1:25, was demonstrated to be stable in viscosity at least for &gt
    1 month. The stability and long pot life of the sol were evidenced in the identical characters including thickness, crystallite size and refractive index and the similar microstructure of the films prepared from the sols aged for 1 and 30 days at room temperature. The formation of homogeneous sol and its long-period stability were thought to result from chelation of the titanium atoms by 2-methoxyethanol molecules. [Figure not available: see fulltext.]

    DOI: 10.1007/s10971-018-4715-x

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  • Evaporation-Driven Deposition of ITO Thin Films from Aqueous Solutions with Low-Speed Dip-Coating Technique

    Takashi Ito, Hiroaki Uchiyama, Hiromitsu Kozuka

    LANGMUIR   33 ( 21 )   5314 - 5320   2017.5

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:AMER CHEMICAL SOC  

    We suggest a novel wet coating process for preparing indium tin oxide (ITO) films from simple solutions containing only metal salts and water via evaporation-driven film deposition during low-speed dip coating. Homogeneous ITO precursor films were deposited on silica glass substrates from the aqueous solutions containing In(NO3)(3)center dot 3H(2)O and SnCl4 center dot 3H(2)O by dip coating at substrate withdrawal speeds of 0.20-0.50 cm min(-1) and then crystallized by the heat treatment at 500-800 degrees C for 10-60 min under N-2 gas flow of 0.5 L min(-1). The ITO films heated at 600 degrees C for 30 min had a high optical transparency in the visible range and a good electrical conductivity. Multiple-coating ITO films obtained with five-times dip coating exhibited the lowest sheet (rho(s)) and volume (rho(v)) resistivities respectively of 188 Omega sq(-1) and 4.23 X 10(-3) Omega cm, respectively.

    DOI: 10.1021/acs.langmuir.7b00823

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  • Transferability and Adhesion of Sol-Gel-Derived Crystalline TiO2 Thin Films to Different Types of Plastic Substrates

    Natsumi Amano, Mitsuru Takahashi, Hiroaki Uchiyama, Hiromitsu Kozuka

    LANGMUIR   33 ( 4 )   947 - 953   2017.1

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:AMER CHEMICAL SOC  

    Anatase thin films were prepared on various plastic substrates by our recently developed sol gel transfer technique. Polycarbonate (PC), poly(methyl methacrylate) (PMMA), polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP), polyether ether ketone (PEEK), and polyvinylidene chloride (PVDC) were employed as plastic substrates. A Si(100) substrate was first coated with a polyimide (PI)/polyvinylpyrroli-done (PVP) mixture layer, and an alkoxide-derived titania gel film was deposited on it by spin-coating. The resulting titania gel film was heated to 600 degrees C, during which the PI/PVP layer decomposed and the gel film was converted into a 60 nm thick anatase film. The anatase film was then transferred from the Si(100) substrate to the plastic substrate. This was achieved by heating the plastic/anatase/Si(100) stack in a near-infrared image furnace to 120-350 degrees C, depending on the type of plastic substrate, under unidirectional pressure. The anatase film cracked during transfer to PE, PP, PEEK, and PVDC substrates but did not crack during transfer to PC, PMMA, and PET substrates. The fraction of the total film area that was successfully transferred was assessed with the aid of image analysis. This fraction tended to be large for plastics with C=O and C-O groups and small for those without these groups. The film/substrate adhesion assessed by cross-cut tape tests also tended to be high for plastics with C=O and C-O groups and low for those without these groups. The adhesion to plastics without C=O or C-O groups could be enhanced and their transfer area fraction increased by oxidizing the native plastic surface by ultraviolet ozone treatment prior to transfer.

    DOI: 10.1021/acs.langmuir.6b04142

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  • Preparation of porous CuO films from Cu(NO3)(2) aqueous solutions containing poly(vinylpyrrolidone) and their photocathodic properties

    H. Uchiyama, K. Isobe, H. Kozuka

    RSC ADVANCES   7 ( 29 )   18014 - 18018   2017

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:ROYAL SOC CHEMISTRY  

    We prepared cupric oxide (CuO) photocathode films by dip coating from Cu(NO3)(2) aqueous solutions containing poly(vinylpyrrolidone) (PVP). The addition of PVP modified the wettability of FTO glass substrates by the aqueous coating solutions, resulting in the formation of CuO coating layers on the substrates. The thermal decomposition of PVP by provided nanoscale pores in the resultant CuO films, and the porosity increased with increasing PVP content. The porous structure thus obtained led to an efficient photocathodic reaction under UV and visible light illumination (wavelength: 300-800 nm). Highly porous CuO films prepared at [PVP] = 0.25 M exhibited the maximum incident photon-to-current efficiency (IPCE) values of 8.7% and 3.9% at 300 and 500 nm, respectively.

    DOI: 10.1039/c6ra26590a

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  • Fabrication of highly crystalline oxide thin films on plastics: Sol–gel transfer technique involving high temperature process

    H. Kozuka, M. Takahashi, K. Niinuma, H. Uchiyama

    Journal of Asian Ceramic Societies   4, 329-336   2016.7

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  • Evaporation-Driven Deposition of WO3 Thin Films from Organic Additive-Free Aqueous Solutions by Low-Speed Dip Coating and Their Photoelectrochemical Properties

    Hiroaki Uchiyama, Seishirou Igarashi, Hiromitsu Kozuka

    LANGMUIR   32 ( 13 )   3116 - 3121   2016.4

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    We prepared tungsten trioxide (WO3) photo electrode films from organic-additive-free aqueous solutions by a low-speed dip-coating technique. The evaporation-driven deposition of the solutes occurred at the meniscus during low speed dip coating, resulting in the formation of coating layer on the substrate. Homogeneous WO3 precursor films were obtained from (NH4)(10)W12O41 center dot 5H(2)O aqueous solutions and found to be crystallized to monoclinic WO3 films by the heat treatment at 400-700 degrees C. All the films showed a photoanodic response irrespective of the heat treatment temperature, where a good photoelectrochemical stability was observed for those heated over 500 degrees C. The highest photoanodic performance was observed for the WO3 film heated at 700 degrees C, where the IPCE (incident photon-to-current efficiency) was 36.2% and 4.6% at 300 and 400 nm, respectively.

    DOI: 10.1021/acs.langmuir.6b00377

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  • Spontaneous Pattern Formation Induced by Benard-Marangoni Convection for Sol-Gel-Derived Titania Dip-Coating Films: Effect of Co-solvents with a High Surface Tension and Low Volatility

    Hiroaki Uchiyama, Tadayuki Matsui, Hiromitsu Kozuka

    LANGMUIR   31 ( 45 )   12497 - 12504   2015.11

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    Evaporation-driven surface tension gradient in the liquid layer often causes the convective flow, i.e., Benard-Marangoni convection, resulting in the formation of cell-like patterns on the surface. Here, we prepared sol-gel-derived titania films from Ti(OC3H7i)(4) solutions by dip coating and discussed the effect of the addition of co-solvents with a high surface tension and low volatility on the spontaneous pattern formation induced by Benard-Marangoni convection. Propylene glycol (PG, with a surface tension of 38.6 mN m(-1)) and dipropylene glycol (DPG, with a surface tension of 33.9 mN m(-1)) were added to the coating solutions containing 2-propanol (2-Pr, with a surface tension of 22.9 mN m(-1)) for controlling the evaporation-driven surface tension gradient in the coating layer on a substrate. During dip coating at a substrate withdrawal speed of 50 cm min(-1) in a thermostatic oven at 60 degrees C, linearly arranged cell-like patterns on a micrometer scale were spontaneously formed on the titania gel films, irrespective of the composition of coating solutions. Such surface patterns remained even after the heat treatment at 200 and 600 degrees C, where the densification and crystallization of the titania films progressed. The width and height of the cell-like patterns increased with increasing PG and DPG contents in the coating solutions, where the addition of PG resulted in the formation of cells with a larger height than DPG.

    DOI: 10.1021/acs.langmuir.5b02929

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  • Thermoplastic softening behavior of organically modified polyoxotitanates: Effects of the amount of water and benzoylacetone for hydrolyzing alkoxides

    S. Oda, H. Uchiyama, H. Kozuka

    J. Appl. Polym. Sci.   132, 42653   2015.7

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  • Evaporation-driven self-organization of sol-gel dip-coating films

    Hiroaki Uchiyama

    JOURNAL OF THE CERAMIC SOCIETY OF JAPAN   123 ( 1438 )   457 - 464   2015.6

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:CERAMIC SOC JAPAN-NIPPON SERAMIKKUSU KYOKAI  

    In this review, we discuss the spontaneous pattern formation of sol-gel dip coating films induced by solvent evaporation, as a novel patterning technique. Linearly arranged striations and cell-like patterns were obtained upon withdrawing the substrate from the coating solution at increasing withdrawal rates. Such highly ordered micropatterns formed by the Benard-Marangoni convection mechanism triggered by solvent evaporation. In contrast, dip-coating at rates below 1.0 cm min(-1) generated periodic stripe patterns arranged on the surface of the films that were perpendicular to the substrate withdrawal direction. Such a formation design was attributed to the onset of capillary flow of the coating solution at the meniscus induced by solvent evaporation. (C)2015 The Ceramic Society of Japan. All rights reserved.

    DOI: 10.2109/jcersj2.123.457

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  • Preparation of metal oxide thin films from organic-additive-free aqueous solutions by low-speed dip-coating

    H. Uchiyama, T. Ito, R. Sasaki, H. Kozuka

    RSC ADVANCES   5 ( 26 )   20371 - 20375   2015

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:ROYAL SOC CHEMISTRY  

    Here we propose a novel coating technique with low-speed dip-coating for preparing metal oxide thin films from organic-additive-free aqueous solutions, where the film formation on the substrate is achieved via an evaporation-driven deposition during dip-coating of extremely low substrate withdrawal speeds below 1.0 cm min(-1) in a thermostatic oven at 25-60 degrees C. Transparent, crack-free SnO2 and TiO2 precursor films were obtained from SnCl4 and TiOSO4 aqueous solutions, respectively, by low-speed dip-coating. The precursor films thus obtained were crystallized to SnO2 and TiO2 films by the heat treatment at 700 degrees C for 10 min in air.

    DOI: 10.1039/c4ra16810k

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  • Biomimetic synthesis of nanostructured SnO particles from Sn6O4(OH)(4) in aqueous solution of gelatin

    H. Uchiyama, S. Nakanishi, H. Kozuka

    CRYSTENGCOMM   17 ( 3 )   628 - 632   2015

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    Nanostructured SnO particles were produced by aging Sn6O4(OH)(4) in aqueous solutions containing HCl and gelatin at 60 degrees C, where the morphologies of the SnO products depended on the pH value and the gelatin concentration of the solutions. Flower-like and spherical architectures consisting of radially-branched platy units were obtained by the addition of gelatin, where the branching of SnO crystals was promoted with decreasing pH value and with increasing gelatin contents. The branched structures thus obtained could be formed via diffusion-controlled growth of SnO crystals in viscous solutions.

    DOI: 10.1039/c4ce01829j

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  • Effect of additives on the formation of bismuth nanoparticles by polyol process

    Naoyuki Kitamura, Naoki Hirao, Kohki Takahashi, Hiroaki Uchiyama, Hiromitsu Kozuka

    JOURNAL OF THE CERAMIC SOCIETY OF JAPAN   122 ( 1430 )   917 - 919   2014.10

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:CERAMIC SOC JAPAN-NIPPON SERAMIKKUSU KYOKAI  

    Formation of bismuth nano-particles by polyol process have been studied in terms of the effect of additives on its size and shape. Bismuth trichloride solved in ethylene glycol was reduced at high temperature with the existence of poly(vinylpyrrolidone) (PVP) and ferric chloride. Spherical particles were mostly formed with the solitary addition of PVP. Sphere size was decreased from 400 to 200 nm with increasing amount of the PVP. Addition of larger weight-average molecular weight (M-w) of the PVP decreased the sphere size slightly. On the other hand, hexagonal or rectangular plate-like particles were obtained at a high number ratio over 70% by the co-addition of ferric chloride with the PVP. Plate size and the fraction of plate-like particles tended to increase slightly with the increase of amount of the PVP. The plate size also increased with increase of molecular weight of the PVP and square plate-like particles larger than 1 micrometer were obtained with the addition of the large molecular size of PVP (M-w similar to 1,300,000). Adequate amount and size of PVP tended to decrease totally the growth speed of particles and to suppress coalescence with each other, and ferric ions suppressed the growth speed toward the c-axis by alternative re-oxidization of bismuth metal. (C) 2014 The Ceramic Society of Japan. All rights reserved.

