2011年度環境物質工学科...

２０１１年度環境物質工学科

研究報告

1． MgO-Al2O3スピネルの耐スラグ侵食性に及ぼす ZrO2添加効果, 藤田基成，北基，伊賀棒公一，崎田真一，紅野安彦，難波徳郎，三浦嘉也，山口明良, 耐火物, Vol. 63, No. 6, pp. 279-286, 2011

2．ガラスの構造解析における INTERGLAD 構造データベースと重回帰分析の利用, 石井久美子，恒岡徹，崎田真一，紅野安彦，難波徳郎, New Glass, Vol.26, No. 4, pp. 21-25, 2011

3．環状ポリエチレンの球晶成長速度から探る高分子の結晶成長に及ぼすトポロジカルな拘束と結び目絡み合いの効果, 北原綱樹, 山崎慎一, 木村邦生, 高分子論文集, Vol. 68, No. 10, pp. 694-701, 2011

4．ガラスの相分離を利用した無機系廃棄物のケミカルリサイクル，難波徳郎，崎田真一，紅野安彦, Phosphorus Letter, Vol. 70, pp. 27-34, 2011

5． Effect of Ultrasonic Surface Treatment on the Transparency and Orientation of Fresnoite Surface Crystallization, A. ENDO, S. SAKIDA, Y. BENINO, T. NANBA, IOP Publishing IOP Conf. Series: Materials Science and Engineering, 18 (2011) 112015

6． Morphology Control of Various Aromatic Polyimidazoles-Preparation of Nanofibers, Jin Gong, Tetsuya Uchida, Shinichi Yamazaki, Kunio Kimura, Journal of Applied Polymer Science, Vol. 121, No. 5, pp. 2851-2860, 2011

7． One-Pot Preparation of Aromatic Poly(azomethine ester) Fibrillar Crystals Using Reaction-Induced Crystallization, Jin Gong, Yasuhide Yakushi, Tetsuya Uchida, Shinichi Yamazaki, Kunio Kimura, Journal of Polymer Science Part A: Polymer Chemistry, Vol. 49, No. 1, pp. 127-137, 2011

8． Selective synthesis of poly(p-oxybenzoyl) by fractional polycondensation: Enhancement of selectivity by shearing, Toshimitsu Ichimori, Shinichi Yamazaki, Kunio Kimura, Journal of Polymer Science Part A: Polymer Chemistry, Vol. 49, No. 21, pp. 4613-4617, 2011

9． Molecular Dynamics Simulation of Lead Borate and Related Glasses in Multicomponent Systems for Low Melting Vitrification of Nuclear Wastes, S. KATO, S. SAKIDA, Y. BENINO, T. NANBA, IOP Publishing IOP Conf. Series: Materials Science and Engineering, 18 (2011) 022014

10． Coloration and Depth Distribution of Cations Electrochemically-inserted into Electrochromic WO3 Thin Films, M. KAWAI, S. SAKIDA, Y. BENINO, T. NANBA, IOP Publishing IOP Conf. Series: Materials Science and Engineering, 18 (2011) 092039

11． Preparation of poly(p-oxybenzoyl) crystals using direct polymerization of p-hydroxybenzoic acid in the presence of boronic anhydrides, Masahiro Kihara, Shin-Ichiro Kohama, Shota Umezono, Kanji Wakabayashi, Shinichi Yamazaki, Kunio Kimura, Journal of Polymer Science Part A: Polymer Chemistry, Vol. 49, No. 5, pp. 1088-1096, 2011

12． Preparation of poly(2-oxy-6-naphthoyl) and copolymers using reaction-induced phase separation during direct polymerization in the presence of boronic anhydride, Masahiro Kihara, Shinichi Yamazaki, Kunio Kimura, Polymer Chemistry, Vol. 2, No. 5, pp. 1195-1202, 2011

13． Fabrication and characterization of Er3+-doped tellurite glass waveguide by Ag+-Na+ ion-exchange method, K. KIMURA, S. SAKIDA, Y. BENINO, T. NANBA, IOP Publishing IOP Conf. Series: Materials Science and Engineering, 18 (2011) 112018

14． Investigation of photocatalytic ozonation treatment of water over WO3 under visible light irradiation, Takayuki Mano, Shunsuke Nishimoto, Yoshikazu Kameshima, Michihiro Miyake, J. Ceram. Soc. Japan, Vol. 119, pp. 822-827, 2011