    DOI: 10.2109/jcersj2.122.917

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  • Hydrothermal synthesis of nanostructured SnO particles through crystal growth in the presence of gelatin

    Hiroaki Uchiyama, Shunsuke Nakanishi, Hiromitsu Kozuka

    JOURNAL OF SOLID STATE CHEMISTRY   217   87 - 91   2014.9

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:ACADEMIC PRESS INC ELSEVIER SCIENCE  

    Crystalline SnO particles were obtained from Sn6O4(OH)(4) by the hydrothermal treatment in aqueous solutions containing gelatin at 150 degrees C for 24 h, where the morphologies of the SnO products changed from blocks to layered disks, stacked plates and unshaped aggregates with increasing amount of gelatin in the solutions. Such morphological changes of SnO particles were thought to be attributed to the suppression of the growth of SnO crystals by the adsorbed gelatin. (C) 2014 Elsevier Inc. All rights reserved.

    DOI: 10.1016/j.jssc.2014.05.023

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  • Evaporation-driven self-organization of photoluminescent organic dye-doped silica-poly(vinylpyrrolidone) hybrid films prepared by low-speed dip-coating

    Hiroaki Uchiyama, Ryosuke Sasaki, Hiromitsu Kozuka

    COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS   453   1 - 6   2014.7

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:ELSEVIER SCIENCE BV  

    We prepared silica-poly(vinylpyrrolidone) (PVP) hybrid films containing a photoluminescent organic dye, rhordamine 6G (R6G), by low-speed dip-coating, where the spontaneous pattern formation was induced in the films. Stripe patterns arranged perpendicular to the substrate withdrawal direction were spontaneously formed by stick-slip motion at the meniscus during dip-coating, and the film structure (i.e., the film thickness, and the height, width and spacing of stripe patterns) was changed with increasing amounts of volatile solvent (C2H5OH) in solutions (C2H5OH/Si(OCH3)(4) mole ratio(x) = 20-150). As a result of the optimization of the film structure, localized photoluminescence at the stripe patterns was achieved over x = 120. (C) 2014 Elsevier B.V. All rights reserved.

    DOI: 10.1016/j.colsurfa.2014.03.066

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  • Thermoplasticity of sol-gel-derived titanoxanes chemically modified with benzoylacetone

    Shinya Oda, Hiroaki Uchiyama, Hiromitsu Kozuka

    JOURNAL OF SOL-GEL SCIENCE AND TECHNOLOGY   70 ( 3 )   441 - 450   2014.6

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:SPRINGER  

    Titanium tetra-n-butoxide was hydrolyzed in the presence of benzoylacetone (BzAc), and the solution obtained was concentrated and served for spin-coating or dropping on substrates, followed by successive drying at 120, 200 and 250 A degrees C. The dried products were transparent and amorphous, and the infrared absorption and Raman spectroscopic studies showed that BzAc forms chelate rings. Thermomechanical analysis showed that the 120 and 200 A degrees C-dried products showed steep, thermoplastic shrinkage at around 30 and 70-85 A degrees C, respectively, whereas the 250 A degrees C-dried product did not show thermoplasticity. Thus as the drying temperature was increased, the thermoplasticity appeared at a higher temperature and finally disappeared. These changes in thermoplasticity with drying temperature were concluded to result from the progress of condensation between titanoxane polymers and/or clusters, which was evidenced in gel permeation chromatographic analysis.

    DOI: 10.1007/s10971-014-3304-x

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  • Effect of the Amount of H2O on the Crystallization of TiO2 Films Prepared from Alkoxide Solutions Containing Acetylacetone

    Hiroaki Uchiyama, Momoto Okada, Hiromitsu Kozuka

    JOURNAL OF THE AMERICAN CERAMIC SOCIETY   97 ( 4 )   1091 - 1095   2014.4

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:WILEY-BLACKWELL  

    Sol-gel-derived TiO2 films were prepared by dip-coating from Ti(OC3H7i)(4)-CH3COCH2COCH3-HNO3-H2O-C2H5OH solutions, and the effect of the H2O content in solutions on the crystallization of TiO2 films during the heat treatment at 800 degrees C was discussed. The crystalline phase, crystallite size, grain size, and refractive index of the TiO2 films depended on the H2O/Ti(OC3H7i)(4) mole ratios (x) in the coating solutions. Highly dense and crystalline rutile films were obtained at x=0.5-10, where the crystallites and grains became larger with increasing x. The further increase in x from 10 to 50 reduced the crystallite size and refractive index of the films, where anatase phase appeared at x=30-50.

    DOI: 10.1111/jace.12860

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  • Superior Properties of Silica Thin Films Prepared from Perhydropolysilazane Solutions at Room Temperature in Comparison with Conventional Alkoxide-Derived Silica Gel Films

    Hiromitsu Kozuka, Koji Nakajima, Hiroaki Uchiyama

    ACS APPLIED MATERIALS & INTERFACES   5 ( 17 )   8329 - 8336   2013.9

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:AMER CHEMICAL SOC  

    Preparation of silica thin films from perhydropolysilazane (PHPS) at room temperature has attracted much attention because it provides a new way to realize silica thin films in a variety of technologies where any high temperature processes should be avoided. Although silica gel films can also be prepared from alkoxides at room temperature by conventional sol-gel method, they are believed to have low mechanical and chemical durability. However, even such alkoxide-derived silica gel films have possibilities to become more durable via condensation reaction and densification when aged at room temperature. In Order to clarify whether or not PHPS-derived silica thin films have critical superiority on properties, the hardness and chemical durability were compared between PHPS- and alkoxide-derived silica thin films, where PHPS films were exposed to the vapor from aqueous ammonia at room temperature for PHPS-to-silica conversion. Alkoxide-derived silica gel films were found to be densified and hardened when stored in air at room temperature, which resulted in pencil hardness even higher than 9H on Si(100) substrates. However, the ultra-microindentation tests demonstrated that the PHPS-derived films are definitely harder than the alkoxide-derived ones. The PHPS-derived films were also found to have higher chemical durability in water and in aqueous ammonia. Such higher mechanical and chemical durability of the PHPS-derived films was ascribed to their higher density, i.e., more highly condensed states, which was evidenced in infrared absorption spectra. Hard coating performance on plastic substrates was also studied, and the PHPS-derived films were demonstrated to have much higher adhesive strength on polymethylmethacrylate substrates. The in-plane stress measurement demonstrated that the PHPS-derived films have much lower or even negligible tensile stress, which may be one of the causes for such higher adhesive strength.

    DOI: 10.1021/am400845y

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  • Conversion of Solution-Derived Perhydropolysilazane Thin Films into Silica in Basic Humid Atmosphere at Room Temperature

    Koji Nakajima, Hiroaki Uchiyama, Takayuki Kitano, Hiromitsu Kozuka

    JOURNAL OF THE AMERICAN CERAMIC SOCIETY   96 ( 9 )   2806 - 2816   2013.9

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:WILEY-BLACKWELL  

    Spin-on perhydropolysilazane (PHPS) thin films were converted into mechanically hard silica thin films by an exposure to the vapor from aqueous ammonia. Infrared absorption and X-ray photoelectron spectroscopic analyses were conducted to clarify the details of the PHPS-to-silica conversion and the nature of the silica thin film products. The PHPS-to-silica conversion was found to proceed rapidly between 2 and 3h of exposure via a reaction-limited process, where the refractive index and the pencil hardness greatly decreased and increased, respectively. Finally, the O/Si mole ratio close to 2 was achieved, which has never been realized in literature for PHPS-derived silica thin films. It was also found that the condensation of Si-OH groups proceeds in films immediately after PHPS hydrolysis, which is similar to the base-catalyzed hydrolysis-condensation reaction of silicon alkoxides. Although the silica thin films obtained had refractive indices similar to that of silica glass, high pencil hardness over 9H on Si(100) substrates, and O/Si mole ratios close to 2, it was concluded that they are nonidentical to silica glass, containing trace amounts of Si-OH and Si-H groups.

    DOI: 10.1111/jace.12513

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  • Sol-gel and transfer technique for fabricating dual ceramic thin film patterns on plastics

    Hiromitsu Kozuka, Takafumi Fukui, Hiroaki Uchiyama

    Journal of Sol-Gel Science and Technology   67 ( 2 )   414 - 419   2013.8

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    A technique that realizes alternating, two kinds of ceramic ribbons on plastics is proposed. An Si(100) plate with periodic trenches coated with a polyimide (PI)-polyvinylpyrrolidone (PVP) mixture layer was used as the mother substrate. An indium-tin-oxide (ITO) thin film was deposited on the mother substrate by the sol-gel method with a firing process, followed by transferring it to a polycarbonate (PC) substrate by melting the PC surface in contact with the ITO thin film. This resulted in patterned ITO ribbons on the PC substrate where the ridges of PC were formed between the ribbons. A ZnO thin film was prepared on a flat Si(100) substrate coated with a PI-PVP mixture layer, followed by firing, and then was transferred on the PC ridges in the same manner, resulting in alternating ITO and ZnO ribbons on the PC substrate. The technique proposed here allows dense, alternating ceramic ribbons to be fabricated on plastics irrespective of the combinations of ceramics and plastics. © 2013 Springer Science+Business Media New York.

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  • Photoelectrochemical properties of ZnO-SnO2 films prepared by sol-gel method

    Hiroaki Uchiyama, Ryosuke Nagao, Hiromitsu Kozuka

    JOURNAL OF ALLOYS AND COMPOUNDS   554   122 - 126   2013.3

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    Zn2SnO4 films were prepared by dip-coating from the solutions consisting of Zn(CH3COO)(2)center dot 2H(2)O, SnCl4 center dot 5H(2)O, H2O, CH3COCH2COCH3 and CH3OC2H4OH, and the photoanodic properties were compared to those of the ZnO and SnO2 films prepared via the same synthetic route. Here, the photoanodic properties were studied in a three-electrode cell with an aqueous buffer solution of pH = 7 as the supporting electrolyte. The Zn2SnO4, ZnO and SnO2 films exhibited photoanodic response under the UV light illumination. The Zn2SnO4 film exhibited the higher IPCE at wavelengths of 250-275 nm than the ZnO and SnO2 films, while the ZnO film showed the highest IPCE at wavelengths of 300-375 nm. The higher photoanodic currents could be attributed to the higher photoabsorbance of the Zn2SnO4 and ZnO films at wavelengths of 200-290 nm and 290-390 nm, respectively. (C) 2012 Elsevier B. V. All rights reserved.

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  • Preparation of nanostructured CeCO3OH particles from aqueous solutions and gels containing biological polymers and their thermal conversion to CeO2

    Hiroaki Uchiyama, Reiko Sakaue, Hiromitsu Kozuka

    RSC ADVANCES   3 ( 43 )   20106 - 20112   2013

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    Nanostructured CeCO3OH particles were prepared from aqueous solutions and gels containing CeCl3 and biological polymers (gelatin and agar) by the addition of (NH4)(2)CO3 solutions. The morphologies of the CeCO3OH products depended on the kind and concentration of the biological polymers. Sheaf- and cocoon-like CeCO3OH particles of ca. 2 mu m in size consisting of fine particles of ca. 10 nm in diameter were obtained from the precursor solutions containing gelatin. On the other hand, CeCO3OH precipitates with inhomogeneous size and shape were obtained from the precursor solutions and gels containing agar. Such morphological variation of CeCO3OH particles was thought to be due to the suppression of nucleation and growth of CeCO3OH crystals by the biological polymers. The CeCO3OH particles thus obtained were converted to CeO2 particles by the heat treatment at 600 degrees C, and the morphology as well as nanostructure remained during the heat treatment.

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  • Crystallization and densification of alkoxide-derived titania films: Effect of the amount of H2O in the precursor solutions

    Hiroaki Uchiyama, Momoto Okada, Dai Ogawa, Hiromitsu Kozuka

    Journal of Asian Ceramic Societies   1 ( 3 )   248 - 256   2013

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    Sol-gel derived TiO2 films were prepared from the solutions containing Ti(OC3H7i)4, H2O, HNO3 and C2H5OH by dip-coating, and the effects of the processing parameters (the heat-treatment temperature and time, and the H2O contents in the coating solutions) on the crystallization and densification of TiO2 films during the heat treatment in air were discussed. Anatase films were obtained by the heat treatments over 400°C, and the increase in heat-treatment temperature and time led to a decrease in film thickness and an increase in grain size, crystallite size and refractive index of the films. Moreover, the crystal growth and grain growth were promoted with increasing H2O content in the coating solutions during the heat treatments over 500°C, while the crystallization and densification were suppressed by the slow condensation of TiOH species below 400°C at larger H2O contents. © 2013 The Ceramic Society of Japan and the Korean Ceramic Society.

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  • Ceramic Thin Films on Plastics: A Versatile Transfer Process for Large Area as Well as Patterned Coating

    Hiromitsu Kozuka, Takafumi Fukui, Mitsuru Takahashi, Hiroaki Uchiyama, Shohei Tsuboi

    ACS APPLIED MATERIALS & INTERFACES   4 ( 12 )   6415 - 6420   2012.12

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    A versatile technique for fabricating ceramic thin films on plastics has been proposed. The technique comprises (i) the deposition of a gel film by spin- or dip-coating on a silicon substrate coated beforehand with a release layer, (ii) the firing of the gel film into a ceramic film, and (iii) its transfer onto plastics by melting or softening the plastics surface. Reflective anatase and electrically conductive indium-tin-oxide (ITO) thin films were prepared on acrylic resin and polycarbonate substrates. Patterned ITO thin films could also be fabricated on plastics by using a mother silicon substrate with periodic grooves.

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  • Spontaneous Formation of Linearly Arranged Microcraters on Sol-Gel-Derived Silica-Poly(vinylpyrrolidone) Hybrid Films Induced by Benard-Marangoni Convection

    Hiroaki Uchiyama, Yuto Mantani, Hiromitsu Kozuka

    LANGMUIR   28 ( 27 )   10177 - 10182   2012.7

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    Complex, sophisticated surface patterns on micrometer and nanometer scales are obtained when solvent evaporates from solutions containing nonvolatile solutes dropped on a solid substrate. Such evaporation-driven pattern formation has been utilized as a fabrication process of highly ordered patterns in thin films. Here, we suggested the spontaneous pattern formation induced by Benard-Marangoni convection triggered by solvent evaporation as a novel patterning process of sol-gel-derived organic-inorganic hybrid films. Microcraters of 1.0-1.5 mu m in height and of 100-200 mu m in width were spontaneously formed on the surface of silica-poly(vinylpyrrolidone) hybrid films prepared via temperature-controlled dip-coating process, where the surface patterns were linearly arranged parallel to the substrate withdrawal direction. Such highly ordered micropatterns were achieved by Benard-Marangoni convection activated at high temperatures and the unidirectional flow of the coating solution on the substrate during dip-coating.

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  • Solvothermal synthesis of size-controlled ZrO2 microspheres via hydrolysis of alkoxides modified with acetylacetone

    Hiroaki Uchiyama, Keiji Takagi, Hiromitsu Kozuka

    COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS   403   121 - 128   2012.6

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    We prepared ZrO2 particles from the solutions containing Zr(OC3H7n)(4). H2O, n-C3H7OH and acetylacetone (acac) via solvothermal treatment at 150 degrees C. The particle size and shape depended on the molar composition of the precursor solutions. Micron-sized spheres consisting of cubic and tetragonal ZrO2 with low crystallinity were obtained via hydrolysis of Zr(OC3H7n)(4) modified with acac, and the size of the spheres decreased from 2-10 mu m to 0.5 mu m with increasing amount of H2O and n-C3H7OH at constant n-C3H7OH/H2O mole ratios. The non-aggregated, homogeneous microspheres can be observed even by optical microscopy. The crystallinity of the ZrO2 spheres were improved by the heat treatment at 600 degrees C, and the spherical shape remained during the heat treatment. (C) 2012 Elsevier B.V. All rights reserved.

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  • Sol-gel-derived titania-hydroxypropylcellulose hybrid thin films of high refractive indices: solution components affecting the refractive index and uncracking critical thickness

    Shinya Oda, Hiroaki Uchiyama, Hiromitsu Kozuka

    JOURNAL OF SOL-GEL SCIENCE AND TECHNOLOGY   61 ( 3 )   484 - 493   2012.3

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    Optically transparent, ca. 200-800 nm thick TiO2-hydroxypropylcellulose (HPC) hybrid thin films were prepared from Ti(OC3H7i)(4)-HPC-HCl-H2O-(C3H7OH)-O-i solutions by the sol-gel method, where the as-deposited films were dried at 120 degrees C. The effects of the amount of HPC, H2O and HCl in the starting solutions on the refractive index and uncracking critical thickness of the films were studied, where the effects on the critical thickness was discussed on the basis of in situ stress measurements during heating. The increase in HPC content increased the critical thickness and lowered the refractive index. The increase in HCl content resulted in a decrease in critical thickness and an increase in refractive index. Larger H2O contents gave rise to a maximum in critical thickness while the refractive index was unaffected. Such variation in critical thickness with varying solution compositions was demonstrated to result from the differences in in-plane stress generated during heating. By optimizing the processing parameters an 810 nm thick TiO2-HPC hybrid film of a refractive index of 1.84 was obtained.

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  • Aqueous dip-coating route to dense and porous silica thin films using silica nanocolloids with an aid of polyvinylpyrrolidone

    Hiromitsu Kozuka, Akihiro Yamano, Masahiro Fujita, Hiroaki Uchiyama

    JOURNAL OF SOL-GEL SCIENCE AND TECHNOLOGY   61 ( 2 )   381 - 389   2012.2

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    An aqueous dip-coating route without using volatile alcohols for preparing dense and porous silica thin films is presented. The films were prepared by dip-coating on Si(100) and silica glass substrates using aqueous suspension of 8-11 nm colloidal silica where no alcohols were added. The addition of polyvinylpyrrolidone (PVP) in the suspension greatly improved the wettability, allowing homogeneous films to be formed on the substrates while the substrates showed poor wettability without PVP. When the as-deposited films were fired at 500-1,000 A degrees C, optically transparent porous films with smooth surface were obtained. The porous films had homogeneous distribution and packing of silica nanoparticles, refractive indices of 1.24-1.33, and pencil hardness lower than 6B. The porous films underwent significant densification by viscous sintering when fired at temperatures over 1,000 A degrees C. The viscous sintering was accompanied by the progress of condensation reaction and by the structural relaxation of siloxane network, which was revealed in the infrared absorption spectra. The resulting dense films had optical transparency, smooth surface, pencil hardness over 9H and refractive indices close to that of silica glass.

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  • Understanding of the development of in-plane residual stress in sol-gel-derived metal oxide thin films

    Kentaro Ohno, Hiroaki Uchiyama, Hiromitsu Kozuka

    JOURNAL OF APPLIED PHYSICS   111 ( 1 )   2012.1

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    The in-plane residual stress in thin films greatly affects their properties and functionality as well as the substrate bending, and hence is an important factor to be controlled. In order to obtain general knowledge on the development of residual stress in sol-gel-derived oxide thin films, the in-plane residual stress was measured for yttria stabilized zirconia gel films on Si(100) wafers as a function of firing temperature by measuring the substrate curvature. The films showed a rather complex variation in residual stress, and the mechanism of the residual stress evolution was discussed, referencing the intrinsic stress and the x-ray diffraction data. At low annealing temperatures of 100-200 degrees C, the residual tensile stress decreased and became compressive partially due to the structural relaxation occurring during cooling. When the firing temperature was increased over 200 degrees C, the residual stress turned tensile, and increased with increasing annealing temperature, which was attributed to the increase in intrinsic stress due to film densification as well as to the reduced structural relaxation due to the progress of densification. The residual tensile stress slightly decreased at firing temperatures of 500-600 degrees C, which was attributed to the reduction in intrinsic stress due to thermally activated atomic diffusion as well as to emergence of thermal stress. At firing temperature over 600 degrees C, the residual tensile stress increased again, which was attributed to the increase in thermal stress generated during cooling due to the increased Young's modulus of the film. Although appearing to be complicated, the whole variation of residual stress with firing temperature could be understood in terms of film densification, structural relaxation, atomic diffusion, progress of crystallization and thermal strain. The illustration presented in the work may provide a clear insight on how the residual stress could be developed in a variety of functional sol-gel-derived, crystalline oxide thin films. (C) 2012 American Institute of Physics. [doi: 10.1063/1.3673330]

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  • Spontaneous Formation of Micrometer-Scaled Cell-like Patterns on Alkoxide-Derived Silica Gels Induced by Benard-Marangoni Convections

    Hiroaki Uchiyama, Yuichiro Miki, Yuto Mantani, Hiromitsu Kozuka

    JOURNAL OF PHYSICAL CHEMISTRY C   116 ( 1 )   939 - 946   2012.1

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    Cell-like patterns were spontaneously formed on the silica gels prepared by dropping acid-catalyzed tetramethyl orthosilicate (Si(OCH3)(4)) solutions containing poly(vinylpyrrolidone) (PVP) on a stationary substrate. The height of the cell-like patterns increased with increasing the contents of PVP in the precursor solutions and the substrate temperature. On the other hand, the width of the patterns decreased with increasing the substrate temperature, while did not change with the addition of PVP. Such pattern formation was caused by the Benard - Marangoni convections occurring in the precursor solutions during the solvent evaporation. The cell-like patterns on the silica gels disappeared during the aging of the gels in the solvent vapor.

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  • Solvothermal synthesis of micron-sized spherical particles in TiO2-ZrO2 binary system

    Hiroaki Uchiyama, Koichi Matsumoto, Hiromitsu Kozuka

    JOURNAL OF CRYSTAL GROWTH   338 ( 1 )   201 - 207   2012.1

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    We prepared TiO2-ZrO2 binary oxide particles with various Ti/(Zr+Ti) mole ratios (x) from the solutions containing Ti(OC3H7i)(4), Zr(OC3H7n)(4) and acetylacetone (acac). The spherical particles of 1-5 mu m in diameter were obtained via solvothermal treatment at 150 degrees C. The spheres were anatase at x=1 and amorphous at x=0-0.8. The spheres were thought to be formed through the moderate hydrolysis and nucleation provided by the chelation of the alkoxides by acac. Crystalline TiO2-ZrO2 particles were obtained by the heat treatment of the as-precipitated spheres, and the crystalline phase changed with the Ti/(Zr+Ti) mole ratios. Pure ZrO2 and TiO2, ZrO2 doped with Ti4+, TiO2 doped with Zr4+ and ZrTiO4 phases were produced, and the spherical shape remained after the heat treatment at 500-750 degrees C. (C) 2011 Elsevier B.V. All rights reserved.

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  • Large area ceramic thin films on plastics: A versatile route via solution processing

    H. Kozuka, A. Yamano, T. Fukui, H. Uchiyama, M. Takahashi, M. Yoki, T. Akase

    JOURNAL OF APPLIED PHYSICS   111 ( 1 )   2012.1

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    A new general route for large area, submicron thick ceramic thin films (crystalline metal oxide thin films) on plastic substrates is presented, where the crystallization of films is guaranteed by a firing process. Gel films are deposited on silicon substrates with a release layer and fired to be ceramic films, followed by transferring onto plastic substrates using adhesives. The ceramic films thus fabricated on plastics exhibit a certain degree of flexibility, implying the possibility of the technique to be applied to high-throughput roll-to-roll processes. Using this technique, we successfully realized transparent anatase thin films that provide high optical reflectance and transparent indium tin oxide thin films that exhibit electrical conductivity on polycarbonate and acrylic resin substrates, respectively. Crystallographically oriented zinc oxide films and patterned zinc oxide films are also demonstrated to be realized on acrylic resin substrates. (C) 2012 American Institute of Physics. [doi: 10.1063/1.3676281]

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  • Spontaneous pattern formation on silica and titania dip-coating films prepared at extremely low substrate withdrawal speeds

    Hiroaki Uchiyama, Masaki Hayashi, Hiromitsu Kozuka

    RSC ADVANCES   2 ( 2 )   467 - 473   2012

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    Linear patterns were spontaneously formed on the silica and titania dip-coating films prepared from tetramethyl orthosilicate (Si(OCH3)(4)) and titanium tetraisopropoxide (Ti(OC3H7i)(4)) solutions, respectively. In both films, the pattern formation occurred at extremely low substrate withdrawal speeds below 1.0 cm min(-1), where the film thickness increased with decreasing substrate withdrawal speed for dip-coating. The linear patterns on micrometre scale were arranged perpendicular to the substrate withdrawal direction. The values of R-Z (10 point height of irregularities) and S (mean spacing of local peaks) of the patterns increased with decreasing substrate withdrawal speed.