15． Effect of Addition of Non-oxides on the Slag Corrosion Resistance of MgO-Al2O3 Refractories, K. MORITA, S. SAKIDA, Y. BENINO, T. NANBA, IOP Publishing IOP Conf. Series: Materials Science and Engineering, 18 (2011) 222015

16． Characterization of Glasses Based on Basicity, Tokuro NANBA, Journal of the Ceramic Society of Japan, Vol. 119 No. 10, pp. 720-725, 2011

17． Phase separation of borosilicate glass containing phosphorus, Y. OHTSUKI, S. SAKIDA, Y. BENINO, T. NANBA, IOP Publishing IOP Conf. Series: Materials Science and Engineering, 18 (2011) 11202213．

18. Fabrication of layered double hydroxide/photoresponsive dendron nanocomposite multilayer film by electrostatic layer-by-layer assembly, Toshiyuki Tanaka, Shunsuke Nishimoto, Yoshikazu Kameshima, Michihiro Miyake, Mater. Lett., Vol. 65, pp. 2315-2318, 2011

19． Micro-flowers of poly(p-phenylene pyromelliteimide) crystals, Kanji Wakabayashi, Tetsuya Uchida, Shinichi Yamazaki, Kunio Kimura, Polymer, Vol. 52, No. 3, pp. 837-843, 2011

20． Preparation of Poly(p-phenylenepyromelliteimide) Microspheres with Rugged Surfaces Using Crystallization During Isothermal Polymerization, Kanji Wakabayashi, Tetsuya Uchida, Shinichi Yamazaki, Kunio Kimura, Macromolecular Chemistry and Physics, Vol. 212, No. 2, pp. 159-167, 2011

岡山大学環境理工学部研究報告 Vol. 17 No.17-4-1

MgO-Al2O3スピネルの耐スラグ侵食性に及ぼす ZrO2添加効果 Effect of ZrO2 addition on the slag corrosion resistance of MgO-Al2O3 spinel 藤田基成 1)，北基 2)，伊賀棒公一 3)，崎田真一 4)，紅野安彦 5)，難波徳郎 6)，三浦嘉也 7)，山口明良 8)

M. Fujita1), H. Kita2), K. Igabo3), S. Sakida4), Y. Benino5), T. Nanba6), Y. Miura7), A. Ymamguchi8)

■ 概要 ■ MgO-Al2O3 系スピネルに ZrO2 を添加することによって，微細構造や耐スラグ侵食性がどのように変化するか検討した。ZrO2添加による緻密化は，特に量論組成の MgO 含有量 50 mol%で顕著であった。また，ZrO2添加により緻密化の開始温度が低下し，その効果は ZrO2添加量が 2 vol%でも認められた。相対密度の上昇に伴い，溶融スラグによる損耗量は減少する傾向が認められた。ZrO2 添加量が 2 vol%の試料では，他の試料と同程度の相対密度であっても損耗量が低くなっていたが，10 vol%添加では無添加試料よりわずかに損耗量が大きくなっていた。これより，ZrO2 は溶融スラグに溶出するが，スラグ粘度が上昇することによってスラグの浸潤が抑制されたと結論付けた。 (a) MgO:Al2O3=50:50

(b) (MgO:Al2O3=50:50) + ZrO2 10vol%

(c) Cr2O3:Al2O3=10:90

Fig. 1 Photographs of the fractured surface of the sintered bodies after the slag corrosion test.

0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

50 60 70 80 90 100

M50M50Zr2M50Zr10M30M30Zr10Cr10

Wea

r dep

th / m

m

Relative density / %

Fig. 2 Relation between the wear depth and relative density of the sintered bodies fired at 1,600°C.

■キーワード■ 耐火物，スピネル，溶融スラグ，溶損，微細構造 ■ 所属 ■ 1) 黒崎播磨㈱，2) 日東紡㈱，3) 品川リフラクトリーズ㈱，4) 環境管理センター助教， 5) 環境物質工学科准教授，6) 環境物質工学科教授，7) 環境物質工学科名誉教授， 8) 岡山セラミックス技術振興財団 ■ 掲載先 ■ 耐火物, Vol.63(6), pp.279-286, 2011.6.

査読：あり，言語：日本語


ガラスの構造解析における INTERGLAD 構造データベースと重回帰分析の利用 Application of INTERGLAD Database and Multiple Regression Analysis for Structural Study of Glasses 石井久美子 1)，恒岡徹 2)，崎田真一 3)，紅野安彦 4)，難波徳郎 5)

Kumiko ISHII1), Toru TSUNEOKA2), Shinichi SAKIDA3), Yasuhiko BENINO4), Tokuro NANBA5)

■ 概要 ■

国際ガラスデータベース（INTERGLAD）は，ガラスの組成と特性に関する情報を収録した優れたデータベースであるが，2009 年にリリースされた Ver. 7 では新しい機能と改良が加えられ，ガラス構造研究の立場からも強力なツールとして利用されている。なかでも，新たに組み込まれたガラ

ス構造データベースは，IR，ラマン，NMR などの各種分析手法により得られるガラス構造情報を収録したものであり，これを活用することにより，従来の重回帰分析に基づく特性予測や組成設計

が対象ガラスの構造やその変化を考慮した高度な予測設計手法へ発展する可能性がある。当研究グループでは，主な研究内容の１つとしてガラス構造の解明を目的とした X 線光電子分光法（XPS）や NMR を利用した実験を行ってきた。既報のものを含めて，当研究グループ内にはこれらの構造解析結果に関する蓄積があり，データベース化による利用価値が高いと判断した。本稿

では，主としてボロシリケートガラスの XPS および 11B MAS NMR 分析結果について，INTERGLAD構造データベースの構築から重回帰分析による利用を紹介した。構造データベースでは，XPS や NMR をはじめ各種構造情報をユーザーデータとして登録する

ことが可能であり，これまでに測定された分析結果を可読状態で蓄積することが可能になるだけで

なく，今後のガラス構造研究において有効に利用されると考えられる。また，構造データの利用と

して重回帰分析の例を示したが，精度の高い多次の回帰式を導くことができ，二次および三次の相

互作用項の理解を含めた研究の進展に向けて，INTERGLAD の利用の更なる拡大が期待される。

図 1 O1s 束縛エネルギー(左)と 4 配位ホウ素の分率 N4(右)の三次重回帰分析結果

■キーワード■

ガラス構造，データベース，重回帰分析 XPS，NMR ■ 所属 ■

1) 環境学研究科資源循環学専攻学生，2) 環境物質工学科学生，3) 環境管理センター助教， 4) 環境物質工学科准教授，5) 環境物質工学科教授 ■ 掲載先 ■

New Glass, Vol.26(4), pp.21-25, 2011.12. 査読：なし，言語：日本語

Journal of The Faculty of Environmental Science and Technology, Okayama University, Vol. 17 No.17-4-3

環状ポリエチレンの球晶成長速度から探る高分子の結晶成長に及ぼすトポロ

ジカルな拘束と結び目絡み合いの効果 Tsunaki Kitahara1), Shinichi Yamazaki2), Kunio Kimura3) ■Summary■

In order to clarify the effects of entanglement species on nucleation of polymers, we studied the growth rate of spherulite G of cyclic and linear polyethylenes (C-PE and L-PE) from the melt as a function of degree of supercooling ΔT by means of polarizing optical microscope. We prepared several C-PEs with different weight average molecular weights Mw=9300, 43600 and 86500, and L-PE with Mw=44000. G of all the sample were obeyed the equation, G=G0exp(−B/ΔT). B of C-PE gradually increased with increasing Mw. B is proportional to the surface free energy of the end surface of the nucleus, and this indicates that the regularity of folding surface increased with increasing Mw. We consider that topological constraint of cyclic polymer becomes large with decreasing Mw of the cyclic polymer.

On the other hand, for C-PE and L-PE having almost the same Mw(=44k), G0 of C-PE is much less than that of L-PE. Due to the topological constraint of cyclic polymer, we speculated that the adsorption mode on the crystal surface of C-PE is different than that of L-PE.

10-2

10-1

100

101

102

G /

μm

min

.-1

0.100.080.060.040.02

ΔT -1 / K-1

L-PE (44k)

C-PE (9k)

C-PE (87k)

C-PE (44k)

⎟⎠⎞

⎜⎝⎛

Δ−=

TBGG exp0

Figure. Plots of growth rate G vs. reciprocal of degree of supercooling ΔT-1 for linear polyethylene (L-PE) and

cyclic polyethylene (C-PE) with different molecular weight. ■Key word■ Entanglement, Topology, Polyethylene, Cyclic Polymer, Spherulite, Growth Rate

■Affiliation■ 1) Graduate School of Environmental Science 2) Associate professor, Dept. of Environmental Chemistry and Materials 3) Professor, Dept. of Environmental Chemistry and Materials ■Printing■ Kobunshi Ronbunshu, Vol. 68, No. 10, pp. 694-701, 2011. DOI: 10.1295/koron.68.694