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  • Hydrothermal synthesis of flower-like SnO2 particles consisting of single-crystalline nanorods through crystal growth in the presence of poly(acrylic acid)

    Hiroaki Uchiyama, Yuya Shirai, Hiromitsu Kozuka

    RSC ADVANCES   2 ( 11 )   4839 - 4843   2012

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    We prepared crystalline SnO2 particles from aqueous solutions of SnCl4 containing poly(acrylic acid) (PAA) by hydrothermal treatment at 150 degrees C. The morphology of the SnO2 particles depended on the concentration of PAA and the pH value of the precursor solutions. The flower-like SnO2 particles of ca. 100 nm in diameter consisting of needle-like units ca. 50 nm in size were obtained from the solution of [SnCl4 center dot 5H(2)O] = 0.1 M and [PAA] = 0.02 M containing the acidic solvents of pH 0.35 via the hydrothermal treatment. The needle-like units were found to consist of nanorods of ca. 50 nm in length and ca. 5 nm in width. The flower-like SnO2 particles were thought to be formed through the moderate nucleation and growth rates that were provided by the relatively high solubility of the Sn4+ species under the acidic conditions and the their coordination by PAA.

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  • Polymer-free organic-inorganic hybrid materials with high refractive indices and thermoplastic properties

    Shinya Oda, Hiroaki Uchiyama, Hiromitsu Kozuka

    Chemistry Letters   41 ( 3 )   319 - 321   2012

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    We prepared a new class of organicinorganic hybrid materials with high refractive indices and thermoplasticity. Titanium and zirconium alkoxides were hydrolyzed in the presence of β- diketones of high melting and boiling points, followed by concentration and heating over 100 °C. Transparent, glass-like solid materials were obtained, exhibiting softening or melting behavior on heating in spite of the absence of organic polymers. The refractive indices of the thermoplastic hybrid materials were as high as 1.7. © 2012 The Chemical Society of Japan.

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  • Spontaneous pattern formation based on the coffee-ring effect for organic-inorganic hybrid films prepared by dip-coating: effects of temperature during deposition

    Hiroaki Uchiyama, Daisuke Shimaoka, Hiromitsu Kozuka

    SOFT MATTER   8 ( 44 )   11318 - 11322   2012

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    We prepared silica-poly(vinylpyrrolidone) (PVP) hybrid films via a temperature-controlled dip-coating process and investigated the influence of the coating temperature (i.e., the temperature of substrates, solutions and atmosphere) on the spontaneous pattern formation based on the "coffee-ring effect". Micron-scale stripe patterns were spontaneously formed on the surface of the films at high coating temperatures over 40 degrees C during dip-coating. The stripe patterns were arranged perpendicular to the withdrawal direction, and the height and width of the patterns increased with increasing coating temperature. Such spontaneous pattern formation is attributed to the evaporation-driven capillary flow of coating solutions at the meniscus, and the stripe patterns with larger heights and widths are thought to be achieved by the capillary flow activated at higher coating temperatures.

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  • Photoelectrochemical Properties of Fe2O3-SnO2 Films Prepared by Sol-Gel Method

    Hiroaki Uchiyama, Masashi Yukizawa, Hiromitsu Kozuka

    JOURNAL OF PHYSICAL CHEMISTRY C   115 ( 14 )   7050 - 7055   2011.4

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    Fe2O3-SnO2 coating films of various Sn/(Fe + Sn) mole ratios, r(sn), were prepared by dip-coating on Nesa silica glass substrates from the solutions consisting of Fe(NO3)(3) center dot 9H(2)O, SnCl4 center dot 5H(2)O, H2O, CH3COCH2COCH3, and CH3OC2H4OH. The photoanodic properties were studied in a three-electrode cell with an aqueous buffer solution of pH = 7 as the supporting electrolyte. The Fe2O3-SnO2 films of r(sn) = 0-0.25 comprised hematite phase and exhibited photoresponse under the UV and visible light. The photoanodic response of the alpha-Fe2O3 film was enhanced by doping with Sn4+; the film of r(sn) = 0.1 exhibited the maximum IPCE (incident photon-to-current efficiency) of 26.9% and 8.6% at the wavelengths of 350 and 425 nm, respectively, which were higher than those of the Fe2O3-TiO2 film of Ti/(Fe + Ti) = 0.1 prepared by similar process. IPCE decreased with increasing r(sn) from 0.1 to 0.25. The films of r(sn) &gt;= 0.5 comprised rutile phase without hematite phase, showing very low IPCE.

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  • Formation of spherical SnO2 particles consisting of nanocrystals from aqueous solution of SnCl4 containing citric acid via hydrothermal process

    Hiroaki Uchiyama, Yuya Shirai, Hiromitsu Kozuka

    JOURNAL OF CRYSTAL GROWTH   319 ( 1 )   70 - 78   2011.3

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    We prepared crystalline SnO2 particles from aqueous solutions of SnCl4 with and without citric acid via hydrothermal treatment. The crystallinity, the crystallite size and shape, and the morphology of the secondary particles depend on the concentration of citric acid, the pH value of the solvents and the hydrothermal treatment temperature. Spherical SnO2 particles of 1-3 mu m in diameter consisting of nanocrystallites below 10 nm in size were obtained via hydrothermal treatment at 150 degrees C from a solution with the citric acid/SnCl4 mole ratio of 0.5 in acidic solvents of pH 3.0-5.5. The SnO2 spheres were thought to be formed through the moderate nucleation rate provided by the relatively high solubility of Sn4+ species and coordination by citric acid. (C) 2011 Elsevier B.V. All rights reserved.

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  • Effects of fundamental processing parameters on the durability of sol-gel-derived silica thin films in water

    Hiromitsu Kozuka, Takahiro Michihata, Hiroaki Uchiyama

    Journal of the Ceramic Society of Japan   119 ( 1390 )   434 - 439   2011

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    Silica gel films were prepared on Si(100) substrates from Si(OC 2H5)4- and Si(OCH3) 4-derived sols by dip-coating, and the gel films were heat-treated at 100700° C. The durability of the films against water was evaluated by measuring the thickness before and after soaking them in 80°C water for 24 h. The durability increased with increasing heat-treatment temperature principally due to the progress of film densification. Higher amounts of water for hydrolyzing Si(OC2H5)4 were greatly effective in achieving higher durability at lower heat-treatment temperatures. Longer sol aging was also effective in improving the durability of the Si(OC2H5)4-derived films. Si(OCH 3)4-derived films exhibited much higher durability than Si(OC2H5)4-derived ones. All of these factors, i.e. the larger amounts of water for hydrolysis, the longer sol aging time and the employment of Si(OCH3)4, may provide more dense film structure and more chance to undergo condensation during gel film heat-treatment, leading to the higher durability at lower heat-treatment temperatures. © 2011 The Ceramic Society of Japan.

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  • Spontaneous Formation of Linear Striations and Cell-like Patterns on Dip-Coating Titania Films Prepared from Alkoxide Solutions

    Hiroaki Uchiyama, Wataru Namba, Hiromitsu Kozuka

    LANGMUIR   26 ( 13 )   11479 - 11484   2010.7

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    Linear striations and cell-like patterns were spontaneously formed on the dip-coating Mania films prepared titanium tetraisopropoxide (Ti(OC3H7i)(4)) solutions. Such unique patterns on micrometer scale were arranged parallel to the substrate withdrawal direction. The values of R-z (10 point height of irregularities) and S (mean spacing of local peaks) of the patterns increased with increasing film thickness depending on the substrate withdrawal speed for dip-coating, the viscosity of the coating solutions, and the distance front the top edge of films. The shape of patterns changed from linear striations to cell-like patterns with increasing viscosity of the coating solutions. Although the heat treatment at 600 degrees C reduced the height (R-z) of stripes and cells without the change in spacing (S), the visibility of patterns was enhanced by the increase in refractive index due to the crystallization of films.

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  • Preparation of Titania Spheres Consisting of Anatase Nanocrystals via Hydrolysis of Chemically Modified Alkoxides under Solvothermal Conditions

    Hiroaki Uchiyama, Koichi Matsumoto, Hiromitsu Kozuka

    CHEMISTRY LETTERS   39 ( 5 )   445 - 447   2010.5

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    Formation of anatase spheres was achieved via hydrolysis of Ti(OC3H7i)(4) modified with acetylacetone (acac) under solvothermal conditions at 150 degrees C. The reduction in the degree of hydrolysis by the modification of Ti(OC3H7i)(4) with acac led to the formation of a spherical shape. The 1-5 mu m in diameter spherical particles consisted of anatase nanocrystals below 10 nm in size.

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  • Preparation of LiFePO4 Mesocrystals Consisting of Nanorods through Organic-Mediated Parallel Growth from a Precursor Phase

    Hiroaki Uchiyama, Hiroaki Imai

    CRYSTAL GROWTH & DESIGN   10 ( 4 )   1777 - 1781   2010.4

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    Olivine-type LiFePO4 crystals were prepared from a precursor phase Fe-3(PO4)(2)(H2O)(8) by a reaction with LiOH under a hydrothermal condition. Particular rod-like units assembled in the same crystallographic orientation were formed in association with L-(+)-ascorbic acid as a reducing and capping agent. Fagot-like mesocrystals were constructed with the oriented rods through parallel growth by supplying abundant Fe2+ and PO43- ions from the precursor phase. An increase in the concentration of the organic additive decreased the unit size, and sheaf-like mesocrystals of LiFePO4 nanorods with high crystallinity and porous structure were obtained

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  • Synthesis and Applications of SnO Nanosheets: Parallel Control of Oxidation State and Nanostructure Through an Aqueous Solution Route

    Ken Sakaushi, Yuya Oaki, Hiroaki Uchiyama, Eiji Hosono, Haoshen Zhou, Hiroaki Imai

    SMALL   6 ( 6 )   776 - 781   2010.3

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    Tin monoxide (SnO) nanosheets 5 nm in thickness are generated on substrates through an aqueous solution process under mild conditions. Parallel control of the oxidation state and morphology is achieved by a urea-mediated approach in aqueous solution. The SnO nanosheets form a porous thin film on substrates such as indium tin oxide and carbon nanofiber (CNF). The porous thin film of SnO nanosheets shows cathodic photo-current generation upon irradiation by UV and visible light. In contrast, the photocurrent is not observed in the bulk SnO microcrystals. Composites of the SnO nanosheets and CNF perform as the anode material of lithium-ion batteries with improved charge discharge reversible stability.

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  • Specific Photocatalytic Performance of Nanostructured Rutile-Type TiO2: Selective Oxidation of Thiazin Dye with a Bundled Architecture Consisting of Oriented Nanoneedles

    Yu Tokunaga, Hiroaki Uchiyama, Yuya Oaki, Hiroaki Imai

    SCIENCE OF ADVANCED MATERIALS   2 ( 1 )   69 - 73   2010.3

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    The photocatalytic activity of a nanostrcutured rutile consisting of oriented nanoneedles was studied by comparing a reaction of a thiazin dye, methylene blue, with dispersed rutile nanoneedles and anatase nanoparticles. Demethylation of methylene blue occurred preferably through partial oxidation under UV irradiation with the bundled rutile nanoneedles having small clearance gaps. On the other hand, most of the dye molecules were directly decolorized through the initiation by a reductive pathway with the dispersed rutile nanorods and the anatase nanoparticles. The reductive sites on (110) of the rutile nanoneedles were dominantly located in the small gaps inside the bundled architecture. Because the diffusion of large-sized organic molecules to the reductive sites would be restricted, the oxidative route for the dye molecule was selectively induced with the rutile bundles under UV irradiation.

    DOI: 10.1166/sam.2010.1078

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  • Aqueous solution synthesis of SnO nanostructures with tuned optical absorption behavior and photoelectrochemical properties through morphological evolution

    Ken Sakaushi, Yuya Oaki, Hiroaki Uchiyama, Eiji Hosono, Haoshen Zhou, Hiroaki Imai

    NANOSCALE   2 ( 11 )   2424 - 2430   2010

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    We have studied the aqueous solution synthesis of divalent tin oxide (SnO) nanostructures, changes in their optical absorption behavior, and their photoelectrochemical properties. A number of SnO nanostructures including sheets and wires, and their composite morphologies were obtained in aqueous solution containing urea at low temperatures. Parallel control of both oxidation state and morphology was achieved through the urea-mediated solution process. Nanoscale morphological variation facilitated changes in optical absorption behavior and the generation of a photocurrent. As for the nanostructured SnO, the absorption of visible light decreased and absorption in UV region increased. In contrast, bulk black SnO crystals showed strong absorption over the entire range of UV to visible light. A photocurrent was generated from the SnO nanostructures with irradiation of UV and visible light.