Refreeing: Full paper, Language: Japanese


ガラスの相分離を利用した無機系廃棄物のケミカルリサイクル Chemical Recycling of Inorganic Wastes by Using Phase Separation of Glass 難波徳郎 1)，崎田真一 2)，紅野安彦 3)

Tokuro Nanba1), Shinichi Sakida2), Yasuhiko Benino3)

■ 概要 ■

当研究グループでは，ガラスの相分離現象を利用した無機系廃棄物のリサイクルプロセスの開発に取

り組んでいる。開始当初は廃棄物中の着色元素の除去を主な目的としていたが，廃棄物に含まれるリン

が一方のガラス相に取り込まれることを見出したため，最近ではリンのリサイクルを目指した研究も進

めている。本稿では，リンのリサイクル研究を含め，廃棄物のリサイクルに関する当研究グループにて

行ってきた一連の研究成果を紹介した。 (a) 焼却灰

(b) 溶融スラグ

図 2 都市ごみの焼却灰，溶融スラグと回収固化体

0 20 40 60 80 100

CaO

SiO2

Al2O3

P2O5

Fe2O3

TiO2

K2O

S

焼却灰a:b=10:0

a:b=9:1

a:b=8:2

相対割合 (重量%)

0 20 40 60 80 100

CaO

SiO2

Al2O3

P2O5

Fe2O3

TiO2

K2O

S

溶融スラグs:b=10:0

s:b=9:1

s:b=8:2

相対割合 (重量%) 図 1 都市ごみの焼却灰，溶融スラグと回収固化体の組成（a : b や s : b は廃棄物と B2O3の重量比）

■キーワード■ 廃棄物，ケミカルリサイクル，ガラス，相分離 ■ 所属 ■ 1) 環境物質工学科教授，2) 環境管理センター助教，3) 環境物質工学科准教授 ■ 掲載先 ■ Phosphorus Letter, Vol.70, pp.27-34, 2011.2.

査読：なし，言語：日本語


Effect of Ultrasonic Surface Treatment on the Transparency and Orientation of Fresnoite Surface Crystallization A. ENDO1), S. SAKIDA2), Y. BENINO3), T. NANBA4) ■Summary■ Surface crystallized glass ceramics with fresnoite (Ba2TiSi2O8) phase were prepared by conventional heat treatment of 30BaO-20TiO2-50SiO2 glass together with ultrasonic surface treatment (UST) technique. The precursor glass was fully crystallized in a bulk form without any cracks, and the optical transparency and crystallographic orientation of the crystalline layers were evaluated by UV-Vis spectroscopy and XRD diffraction analyses, respectively. These properties were both enhanced significantly by applying UST using fresnoite/water suspension before the crystallization process, which is advantage for nonlinear optical applications of bulk glass ceramics. The effects of UST on the crystallization behavior were investigated by applying UST with various conditions. As the results, transparency and c-axis orientation of surface crystallized glass-ceramics were successfully enhanced by applying UST before the conventional heat treatment and the effective parameters of UST conditions were determined. However, the SEM observation of the glass surface after UST did not show any significant changes. The effect and mechanism of UST resulting in the enhancement of transparency and c-axis orientation are not yet explained at present, but the practical importance should be emphasized in order to develop new series of transparent glass ceramics with oriented crystals.

Figure 1. XRD analyses of surface orientation of fresnoite layer, (a) surface XRD patterns and (b) fresnoite-(004) rocking curves for various UST conditions.

■Key word■ Glass Ceramics, Crystallization, Ultrasonic Surface Treatment ■Affiliation■ 1) Graduate School of Environmental Science 2) Assistant Professor, Environmental Management Center 3) Associate Professor, Dept. of Environmental Chemistry and Materials 4) Professor, Dept. of Environmental Chemistry and Materials ■Printing■ IOP Publishing IOP Conf. Series: Materials Science and Engineering 18 (2011) 112015 doi:10.1088/1757-899X/18/11/112015 Peer-reviewed paper, Language: English


Morphology Control of Various Aromatic Polyimidazoles-Preparation of Nanofibers Jin Gong1), Tetsuya Uchida2), Shinichi Yamazaki3), Kunio Kimura4)

■Summary■ Morphology of four kinds of aromatic polyimidazoles

was examined by using reaction-induced crystallization during solution polymerization at a concentration of 1% at 350 oC in liquid paraffin (LPF), dibenzyltoluene (DBT), and the mixture of these solvents. Aggregates of ribbon-like crystals of poly[2,6-(2,6-naphthalene)-benzobisimidazole] were obtained in LPF, and those of plate-like crystals were obtained in DBT/LPF-50 and in DBT. In contrast to this, the network structures of poly[2,2'-(2,6-naphthalene)-5,5'-bibenzimidazole)] (PNT-BBI) nanofibers with the diameter of 25 to 90 nm was mainly obtained in DBT. The network structures of the PNT-BBI nanofibers could be recognized as nonwoven fabrics of the high-performance polymers. Imidazole trimers were precipitated to form the ribbon-like crystals and then they were continuously supplied from solution to grow the crystals. Molecular weight increased by the polymerization on the surface of the crystals when they crystallized and in the crystals. The initially formed aggregates of ribbon-like crystals changed to the nanofibers with time. In the case of poly[2,6-(4,4'-biphenylene)-benzobisimidazole] and poly[2,2'-(4,4'-biphenylene)-5,5'-bibenzimidazole)], they exhibited various morphologies such as spheres, lath-like crystals, and the spherical aggregates of lath-like crystals depending on the solvent, but fibers like PNT-BBI were not formed. The crystals obtained in this study possessed very high crystallinity and the outstanding thermal stability measured by TGA. ■Key word■ crystallization; fibers; high performance polymers; morphology; polyimidazole

■Affiliation■ 1) Graduate School of Environmental Science 2) Graduate School of Natural Science and Technology 3) Associate professor, Dept. of Environmental Chemistry and Materials 4) Professor, Dept. of Environmental Chemistry and Materials ■Printing■ Journal of Applied Polymer Science Vol. 121, No. 5, pp. 2851-2860, 2011. DOI: 10.1002/app.33914

Refreeing: Full paper, Language: English

Figure. Morphologies of PNT-BI crystals prepared in (a) LPF, (b) DBT, and PNT-BBI crystals prepared in (c) LPF, (d) DBT/LPF-70, (e) DBT/LPF-50, (f, g) DBT/LPF-30, and (h) DBT.


One-Pot Preparation of Aromatic Poly(azomethine ester) Fibrillar Crystals Using

Reaction-Induced Crystallization Jin Gong1), Yasuhide Yakushi2), Tetsuya Uchida3), Shinichi Yamazaki4), Kunio Kimura5) ■Summary■

Polymerizations of 4-(4-acetoxybenzylideneamino)-benzoic acid were performed in dibenzyltoluene (DBT) and a mixture of DBT and liquid paraffin at 350 oC for 6 h. Fibrillar crystals of poly[4-(4-oxybenzylideneamino)benzoyl] (POAB) having the width of 50-450 nm and the length of over 15 pm were obtained by the crystallization during the polymerization. The fibrillar crystals possessed high crystallinity and the molecular chains aligned perpendicular to the long axis of the fibrillar crystals. Plate-like crystals were initially formed by the crystallization of oligomers, and then they changed to the fibrillar crystals via the formation of bundle-like crystals after 1 h. Molecular weight increased by the further polymerization in the crystals. Based on these results, one-pot preparation of the fibrillar POAB crystals was examined by the polymerization of 4-acetoxybenzaldehyde and 4-aminobenzoic acid. The polymerization at 180 oC for 2 h and then at 350 oC for 6 h afforded the fibrillar crystals with a small amount of the ribbon-like crystals. Although the side-reaction to generate the p-benzamide sequences was not completely depressed, the sequence of heating in which 180 oC for the formation of the azomethine linkage and then 350 oC for the formation of the ester linkage was preferable to prepare the fibrillar POAB crystals. ■Key word■ fibers, high performance polymers, morphology, poly(azomethine ester), reaction-induced crystallization

■Affiliation■ 1) Graduate School of Environmental Science 2) Faculty of Environmental Science and Technology 3) Graduate School of Natural Science and Technology 4) Associate professor, Dept. of Environmental Chemistry and Materials 5) Professor, Dept. of Environmental Chemistry and Materials ■Printing■ Journal of Polymer Science Part A: Polymer Chemistry Vol. 49, No. 1, pp. 127-137, 2011. DOI: 10.1002/pola.24427


Figure. Morphology of POAB prepared from ABBA for 6 h at a concentration of 1% (a) in LPF at 300 °C, (b) in DBT at 300 °C, (c) in LPF at 350 °C, (d) in DBT at 350 °C, (e) in DBT-LPF at 350 °C, and (f) at a conc. of 5% in DBT-LPF at 350 °C.