    DOI: 10.1039/c0nr00370k

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  • Biomimetic Synthesis of Metal Ion-Doped Hierarchical Crystals Using a Gel Matrix: Formation of Cobalt-Doped LiMn2O4 with Improved Electrochemical Properties through a Cobalt-Doped MnCO3 Precursor

    Takao Kokubu, Yuya Oaki, Hiroaki Uchiyama, Eiji Hosono, Haoshen Zhou, Hiroaki Imai

    CHEMISTRY-AN ASIAN JOURNAL   5 ( 4 )   792 - 798   2010

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    We have synthesized spinel type cobalt-doped LiMn2O4 (LiMn2-y,CoyO4, 0 &lt;= y &lt;= 0.367), a cathode material for a lithium-ion battery, with hierarchical sponge structures via the cobalt-doped MnCO3 (Mn1-xCoxCO3, (0 &lt;= x &lt;= 0.204) formed in an agar gel matrix. Biomimetic crystal growth in the gel matrix facilitates the generation of both an homogeneous solid solution and the hierarchical structures under ambient condition. The controlled composition and the hierarchical structure of the cobalt-doped MnCO3 precursor played an important role in the formation of the cobalt-doped LiMn2O4. The charge discharge reversible stability of the resultant LiMn1.947Co0.053O4 was improved to ca. 12% loss of the discharge capacity after 100 cycles, while pure LiMn2O4 showed 24% loss of the discharge capacity after 100 cycles. The parallel control of the hierarchical structure and the composition in the precursor material through a biomimetic approach, promises the development of functional materials under mild conditions.

    DOI: 10.1002/asia.200900494

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  • Lithium insertion into nanometer-sized rutile-type TixSn1 (-) O-x(2) solid solutions

    Hiroaki Uchiyama, Eiji Hosono, Haoshen Zhou, Hiroaki Imai

    SOLID STATE IONICS   180 ( 14-16 )   956 - 960   2009.6

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    The electrochemical properties of rutile-type TixSn1-xO2 solid solutions (x = 0-1.0) as an anode for a lithium-ion battery were investigated using nanosized crystals prepared by an aqueous solution process. The reduction of the crystal size to nanoscale allowed a smooth lithium insertion into the rutile framework at room temperature. The lithium-insertion behavior of TiO2, SnO2, and the solid solutions was evaluated without any structural change of the rutile-type crystal structure in the potential range of 1.2-3.5 V (versus Li/Li+). The intersitial space for lithium ions were found to be derived from the crystal structure of the rutile framework and independent of the metal species. (C) 2009 Elsevier B.V. All rights reserved.

    DOI: 10.1016/j.ssi.2009.04.016

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  • Epitaxial growth of winding ZnO nanowires on a single-crystalline substrate

    Tetsuo Kawano, Hiroaki Uchiyama, Takanori Kiguchi, Satoshi Wada, Hiroaki Imai

    JOURNAL OF THE CERAMIC SOCIETY OF JAPAN   117 ( 1363 )   255 - 257   2009.3

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    Crystallographically oriented yet morphologically squiggly nanoscale ZnO architecture was produced through epitaxial growth by using a simple aqueous solution system. Specific adsorption of pyranine, an organic dye molecule having three sulfonic groups, suppressed regular growth in the c direction, and thus induced lateral growth of winding ZnO nanowires with diameters ranging from 20 to 100 rim on a single-crystalline ZnO (001) substrate. Although resultant wool-like structures consisted of tangled wires, the crystalline lattice of the whole architecture was found to be continuous and have six-fold symmetry originating from the single-crystalline substrate. (C) 2009 The Ceramic Society of Japan. All rights reserved.

    DOI: 10.2109/jcersj2.117.255

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  • Three-dimensional architectures of spinel-type LiMn2O4 prepared from biomimetic porous carbonates and their application to a cathode for lithium-ion batteries

    Hiroaki Uchiyama, Eiji Hosono, Haoshen Zhou, Hiroaki Imai

    JOURNAL OF MATERIALS CHEMISTRY   19 ( 23 )   4012 - 4016   2009

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    We demonstrated nanostructural control of a functional material for electrochemical applications by using a biomimetic solution route. A nanoscopically ordered architecture of calcite-type MnCO3 nanocrystals mimicking hierarchical structures of biological CaCO3 was successfully produced in an organic gel matrix. A highly porous structure of spinel-type LiMn2O4 was produced as a cathode material for lithium-ion batteries from the ordered MnCO3 architecture through nanocrystalline Mn2O3 as an intermediate phase. The rigid framework consisting of connected LiMn2O4 nanoparticles provided high durability in a lithium insertion/extraction process at a high current density due to a high porosity for the electrochemical reaction and three-dimensional channels for ion diffusion.

    DOI: 10.1039/b900397e

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  • Photoluminescence of nitrogen-doped anatase

    Terufumi Okumura, Yasuhiro Kinoshita, Hiroaki Uchiyama, Hiroaki Imai

    MATERIALS CHEMISTRY AND PHYSICS   111 ( 2-3 )   486 - 490   2008.10

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    Photoluminescence depending on nitrogen concentration was investigated using anatase-type TiO2 prepared by the calcination of a mixture of titanyl sulfate hydrate and urea. The substitutional ratio (x) of nitrogen in TiO2 was successfully varied from 0.004 to 0.022 by changing the molar ratio of the mixture. The absorbance at 380-560 nm due to the formation of mid-gap states was proportional to the substitutional ratio of nitrogen controlled by the preparation conditions. In contrast, the fluorescent intensity at 382 nm originating from the band-to-band transition monotonically decreased with an increase in the substitutional ratio with an expansion of the anatase lattice. On the other hand, the maximum intensity of photoluminescence at 560 nm excited at 350 nm, which could be associated with the transition from the conduction band to the mid-gap states, was observed at x = 0.01. The optimal substitutional ratio for the emission was almost agreed with that for the photocatalytic decomposition of methylene blue and acetaldeyde under visible-light illumination. The photoluminescence was fundamentally determined by the balance between photoexcitation originating from a sufficient number of mid-gap states and deactivation of excited electrons and holes due to lattice distortion or defective states induced with the nitrogen doping. (C) 2008 Elsevier B.V. All rights reserved.

    DOI: 10.1016/j.matchemphys.2008.04.053

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  • Matrix-mediated formation of hierarchically structured SnO crystals as intermediates between single crystals and polycrystalline aggregates

    Hiroaki Uchiyama, Hiroaki Imai

    LANGMUIR   24 ( 16 )   9038 - 9042   2008.8

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    Crystalline SnO grown in a Sn6O4(OH)(4) matrix exhibited hierarchical architectures, such as stepped bipyramids, stacked meshes, and rosettes, which were not categorized into the classical assortment of crystal morphologies. The complex architectures consisting of small building units were found to be produced through stacking and/or branching growth accompanied with a decrease in the unit size and degradation of the crystallographic symmetry in their assembly. This particular morphological evolution is presumed to be achieved by increasing the driving force of crystallization in the presence of abundant precursor species supplied from the matrix.

    DOI: 10.1021/la800955r

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  • Tin oxide meshes consisting of nanoribbons prepared through an intermediate phase in an aqueous solution

    Hiroaki Uchiyama, Hiroaki Imai

    CRYSTAL GROWTH & DESIGN   7 ( 5 )   841 - 843   2007.5

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    Novel nanoarchitectures of SnO and SnO2 crystals that had two- and three-dimensionally meshed structures consisting of nanoribbons were prepared through Sn6O4(OH)(4) as an intermediate state. Two-dimensional meshes consisting of oriented nanoribbons of single-crystalline tin monoxide (SnO) that was 50-300 nm wide were grown via Sn6O4(OH)(4), which was initially produced at room temperature. Textured spherical particles with three-dimensional meshed nanostructures were produced at 60 degrees C in the presence of citric acid in the aqueous system. The formation of the specific architectures is ascribed to the densely branching growth of SnO crystals in a matrix of Sn6O4(OH)(4) as a reactant. The meshed nanostructures of rutile-type tin dioxide were successfully obtained by oxidation of the SnO crystals without deformation of their architectures.

    DOI: 10.1021/cg070205k

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  • A nanoscale meshed electrode of single-crystalline SnO for lithium-ion rechargeable batteries Reviewed

    H. Uchiyama, E. Hosono, I. Honma, H. Zhou, H. Imai

    Electrochemistry Communications   10, 52-55   2007

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  • Selective preparation of SnO2 and SnO crystals with controlled morphologies in an aqueous solution system

    Hiroaki Uchiyama, Hirotoshi Ohgi, Hiroaki Imai

    CRYSTAL GROWTH & DESIGN   6 ( 9 )   2186 - 2190   2006.9

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    The oxidation state of tin oxide crystals grown in an aqueous solution of Sn( II) was successfully controlled. Rutile-type SnO2 and tetragonal SnO were selectively produced under acidic conditions below pH 3.3 and alkaline conditions above pH 13.1, respectively. The nanostructures, including the grain size and shape, and the mesoscopic assembled states of the crystals were changed with the concentration of the Sn( II) species and a subtle variation of the pH. This versatile fabrication process for functional oxides is based on the difference in the stability of Sn( II) and Sn(IV) depending on the pH in an aqueous solution system.

    DOI: 10.1021/cg060328p

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  • A novel adsorbent photocatalyst consisting of titania and mesoporous silica nanoparticles

    H Uchiyama, K Suzuki, Y Oaki, H Imai

    MATERIALS SCIENCE AND ENGINEERING B-SOLID STATE MATERIALS FOR ADVANCED TECHNOLOGY   123 ( 3 )   248 - 251   2005.11

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    The nanoscale combination of crystalline titania and mesoporous silica particles was successfully applied as a photocatalytic adsorbent for the rapid removal from air and complete decomposition of organic molecules. The composites consisted of anatase particles ca. 7 nm in diameter and mesoporous silica particles 10-100 nm in diameter, which provided a specific surface area of more than 1000m(2)/g. The composites were prepared through the assembly of surfactant micelles and siliceous species in the presence of the titania nanoparticles. Acetaidehyde was quickly removed from air due to the large surface area of the mesoporous silica and then was gradually decomposed into carbon dioxide under UV illumination with mass transfer between the adsorbent and the titania photocatalyst. (c) 2005 Elsevier B.V. All rights reserved.

    DOI: 10.1016/j.mseb.2005.08.007

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  • Crystal growth of metastable rutile-type TixSn1-xO2 solid solutions in an aqueous system

    H Uchiyama, H Imai

    CHEMICAL COMMUNICATIONS   48, 6014-6016 ( 48 )   6014 - 6016   2005

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    Nanoscale grains of crystalline TixSn1-xO2 were directly grown over the whole range of [Ti]/([Ti] + [Sn]) ratio (x = 0.00-1.00) in aqueous solutions at near room temperature.

    DOI: 10.1039/b511223k

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  • Neonate production potential of Moina macrocopa females hatched from parthenogenetic eggs and resting eggs Reviewed

    S. Yamasaki, H. Uchiyama

    Fisheries Science   67 ( 4 )   758 - 760   2001

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    DOI: 10.1046/j.1444-2906.2001.00318.x

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Books

  • 超低速ゾルーゲルディップコーティングの現状と課題

    内山 弘章, 幸塚 広光

    技術情報協会、、「“ウェブ”ロール toロールの搬送、巻取り技術 そのトラブル発生メカニズムと対策  2013.11 

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Presentations

  • Evaporation-driven deposition of functional metal oxide films from aqueous solutions by low-speed dip coating

    H. Uchiyama

    PACRIM 13  2019.10 

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    Venue:Okinawa, Japan  

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  • Evaporation-driven deposition of functional metal oxide thin films from organic-additive-free aqueous solutions by low-speed dip coating

    H. Uchiyama

    EUROMAT 2019  2019.9 

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    Venue:Stocholm, Sweden  

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  • Evaporation-driven deposition of WO3 electrochromic films by low-speed dip-coating technique

    H. Uchiyama

    20th International Sol-Gel conference  2019.8 

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    Venue:St. Petersburg, Russia  

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  • Biomimetic synthesis of nanostructured WO3 particles from aqueous solutions containing gelatin

    H. Uchiyama, S. Mizuguchi, Y. Nagayasu

    5th International Conference on Competitive Materials and Technology Processes  2018.10 

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    Venue:Miskolc, Hungary  

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  • Biomimetic synthesis of nanostructured WO3 particles from aqueous solutions containing biological polymers

    H. Uchiyama, S. Mizuguchi, Y. Nagayasu

    6th International Solvothermal and Hydrothermal Association Conference (ISHA2018)  2018.8 

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    Venue:Sendai, Japan  

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  • Spontaneous pattern formation induced by Bénard-Marangoni convection for sol-gel-derived titania dip-coating films

    H. Uchiyama, T. Matsui, H. Kozuka

    19th International Sol-Gel conference  2017.9 

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    Venue:Liege, Belgium  

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  • Preparation of ITO thin films from organic-additive-free aqueous solutions by low-speed dip-coating

    H. Uchiyama, T. Ito, H. Kozuka

    Euromat 2015 European Congress and Exhibition of Advances Materials and Processes  2015.9 

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    Venue:Warsaw, Poland  

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  • Molecular Design Approach to Single-Source Precursors of Perovskite Stannate Materials

    H. Uchiyama, G. Seisenbaeva, S. D. Topel, V. Kessler

    Oorgandagarna 2015  2015.6 

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    Venue:Wisby, Sweden  

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  • ゾル-ゲル法により作製されるセラミック薄膜のプラスチックス曲面への転写

    幸塚 広光, 井筒 功祐, 内山 弘章

    日本セラミックス協会 2014年年会  2014.3 

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  • ゾル-ゲル法によりSi(100) 基板上に作製されるTiO2薄膜の残留応力に及ぼす焼成時間の効果

    幸塚 広光, 坂本 翼, 内山 弘章

    日本セラミックス協会 2014年年会  2014.3 

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  • BaO-Nb2O5-P2O5系ガラスの構造と光学特性の関係

    北村 直之, 久野 祐輔, 福味 幸平, 内山 弘章, 幸塚 広光

    日本セラミックス協会 2014年年会  2014.3 

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  • Li2O-Bi2O3-B2O3ガラスの構造に関するラマン分光学的研究

    福味 幸平, 辻 俊, 北村 直之, 幸塚 広光, 内山 弘章

    日本セラミックス協会 2014年年会  2014.3 

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  • ポリオール法による板状ビスマス粒子の作製

    北村 直之, 平尾 直樹, 福味 幸平, 内山 弘章, 幸塚 広光

    日本セラミックス協会 2014年年会  2014.3 

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  • ゾル-ゲルコーティング膜におけるBénard-Marangoni 対流による自発的なパターン形成に及ぼす溶液の表面張力の効果

    内山 弘章, 松井 忠幸, 榮木 孝夫, 幸塚 広光

    日本セラミックス協会 2014年年会  2014.3 

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  • ゾル-ゲル法によるM+ドープCuO (M+ = Li+, Na+, K+) 薄膜の作製と光電極特性の評価

    内山 弘章, 磯部 公太, 幸塚 広光

    日本セラミックス協会 2014年年会  2014.3 

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  • ゾル-ゲル法により作製されるセラミック薄膜の残留応力に及ぼす有機高分子アンダーコート相の影響

    幸塚 広光, 住田 慎太郎, 内山 弘章

    日本セラミックス協会 2014年年会  2014.3 

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  • 酸化物ゲル膜の硬さに関する基礎的研究

    幸塚 広光, 小塩 知也, 内山 弘章

    日本セラミックス協会 2014年年会  2014.3 

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  • 超低速ディップコーティングによるSnCl4水溶液からのSnO2薄膜の作製

    内山 弘章, 伊藤 峻, 幸塚 広光

    日本セラミックス協会 2014年年会  2014.3 

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  • ゾル-ゲル法によりSi(100)基板上に作製されるSiO2薄膜の面内残留応力と焼成条件の関係

    小島 良平, 内山 弘章, 幸塚 広光

    第52 回セラミックス基礎科学討論会  2014.1 

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  • ゾルーゲル法により作製されるTiO2 膜の結晶化挙動に及ぼすポリビニルピロリドン添加の効果

    岡田 百人, 内山 弘章, 幸塚 広光

    第52 回セラミックス基礎科学討論会  2014.1 

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  • ゾルーゲル法による高価数金属酸化物(WO3、MoO3 およびV2O5)薄膜の作製と光電極特性の評価

    長尾 亮介, 内山 弘章, 幸塚 広光

    第52 回セラミックス基礎科学討論会  2014.1 

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  • マイクロパターンを有する色素ドープシリカ薄膜の超低速ディップコーティングによる作製

    内山 弘章, 佐々木 亮祐, 幸塚 広光

    第52 回セラミックス基礎科学討論会  2014.1 

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  • ゾル-ゲル法により作製されるTiO2ゲル膜の結晶化に及ぼすH2O量の効果

    内山 弘章, 岡田 百人, 幸塚 広光

    日本セラミックス協会第54回ガラスおよびフォトニクス材料討論会  2013.11 

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  • Sn6O4(OH)4の水熱処理によるSnO結晶の作製:ゼラチン添加によるナノ構造制御

    中西 俊介, 内山 弘章, 幸塚 広光

    日本セラミックス協会第26回秋季シンポジウム  2013.9 

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  • ポリシラザンをシリカ源として作製されるシリカ膜および有機高分子・シリカハイブリッド膜のハードコート特性

    北野 誉幸, 内山 弘章, 幸塚 広光

    日本セラミックス協会第26回秋季シンポジウム  2013.9 

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  • 熱可塑性と高い屈折率をもつ新規有機高分子フリー有機・チタニアハイブリッド材料の合成と評価

    小田 進也, 内山 弘章, 幸塚 広光

    日本セラミックス協会第26回秋季シンポジウム  2013.9 

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  • 有機高分子共存下での結晶成長による酸化物ナノ構造体の作製

    内山 弘章, 阪上 玲子, 中西 俊介, 幸塚 広光

    日本セラミックス協会第26回秋季シンポジウム  2013.9 

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  • Ceramic Thin Films on Plastics: A Versatile Sol-Gel Route Realizing Large Area as Well as Patterned Coating

    H. Kozuka, T. Fukui, M. Takahashi, S. Tsuboi, H. Uchiyama

    The 8th International Symposium in Science and Technology at Kansai University 2013  2013.8 

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    Venue:Osaka, Japan  

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  • Bénard-Marangoni対流によりゾル-ゲルディップコーティング膜に形成されるマイクロパターンの形状に及ぼす溶液組成の効果

    松井 忠幸, 内山 弘章, 幸塚 広光

    日本ゾル-ゲル学会第11会討論会  2013.8 

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  • PVP含有金属塩水溶液から作製されるZnO膜における自発的なシワ構造の形成

    榮木 孝夫, 内山 弘章, 幸塚 広光

    日本ゾル-ゲル学会第11会討論会  2013.8 

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  • アセチルアセトン含有アルコキシド溶液から作製されるTiO2ゲル膜の結晶化に及ぼすH2O量の効果

    内山 弘章, 岡田 百人, 幸塚 広光

    日本ゾル-ゲル学会第11会討論会  2013.8 

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  • 超低速ディップコーティングにより作製される色素ドープシリカ薄膜における自発的なマイクロパターン形成

    佐々木 亮祐, 内山 弘章, 幸塚 広光

    日本ゾル-ゲル学会第11会討論会  2013.8 

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  • 高屈折率と熱可塑性をもつ有機高分子フリー新規有機・チタニアハイブリッド材料の合成と物性

    小田 進也, 内山 弘章, 幸塚 広光

    日本ゾル-ゲル学会第11会討論会  2013.8 

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  • ランタン配位多面体とβ-ジケトンからなる有機・無機ハイブリッド材料の生成と熱可塑性に及ぼす合成条件の効果

    鈴木 康太, 内山 弘章, 幸塚 広光

    日本ゾル-ゲル学会第11会討論会  2013.8 

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  • ゾル-ゲルセラミック薄膜のプラスチック基板への加熱転写

    坪井 翔平, 内山 弘章, 幸塚 広光

    日本ゾル-ゲル学会第11会討論会  2013.8 

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  • Spontaneous pattern formation on organic-inorganic hybrid films prepared at extremely low substrate withdrawal speeds

    H. Uchiyama, D. Shimaoka, R. Sasaki, H. Kozuka

    17th International Sol-Gel Conference  2013.8 

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    Venue:Madrid. Spain  

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  • Ceramic thin films on plastics: a versatile route realizing large area as well as patterned coating

    H. Kozuka, T. Fukui, M. Takahashi, H. Uchiyama, S. Tsuboi

    17th International Sol-Gel Conference  2013.8 

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    Venue:Madrid. Spain  

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  • Spontaneous pattern formation on sol-gel-derived dip-coating films prepared at extremely low substrate withdrawal speeds

    H. Uchiyama, D. Shimaoka, R. Sasaki, H. Kozuka

    The 8th International Symposium in Science and Technology at Kansai University 2013  2013.8 

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    Venue:Osaka, Japan  

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  • Effects of the addition of acetylacetone on the crystallization of TiO2 films prepared by sol-gel method

    M. Okada, H. Uchiyama, H. Kozuka

    17th International Sol-Gel Conference  2013.8 

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    Venue:Madrid. Spain  

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  • Preparation and Characterization of new polymer-free organic-inorganic hybrid materials with thermoplastic properties and high refractive indicies

    S. Oda, H. Uchiyama, H. Kozuka

    17th International Sol-Gel Conference  2013.8 

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    Venue:Madrid. Spain  

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  • Preparation and Characterization of new organic-titania hybrid materials with thermoplastic properties and high refractive indicies

    S. Oda, H. Uchiyama, H. Kozuka

    The 8th International Symposium in Science and Technology at Kansai University 2013  2013.8 

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    Venue:Osaka, Japan  

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  • Preparation of SnO2 films from aqueous solutions of SnCl4 via dip-coating at extremely low substrate withdrawal speeds

    H. Uchiyama, T. Ito, H. Kozuka

    The 8th International Symposium in Science and Technology at Kansai University 2013  2013.8 

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    Venue:Osaka, Japan  

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  • ゾル-ゲル法によるFe-M-O (M = Zn, Mg, Ni, Bi)系薄膜の作製と光電極特性の評価

    長尾 亮介, 内山 弘章, 幸塚 広光

    日本セラミックス協会関西支部第8回学術講演会  2013.7 

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  • Sn6O4(OH)4の水熱処理によるSnO粒子の作製:ゼラチン添加によるナノ構造制御

    中西 俊介, 内山 弘章, 幸塚 広光

    日本セラミックス協会関西支部第8回学術講演会  2013.7 

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  • ゾル-ゲル法により作製される焼成セラミック薄膜をプラスチック基材に転写する技術の開発

    高橋 充, 内山 弘章, 幸塚 広光

    日本セラミックス協会関西支部第8回学術講演会  2013.7 

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  • アセチルアセトン含有アルコキシド溶液から作製されるTiO2膜の結晶化挙動に及ぼすH2O量の効果

    岡田 百人, 内山 弘章, 幸塚 広光

    日本セラミックス協会関西支部第8回学術講演会  2013.7 

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  • ビスマスホウリン酸塩ガラスにおける吸収端エネルギーとBi3+イオン周囲の構造の関連性

    福味 幸平, 北村 直之, 大塚 遼平, 幸塚 広光, 内山 弘章

    日本セラミックス協会関西支部第8回学術講演会  2013.7 

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  • ゾル-ゲル法により作製される酸化物薄膜の残留応力に関する基礎的研究

    小島 良平, 内山 弘章, 幸塚 広光

    日本セラミックス協会関西支部第8回学術講演会  2013.7 

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  • 超低速ディップコーティングにより作製されるゾル-ゲル薄膜における自発的なマイクロパターン形成

    内山 弘章, 佐々木 亮祐, 幸塚 広光

    日本セラミックス協会関西支部第8回学術講演会  2013.7 

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  • ポリシラザンをシリカ源として作製されるシリカ膜およびPMMA・シリカハイブリッド膜のハードコート特性

    北野 誉幸, 内山 弘章, 幸塚 広光

    日本セラミックス協会関西支部第8回学術講演会  2013.7 

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  • PVP 含有金属塩水溶液から作製されるZnO 膜における自発的なシワ構造の形成に関する基礎的研究

    内山 弘章, 榮木 孝夫, 幸塚 広光

    日本セラミックス協会 2013年年会  2013.3 

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  • ランタン配位多面体とβ-ジケトンからなる有機・無機ハイブリッド材料の合成と熱可塑性

    幸塚 広光, 鈴木 康太, 内山 弘章

    日本セラミックス協会 2013年年会  2013.3 

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  • ゾル‐ゲル法により作製されるITO薄膜のプラスチック基板への加熱転写