Selective synthesis of poly(p-oxybenzoyl) by fractional polycondensation:

Enhancement of selectivity by shearing Toshimitsu Ichimori1), Shinichi Yamazaki2), Kunio Kimura3) ■Summary■

The influence of shear flow, especially the timing for the application of shearing, was examined to enhance the selectivity for the preparation of poly(p-oxybenzoyl) (Pp-OB) by using hydrodynamically induced phase separation during polymerization of 4-(4-acetoxybenzoyloxy)benzoic acid (p-ABAD) and m-acetoxybenzoic acid (m-ABA). The polymers containing few m-oxybenzoyl (m-OB) moieties were obtained as precipitates even at high content of m-OB moiety in feed (χf) under shear flow. The content of m-OB moiety in the precipitates (χp) prepared under shearing throughout the polymerization at the shear rate (γ) of 489 s−1 was 6.3 mol % even at χf of 60 mol %. Especially, the Pp-OB was obtained as the precipitates at χf of less than 50 mol %. The timing of the application of the shearing influenced the selectivity significantly, and the shearing just after the precipitation of the oligomers started was quite efficient to enhance the selectivity more. The χp of the precipitates prepared with shearing at γ of 489 s−1 just after the precipitation was only 3.9 mol % even at χf of 60 mol %. The shear flow reduced the difference in the reactivity between p-ABAD and m-ABA, resulting in the decrease in the selectivity with regard to the formation of p-oxybenzoyl homo-oligomer. However, the shear flow enhanced the difference in the miscibility between homo-oligomers and co-oligomers. This change in the miscibility by shear flow brought about the more rapid precipitation of homo-oligomers, leading to the enhancement of the selectivity.

Figure. Plots of yield (triangle) and value of χp (circle) during polymerization of p-ABAD and m-ABA at χf of 60 mol % at γ of 0 (○, ▵) and 489 s−1 (•, ▴). Shearing was applied after (a) 70 min and (b) 30 min.

■Key word■ crystallization, polycondensation, polyesters, selective synthesis, shear

■Affiliation■ 1) Graduate School of Environmental Science 2) Associate professor, Dept. of Environmental Chemistry and Materials 3) Professor, Dept. of Environmental Chemistry and Materials

■Printing■ Journal of Polymer Science Part A: Polymer Chemistry Vol. 49, No. 21, pp. 4613-4617, 2011. DOI: 10.1002/pola.24904


Journal of The Faculty of Environmental Science and Technology, Okayama University, Vol. 17 No.17-4-9 Molecular Dynamics Simulation of Lead Borate and Related Glasses in Multicomponent Systems for Low Melting Vitrification of Nuclear Wastes S. KATO1), S. SAKIDA2), Y. BENINO3), T. NANBA4) ■Summary■ Glasses based on lead oxide have excellent properties in general such as low melting point, high chemical durability and high stability of glassy form, which are suitable for the preservation of volatile nuclear wastes in a permanent vitrified form. In order to confirm the long-term performance of lead borate based glasses it is necessary to establish dissolution and diffusion processes based on a reliable model of the glass structure. In the present study molecular dynamics (MD) simulation of lead borate based glasses was carried out introducing a dummy negative point charge to reproduce asymmetric PbOn units. Parameters for the dummy charge were optimized based on the comparison between calculated radial distribution function and experimental one. Asymmetric coordination around Pb, for example trigonal bipyramid, was successfully reproduced in the MD simulated binary and ternary glass models. The simple model using the dummy charge was confirmed to be valid for further simulations of multicomponent glasses containing nuclear wastes and heavy elements.

Table 1. Change in coordination number of Pb (NPb-O) by varying QDC and dDC. for 66.7PbO-33.3B2O3 glass

dDC QDC NPb-O (r < 2.85Å)None 4.66 2.0 −0.5 4.55 1.6 −0.5 4.40 1.2 −0.5 4.29 0.8 −0.5 4.32 0.4 −0.5 4.54 1.2 −0.7 4.34 1.2 −0.9 4.32

Fig. 1. MD model for 66.7PbO-33.3B2O3 glass

obtained from the best parameter set

0 2 4 6 8 100

20

40

60

80

r (Å)

4π

r2ρ

(r)(Å

-1)

Pb-O peak

Pb-Pb peak

experimental simulation

Fig. 2. X-ray weighted RDF for 66.7PbO-33.3B2O3 glass calculated from the MD model shown in Fig. 1