    幸塚 広光, 坪井 翔平, 内山 弘章

    日本セラミックス協会 2013年年会  2013.3 

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  • ゾル-ゲル法により作製されるY2O3薄膜の 残留応力に関する基礎的研究

    幸塚 広光, 中原 裕喜, 内山 弘章

    日本セラミックス協会 2013年年会  2013.3 

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  • ビスマスホウ酸塩ガラスの構造と透過特性の関連性

    福味 幸平, 大塚 遼平, 北村 直之, 内山 弘章, 幸塚 広光

    日本セラミックス協会 2013年年会  2013.3 

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  • 低速ディップコーティングにより作製される色素ドープシリカ・ポリビニルピロリドンハイブリッド薄膜における自発的なマイクロパターン形成

    内山 弘章, 佐々木 亮祐, 幸塚 広光

    日本セラミックス協会 2013年年会  2013.3 

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  • Bénard-Marangoni 対流によりゾル-ゲルディップコーティング膜に形成されるパターンの形状に及ぼす溶液組成の効果

    内山 弘章, 松井 忠幸, 幸塚 広光

    日本セラミックス協会 2013年年会  2013.3 

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  • ゾル-ゲル法で作製されるコーティング膜における自発的なパターン形成

    内山 弘章

    日本セラミックス協会 2013年年会  2013.3 

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  • アセチルアセトン含有アルコキシド溶液から作製されるTiO2ゲル膜の結晶化挙動に及ぼすH2O量の効果

    内山 弘章, 岡田 百人, 幸塚 広光

    日本セラミックス協会 2013年年会  2013.3 

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  • ポリシラザンをシリカ源として作製されるシリカ膜および有機・無機ハイブリッド膜のハードコート特性

    北野 誉幸, 中島 晃仁, 福嶋 泰基, 内山 弘章, 幸塚 広光

    第51 回セラミックス基礎科学討論会  2013.1 

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  • アルコキシド溶液から作製されるゾル-ゲル薄膜の結晶化挙動に及ぼすH2O量の効果

    内山 弘章, 岡田 百人, 幸塚 広光

    第51 回セラミックス基礎科学討論会  2013.1 

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  • 有機高分子共存下での結晶成長によるCeCO3OHナノ構造体の合成ならびにそれを中間体とするCeO2ナノ構造体の作製

    阪上 玲子, 内山 弘章, 幸塚 広光

    第51 回セラミックス基礎科学討論会  2013.1 

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  • Self-organization of linearly-arranged cell-like patterns on sol-gel dip-coating films induced by Bénard-Marangoni convection

    H. Uchiyama, Y. Mantani, H. Kozuka

    2012 Materials Research Society Fall Meeting  2012.11 

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    Venue:Boston, USA  

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  • Spontaneous Formation of Micrometer-Scaled Cell-like Patterns on Alkoxide-Derived Silica Films induced by Bénard-Marangoni Convection

    H. Uchiyama, Y. Mantani, H. Kozuka

    2nd International Conference on Competitive Materials and Technology Processes  2012.10 

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    Venue:Miskolc, Hungary  

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  • ゾル-ゲル法により作製されるセラミック薄膜の種々のプラスチック基材への転写性

    高橋 充, 内山 弘章, 幸塚 広光

    日本セラミックス協会第25回秋季シンポジウム  2012.9 

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  • 低速ディップコーティングにより作製されるゾル-ゲル薄膜における自発的なマイクロパターン形成

    内山 弘章, 嶋岡 大介, 幸塚 広光

    日本セラミックス協会第25回秋季シンポジウム  2012.9 

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  • 湿式プロセスによりペルヒドロポリシラザンから室温で作製されるシリカ膜の構造と性質

    中島 晃仁, 内山 弘章, 幸塚 広光

    日本セラミックス協会第25回秋季シンポジウム  2012.9 

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  • プラスチック基材表面に焼成ITO薄膜を転写する技術の開発

    福井 隆文, 内山 弘章, 幸塚 広光

    日本セラミックス協会第25回秋季シンポジウム  2012.9 

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  • 高い屈折率と熱可塑性をもつ新規有機・無機ハイブリッド材料の合成

    小田 進也, 内山 弘章, 幸塚 広光

    日本セラミックス協会第25回秋季シンポジウム  2012.9 

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  • ゾル-ゲル法により作製されるTiO2薄膜の結晶化挙動に及ぼすアセチルアセトン添加の効果

    岡田 百人, 内山 弘章, 幸塚 広光

    日本セラミックス協会第25回秋季シンポジウム  2012.9 

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  • Spontaneous formation of linearly-arranged microcraters on alkoxide-derived silica films induced by Bénard-Marangoni convection

    H. Uchiyama, Y. Mantani, H. Kozuka

    7th International Symposium in Science and Technology  2012.8 

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    Venue:Penang, Malaysia  

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  • Preparation and characterization of new organic-inorganic hybrid materials with high refractive indices and thermoplastic properties

    S. Oda, H. Uchiyama, H. Kozuka

    7th International Symposium in Science and Technology  2012.8 

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    Venue:Penang, Malaysia  

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  • アガロースゲルを反応場とする結晶成長によるCeCO3OHナノ構造体の合成ならびにそれを中間体とするCeO2ナノ構造体の作製

    阪上 玲子, 内山 弘章, 幸塚 広光

    日本セラミックス協会関西支部第7回学術講演会  2012.7 

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  • 高い屈折率と熱可塑性をもつ新規有機・チタニアハイブリッド材料の合成と評価

    小田 進也, 内山 弘章, 幸塚 広光

    日本ゾル-ゲル学会第10会討論会  2012.7 

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  • ゾル-ゲル法により作製されるTiO2薄膜の面内残留応力と熱処理温度の関係

    中西 俊介, 内山 弘章, 幸塚 広光

    日本ゾル-ゲル学会第10会討論会  2012.7 

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  • ゾル-ゲル法によるZnO-SnO2系薄膜の作製と光電極特性の評価

    長尾 亮介, 内山 弘章, 幸塚 広光

    日本ゾル-ゲル学会第10会討論会  2012.7 

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  • ゾル-ゲル法によりSi基板上に作製されるSiO2薄膜の残留応力と熱処理温度の関係

    小島 良平, 内山 弘章, 幸塚 広光

    日本ゾル-ゲル学会第10会討論会  2012.7 

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  • ゾル-ゲル法により作製されるセラミック薄膜の種々のプラスチック基材への転写性

    高橋 充, 内山 弘章, 幸塚 広光

    日本ゾル-ゲル学会第10会討論会  2012.7 

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  • ゾル-ゲル法により作製されるITO焼成膜のプラスチック基材への転写

    福井 隆文, 内山 弘章, 幸塚 広光

    日本セラミックス協会関西支部第7回学術講演会  2012.7 

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  • Bénard-Marangoni 対流を利用したシリカ-ポリビニルピロリドンハイブリッド膜のマイクロパターニング

    内山 弘章, 萬谷 裕人, 幸塚 広光

    日本ゾル-ゲル学会第10会討論会  2012.7 

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  • アルコキシド溶液から作製されるTiO2薄膜の結晶化挙動に及ぼすH2O量の効果

    岡田 百人, 内山 弘章, 幸塚 広光

    日本ゾル-ゲル学会第10会討論会  2012.7 

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  • ペルヒドロポリシラザンをシリカ源とする湿式プロセスにより作製されるPMMA・シリカハイブリッド膜のキャラタクタリゼーション

    中島 晃仁, 内山 弘章, 幸塚 広光

    日本セラミックス協会関西支部第7回学術講演会  2012.7 

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  • ビスマスホウ酸塩ガラスの光透過特性に及ぼす溶融条件の影響

    福味 幸平, 北村 直之, 北野 誉幸, 内山 弘章, 幸塚 広光

    日本セラミックス協会関西支部第7回学術講演会  2012.7 

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  • 化学修飾したアルコキシドの加水分解によるZrO2球状粒子の作製

    高木 啓次, 内山 弘章, 幸塚 広光

    日本セラミックス協会関西支部第7回学術講演会  2012.7 

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  • ゾル-ゲルディップコーティング膜におけるBénard-Marangoni 対流による自発的なパターン形成

    内山 弘章, 萬谷 裕人, 幸塚 広光

    日本セラミックス協会関西支部第7回学術講演会  2012.7 

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  • Spontaneous Formation of Micrometer-Scaled Cell-like Patterns on Sol-gel Films Induced by Bénard-Marangoni Convection

    H. Uchiyama, Y. Mantani, H. Kozuka

    The 6th International Conference on the Science and Technology for Advanced Ceramics (STAC-6)  2012.6 

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    Venue:Yokohama, Japan  

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  • ソルボサーマル法によるアルコキシド溶液からのZrO2およびZrTiO4球状粒子の作製

    内山 弘章, 高木 啓次, 幸塚 広光

    粉体粉末冶金協会平成24年度春季大会  2012.5 

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  • Deposition of functional crystalline metal oxide thin films on plastic substrates via sol-gel "firing" process

    H. Kozuka, A. Yamano, T. Fukui, H. Uchiyama, M. Takahashi

    10th CMCEE (International Symposium on Ceramic Materials and Components for Energy and Environmental Applications)  2012.5 

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    Venue:Dresden, Germany  

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  • Crystalline Metal Oxide Thin Films on Plastics: A Potential Deposition Technique with Sol-Gel-Based Firing Process

    H. Kozuka, A. Yamano, T. Fukui, H. Uchiyama, M. Takahashi, M. Yoki, T. Akase

    2012 Materials Research Society Spring Meeting  2012.4 

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    Venue:San Francisco, USA  

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  • Self-organized linear and cell-like patterns on alkoxide-derived dip-coating films

    H. Uchiyama, W. Namba (B), Y. Miki (B), H. Kozuka

    15th International Conference on Thin Films (ICTF 15), Kyoto (Japan)  2011.11 

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  • Spontaneous formation of linear patterns on silica and titania dip-coating films prepared at extremely low substrate withdrawal speeds

    H. Uchiyama, M. Hayashi (B), H. Kozuka

    16th International Sol-Gel Conference, Hangzhou (China)  2011.9 

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  • Spontaneous pattern formation on alkoxide-derived dip-coating films prepared at extremely low substrate withdrawal speeds

    H. Uchiyama, M. Hayashi (B), H. Kozuka

    6th International Symposium in Science and Technology at Kansai University 2011, Collaboration between Asian Countries in Science and Technology, Suita (Japan)  2011.8 

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  • Preparation of TiO2, ZrO2 and ZrTiO4 Spheres via Hydrolysis of Chemically Modified Alkoxides under Solvothermal Conditions

    H. Uchiyama, K. Matsumoto (D), H. Kozuka

    PAC RIM 9 (The 9th international meeting of pacific rim ceramic societies), Cairns, Queensland (Australia)  2011.7 

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  • Spontaneous formation of linear and cell-like patterns on alkoxide-derived dip-coating films induced by Benard-Marangoni convection

    H. Uchiyama, W. Namba (B), Y. Miki (B), H. Kozuka

    The 12th International Symposium on Biomimetic Materials Processing (BMMP-12), Nagoya (Japan)  2011.1 

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  • Three-dimensional architectures of spinel-type LiMn2O4 prepared from biomimetic porous carbonates and their application to a cathode for lithium-ion batteries

    H. Uchiyama, E. Hosono, I. Honma, H. Zhou, H. Imai

    International Symposium in Science and Technology at Kansai University 2009: Collaboration between Asian Countries in Life Science, Information Technology, and Civil Engineering, Suita, Aug. 23-25  2009 

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  • Preparation of nanostructured TiO2 via solvothermal process using chemically modified alkoxides

    H. Uchiyama, K. Matsumoto, H. Kozuka

    2009 MRS fall meeting, November 29-December 4, 2009, Hynes Convention Center&Sheraton Boston Hotel (USA)  2009 

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  • ルチル型TixSn1-xO2固溶体(x = 0.0‐1.0)のLiイオン二次電池電極特性評価

    内山弘章, 細野英司, 周豪慎, 本間格, 今井宏明

    電気化学会大75回大会, 2008年3月29~31日, 山梨大学甲府キャンパス(山梨県).  2008 

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  • Preparation of Hierarchically Structured SnO from Sn6O4(OH)4 as a Precursor Phase

    H. Uchiyama, H. Imai

    The 1st Korea-Japan Joint Forum on Sol-Gel Science and Technology, December 4-6, 2008, KAIST (Korea)  2008 

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  • Spinel-type Porous LiMn2O4 Prepared from Nanostructured MnCO3 and the application to a Cathode for Lithium Ion Secondary Batteries

    H. Uchiyama, E. Hosono, I. Honma, H. Zhou, H. Imai

    Pacific Rim Meeting on Electrochemical and Solid-State Science 2008, October 12-17, 2008, Hilton Hawaiian Village (USA)  2008 

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  • 階層構造を有するLiMn2O4の合成およびLi+イオン二次電池正極への応用

    内山弘章, 細野英司, 周豪慎, 本間格, 今井宏明

    日本セラミックス協会 2008年度年会, 2008年3月20~22日, 長岡技術科学大学(新潟県).  2008 

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  • 中間体を用いた水溶液プロセスによるLiFePO4の形態制御およびLiイオン二次電池正極への応用

    内山弘章, 細野英司, 周豪慎, 本間格, 今井宏明

    日本セラミックス協会 第21回 秋季シンポジウム, 2008年9月17~19日, 北九州国際会議場(福岡県).  2008 

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  • Crystal growth of metastable rutile-type TiXSn1-XO2 solid solutions in an aqueous system and their electrochemical applications

    H. Uchiyama, E. Hosono, H. Zhou, H. Imai

    TOEO-5, May 21-22, 2007, Shonan Village Center (Japan)  2007 

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  • 水酸化物の溶解再析出による一酸化スズ結晶の形態制御およびLiイオン二次電池への応用

    内山弘章, 今井宏明

    日本セラミックス協会 第45回 セラミックス基礎科学討論会, 2007年1月22~23日, 仙台国際センター(仙台市).  2007 

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  • Preparation of hierarchically structured SnO for Li ion batteries by an aqueous solution system

    H. Uchiyama, H. Imai

    EUROMAT 2007, September 10- 13, 2007, Congress Center Nürnberg, (Germany)  2007 

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  • Sn4+含有ポリマーからのSnO2ナノ結晶の合成およびリチウムイオン二次電池への応用

    内山弘章, 今井宏明

    日本セラミックス協会 2007年年会, 2007年3月21~23日, 武蔵工業大学世田谷キャンパス(東京都).  2007 

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  • 二酸化チタン‐メソ多孔質シリカナノ粒子複合型吸着性光触媒の作製

    内山弘章, 今井宏明

    日本セラミックス協会 2006年年会, 2006年3月14~16日, 東京大学駒場キャンパス(東京都).  2006 

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  • 水酸化物の溶解再析出による一酸化スズ結晶の形態制御

    内山弘章, 今井宏明

    日本セラミックス協会 第19回 秋季シンポジウム, 2006年9月19~21日, 山梨大学甲府キャンパス(山梨県).  2006 

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  • 水溶液プロセスによる一酸化スズ結晶の形態制御

    内山弘章, 今井宏明

    日本セラミックス協会 2006年年会, 2006年3月14~16日, 東京大学駒場キャンパス(東京都).  2006 

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  • Preparation of hierarchically structured SnO crystal by dissolution-reprecipitation from Sn6O4(OH)4 by hydrothermal process

    H. Uchiyama, H. Imai

    2006 MRS fall meeting, November 27-December 1, 2006, Hynes Convention Center&Sheraton Boston Hotel (USA)  2006 

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  • Preparation of hierarchically structured SnO crystal by dissolution-reprecipitation from Sn6O4(OH)4 in an aqueous solution system

    H. Uchiyama, H. Imai

    ISHR&ICSTR 2006, August 5-9, 2006, Sendai International Center (Japan)  2006 

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  • Crystal growth of SnO2 and SnO via aqueous solution process

    H. Uchiyama, H. Imai

    Three-Dimensional Multifunctional Ceramic Composites Workshop, October 3-5, 2005, Beckman Institute, University of Illinois at Urbana-Champaign (USA)  2005 

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  • 水溶液中における一酸化スズ結晶の直接合成および有機添加物による形態制御

    内山弘章, 今井宏明

    日本セラミックス協会 第18回 秋季シンポジウム, 2005年9月27~29日, 大阪府立大学中百舌鳥キャンパス(大阪府)  2005 

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  • ルチル型に酸化チタン‐二酸化スズ固溶体の水溶液からの直接析出

    内山弘章, 今井宏明

    日本セラミックス協会 2005年年会, 2005年3月22~24日, 岡山大学津島キャンパス(岡山県).  2005 

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  • Crystal growth of rutile-type TiO2-SnO2 solid solutions from aqueous solutions

    H. Uchiyama, H. Imai

    Fifth International Symposium on Biomimetic Materials Processing (BMMP-5), January 26- 28, 2005, Nagoya University (Japan)  2005 

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  • 水溶液からの結晶成長によるルチル型TixSn1-xO2固溶体の合成と組成制御

    内山弘章, 今井宏明

    日本セラミックス協会 第18回 秋季シンポジウム, 2005年9月27~29日, 大阪府立大学中百舌鳥キャンパス(大阪府).  2005 

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  • 二酸化チタン‐メソ多孔質シリカ複合型光触媒の作製

    内山弘章, 今井宏明

    日本セラミックス協会 第17回 秋季シンポジウム, 2004年9月17~19日,北陸先端科学技術大学院大学 石川ハイテク交流センター(石川県).  2004 

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Industrial property rights

  • セラミック薄膜の製造方法

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    Application no:2014-16445  Date applied:2014.1

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Research Projects

  • Preparation of highly-ordered nanostructured materials via novel aqueous process with biological polymers

    Grant number:19K05660  2019.4 - 2022.3

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research  Grant-in-Aid for Scientific Research (C)

    UCHIYAMA Hiroaki

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    Grant amount:\4290000 ( Direct Cost: \3300000 、 Indirect Cost:\990000 )

    We address the preparation of three-dimensionally nanostructured inorganic materials by biomimetic aqueous route.
    We achieved the morphological control of WO3 film materials by an aqueous solution process. WO3 hydrate layers were prepared on glass substrates via heterogeneous nucleation from aqueous solutions, and then thermally converted to monoclinic WO3 films. Micron-scale platy-particle WO3 films were obtained from WO3 hydrate layers. Hureaulite (Mn5(PO3OH)2(PO4)2 4H2O) crystals were obtained from the aqueous suspensions containing the as-deposited phases. The crystal size of the hureaulite products increased by increasing heating temperature and by addition of citric acid. Large hureaulite single crystals of ca. 500 μm in size was prepared from the precursor solutions containing citric acid.
    These results are beneficial for the development of novel aqueous solution techniques for making nanostructured inorganic materials.

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  • Spontaneous pattern formation induced by Benard-Marangoni convection for sol-gel-derived metal oxide films: Effect of molecule design of precursor materials

    Grant number:16H06054  2016.4 - 2019.3

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research  Grant-in-Aid for Young Scientists (A)

    UCHIYAMA HIROAKI

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    Grant amount:\16900000 ( Direct Cost: \13000000 、 Indirect Cost:\3900000 )

    We improved the spontaneous pattern formation induced by Benard-Marangoni convection triggered by solvent evaporation. Here, we attempted to control more precisely the pattern size by the molecule design of the precursor materials of sol-gel-derived ceramic films. Cell-like patterns of 1.0-1.5 μm in height and of ca. 20 μm in width were spontaneously formed on the surface of ceramic films prepared by sol-gel dip-coating process. We found that the size of the cell-like patterns induced by Benard-Marangoni convection increased with increasing molecule size of the precursor mateirals, which could be caused by the higher surface tension. Moreover, novel pattern formation was observed on ceramic films obtained from metal-acetylacetonate complexes, where dendrite patterns formed with decreasing substrate withdrawal speed. These results are beneficial for the development of novel self-organization triggered by solvent evaporation.

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  • Development of innovative organic-inorganic hybrid materials composed of polyoxometalates

    Grant number:26620199  2014.4 - 2016.3

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research  Grant-in-Aid for Challenging Exploratory Research

    Kozuka Hiromitsu, UCHIYAMA Hiroaki

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    Grant amount:\3900000 ( Direct Cost: \3000000 、 Indirect Cost:\900000 )

    Organically modified polyoxometalates were prepared by hydrolyzing metal alkoxides in the presence of chelating agents like benzoylacetone (BzAc), followed by concentration and drying. The softening temperature was found to be affected by the molecular weight of the polymerized species, which are varied with the amounts of the chelating agents and of the water for hydrolysis. Structural analysis based on pair distribution function suggested that the BzAc-modified polyoxotitanates are composed of TiO6 octahedra that are liked by corner- and edge-sharing. The BzAc-modified polyoxotitanates showed glass transition in their low-temperature TMA and DSC curves, suggesting that such organically modified polyoxometalates could be a new class of glassy materials.

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  • Development of an Innovative Technique for Fabricating Functional Ceramic Thin Films on Plastics Surface

    Grant number:24360277  2012.4 - 2015.3

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research  Grant-in-Aid for Scientific Research (B)

    KOZUKA Hiromitsu, UCHIYAMA Hiroaki

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    Grant amount:\17940000 ( Direct Cost: \13800000 、 Indirect Cost:\4140000 )

    We conducted experimental studies on our technique that allows the fabrication of ceramic thin films on plastic substrates. First, even when fired at temperatures higher than 600℃, the ceramic thin films could be transferred to plastic substrates. Second, we noticed that there is an optimized thickness of release layers that enables successful transfer of ceramic thin films onto plastic subsrates. Third, plastic substrates with polar groups were demonstrated to have good adhesion, while those with no polar groups have poor adhesion. However, even such plastic substrates with no polar groups exhibit good adhesion when subjected beforehand by UV/ozone treatment, which oxidizes the substrate surface. Finally the degree of plastic substrate bending that is not accompanied by film cracking was found to decrease with increasing firing temperature.

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  • Development of novel technique for patterning of ceramic thin films based on Benard convection

    Grant number:24760554  2012.4 - 2014.3

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research  Grant-in-Aid for Young Scientists (B)

    UCHIYAMA Hiroaki

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    Grant amount:\4420000 ( Direct Cost: \3400000 、 Indirect Cost:\1020000 )

    We suggested the spontaneous pattern formation induced by Benard-Marangoni convection as a novel patterning process of sol-gel-derived ceramic films. Cell-like micropatterns were spontaneously formed on the surface of silica films prepared via dip-coating process, where the surface patterns were linearly arranged parallel to the substrate withdrawal direction. Such highly-ordered micropatterns were achieved by Benard-Marangoni convection and the unidirectional flow of the coating solution on the substrate during dip-coating. We found that the size of the cell-like patterns induced by Benard-Marangoni convection increased with increasing coating temperature and surface tension of coating solutions. Moreover, novel pattern formation induced by capillary force was observed with decreasing substrate withdrawal speeds. These results are beneficial for the development of novel self-organization triggered by solvent evaporation.

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  • Development of Organic-Inorganic Hybrid Thin films of Extremely High Hardness and Chemical Durability

    Grant number:23656407  2011 - 2012

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research  Grant-in-Aid for Challenging Exploratory Research

    KOZUKA Hiromitsu, UCHIYAMA Hiroaki

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    Grant amount:\3900000 ( Direct Cost: \3000000 、 Indirect Cost:\900000 )

    Silica thin films were prepared from perhydropolysilazane (PHPS) via exposure to the vapor from aqueous ammonia. PHPS-derived silica films had higher hardness, chemical durability and adhesion to plastics than alkoxide-derived silica gel films. Polycarbonate plates were coated with polymethylmethacrylate, and then with PHPS, followed by the exposure to the vapor from aqueous ammonia, which successfully increased pencil hardness from under 10B to H - 2H.

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Devising educational methods

  • 学生実験を主に担当しており(1年次「フレッシュマンゼミナール:化学実験入門」、2年次「マテリアル科学実験1,2」、3年次「マテリアル工学実験1,2」)、実験前に実験概要や基礎的な知識の要点を提示し、学生に課題を明確に示した上で実験に行うようにしている。 また、実験終了時に課題レポートに最低限のまとめるべき内容を指示し、学生がレポートのまとめ方を学べるように意識した指導をしている。その際に、指示した内容に加えて各自で自由課題に取り組むように促し、学生が自主学習の意識を忘れないように配慮している。 これらの指導方法は、授業評価アンケートにおいて、この方法が理解を深めるのに非常に役立っているとの感想が多い。

Teaching materials

  •  特になし

Teaching method presentations

  •  特になし

Special notes on other educational activities

  • 自身が所属する化学・物質工学科において、主担当のマテリアル科学コースの教育はJABEEの認定を受けており、JABEEの基準に基づく継続的なコース教育改善に取り組んでいる。