■Key word■ Glass Structure, Molecular Dynamics Simulation, Low Melting Glass, Heavy Metal Oxides ■ Affiliation ■ 1) Graduate School of Environmental Science 2) Assistant Professor, Environmental Management Center 3) Associate Professor, Dept. of Environmental Chemistry and Materials 4) Professor, Dept. of Environmental Chemistry and Materials ■Printing■ IOP Publishing IOP Conf. Series: Materials Science and Engineering 18 (2011) 022014 doi: 10.1088/1757-899X/18/2/022014 Peer-reviewed paper, Language: English

Journal of The Faculty of Environmental Science and Technology, Okayama University, Vol. 17 No.17-4-10 Coloration and Depth Distribution of Cations Electrochemically-inserted into Electrochromic WO3 Thin Films M. KAWAI1), S. SAKIDA2), Y. BENINO3), T. NANBA4) ■Summary■ Amorphous tungsten trioxide (WO3) film is a promising material for electrochromic device applications, and it has been researched widely. Electrochromism is a phenomenon that accompanies the electrochemical redox reaction together with the change in color and optical transmittance. Li+ and H+ ions were electrochemically inserted into amorphous WO3 films prepared on an ITO-coated glass substrate by an R.F. magnetron sputtering method under Ar/O2 flow ratios of 4/1 (SP1) and 1/1 (SP2). The cation distribution was estimated indirectly by depth profiles of refractive-index obtained from prism coupler measurements and was evaluated directly by glow discharge spectrometry (GDS). H+ ions inserted were segregated only at deeper region around ITO electrode, which was independent to the preparing condition. In the case of Li+ insertion into SP1 film, Li+ ions were initially segregated at around ITO electrode, and after further insertions, they were also distributed at around the surface of WO3 film. In SP1 film, Li+ ions at around ITO electrode seemed to contribute to coloration. In SP2 film, however, Li+ ions subsequently inserted, which were uniformly distributed in the film, were only involved in coloration. The difference in depth distribution and coloration was due to the difference in atomic structure of WO3 films.

0 5 10 15 20 25

x=0.20x=0.10as-deposited

Inte

nsity

(a.u

.)

Sputtering time (sec)

Air ITO

Figure 1. Distribution profiles of Li+ ions obtained from GDS measurements for LixWO3 (x = 0 − 0.20) films, Ar/O2 = 4/1.

0

0.2

0.4

0.6

0.8

1.0

1.2

0 0.2 0.4 0.6 0.8 1.0 1.2

Li(20%)#17

H(20%)#35

Li(50%)#194

H(50%)#139

Abs

orba

nce

@80

0nm

M+ content, x in MxWO3 Figure 2. Change in absorbance at λ = 800 nm against cation content x.

■Key word■ Electrochromism, Thin Film, Sputtering, Depth Distribution ■Affiliation■ 1) Graduate School of Environmental Science 2) Assistant Professor, Environmental Management Center 3) Associate Professor, Dept. of Environmental Chemistry and Materials 4) Professor, Dept. of Environmental Chemistry and Materials

■Printing■ IOP Publishing IOP Conf. Series: Materials Science and Engineering 18 (2011) 092039 doi:10.1088/1757-899X/18/9/092039 Peer-reviewed paper, Language: English


Preparation of poly(p-oxybenzoyl) crystals using direct polymerization of p-hydroxybenzoic acid in the presence of boronic anhydrides Masahiro Kihara1), Shin-Ichiro Kohama1), Shota Umezono1), Kanji Wakabayashi1), Shinichi Yamazaki2), Kunio Kimura3) ■Summary■

Poly(p-oxybenzoyl) (POB) crystals were prepared by reaction-induced crystallization during direct polymerization of p-hydroxybenzoic acid in the presence of boronic anhydrides. Polymerizations were carried out at 300 oC in dibenzyltoluene at a concentration of 1% with three kinds of anhydrides of boronic acid such as 3,4,5-trifluorophenylboronic acid (TFB), 4-methoxyphenylboronic acid (MPB) and 4-biphenylboronic acid (BPB). The POB crystals were formed as precipitates in the solution and the morphology was considerably influenced by both the structure of the boronic anhydride and its concentration (cB). Needle-like crystals were firmed in the presence of TFB anhydride (TFBA) at cBs of 5 and 10 mol % by the spiral growth of lamellae. Spherical aggregates of slab-like crystals were formed at cBs from 50 to 100 mol %. The polymerization with MPB anhydride and BPB anhydride (BPBA) also yielded the needle-like crystals at cBs of 50 and 5 mol %, respectively. The polymerization with TFBA at lower cBs was favorable to prepare the needle-like crystal. Molecular weight was also influenced by the structure of the boronic anhydride and cBs. Mn increased generally with cBs and BPBA gave the highest Mn of 14.7 x 103 at cBs of 100 mol %. The loose packing of the molecules in the crystal caused by the bulkiness of the end-groups made the polymerization in the crystals more efficiently. Morphology and molecular weight of the POB crystals could be controlled by the chemical structure and the content of boronic anhydride. ■Key word■ crystallization, high performance polymers, morphology, polycondensation, polyesters


■Printing■ Journal of Polymer Science Part A: Polymer Chemistry Vol. 49, No. 5, pp. 1088-1096, 2011. DOI: 10.1002/pola.24521


Figure. POB crystals prepared in the presence of TFBA at cB of (a) 10 mol %, (b) 100 mol %, and MPBA at cB of (c) 10 mol %; (d) 50 mol %, (e) 100 mol %, and BPBA at cB of (f) 5 mol %; (g) 100 mol %.


Preparation of poly(2-oxy-6-naphthoyl) and copolymers using reaction-induced

phase separation during direct polymerization in the presence of boronic anhydride Masahiro Kihara1), Shinichi Yamazaki2), Kunio Kimura3) ■Summary■

Poly(2-oxy-6-naphthoyl) (PON) was obtained as precipitates by direct polymerization of 2-hydroxy-6-naphthoic acid (HNA) in the presence of boronic anhydrides such as 2,4,6-tris(3,4,5-trifluorophenyl)-1,3,5,2,4,6-trioxatriborinane (TFBA) and 2,4,6-tri(biphenyl-4-yl)-1,3,5,2,4,6-trioxatriborinane (BPBA). The polymerizations were carried out in an aromatic solvent at 300 °C for 24 h. Both morphology and molecular weight of the PON precipitates were considerably influenced by not only the structure of the boronic anhydride but also its concentration (cB). Spheres with needles on their surface were formed in the polymerization with TFBA at cB of 50–70 mol%, and those having smooth surface were obtained at cB of 100 mol%. The Mn increased with the value of cB in the range from 2.7 × 103 to 9.0 × 103. Aggregates of cone-like crystals were prepared in the polymerization with BPBA at cB of 10–30 mol%, and spheres having rugged surface were formed at cB of 50–100 mol%. The Mn also increased with the value of cB in the range from 5.4 × 103 to 12.9 × 103. These PON precipitates possessed high crystallinity in spite of the morphology. The copolymerization of HNA and 4-hydroxybenzoic acid (HBA) was also examined in the presence of BPBA at cB of 100 mol% with varying the content of HBA in feed (rf). Copolymers were obtained as spheres of which the content of 4-oxybenzoyl moiety was lower than the value of rf due to the difference in the solubility of the oligomers.

■Key word■ Liquid-crystalline polymers, X-ray diffraction, Poly(oxy-2,6-naphthalenediylcarbonyl), whiskers


■Printing■ Polymer Chemistry Vol. 2, No. 5, pp. 1195-1202, 2011. DOI: 10.1039/C0PY00420K



Fabrication and characterization of Er3+-doped tellurite glass waveguide by Ag+-Na+ ion-exchange method K. KIMURA1), S. SAKIDA2), Y. BENINO3), T. NANBA4) ■Summary■ It is requested to enhance the speed and density of telecommunication with increasing in the demand for optical communication. As one of the solutions, the wavelength division multiplexing (WDM) method attracts attention. A wideband optical amplifier as one of optical devices is indispensable in order to amplify communication light that attenuates by transmission. An Er3+-doped tellurite glass is an attractive material as a broadband amplifier at 1.5 μm in WDM network. An optical waveguide forms the basis for an integrated optical device applicable to an amplifier and laser for high-speed signal processing in telecommunication. The optical waveguides have been fabricated on substrate glasses by means of various techniques such as ion-exchange, sol-gel, plasma enhanced chemical vapor deposition (PECVD), physical vapor deposition (PVD), flame hydrolysis deposition (FHD), pulsed laser deposition (PLD), rf-sputtering and laser writing. Among these techniques, an ion-exchange method is effective to make an optical waveguide on a substrate glass owing to its simplicity, flexibility, reliability and low cost. So far, many studies about optical waveguides fabricated on silicate, soda-lime, borosilicate and phosphate substrate glasses by ion-exchange have been reported. However, studies about the fabrication and characterization of tellurite glass waveguides by ion-exchange are a few although the waveguide amplifier in a tellurite glass is expected to exhibit high optical gain and to be low-cost and compact. Hence, the further information about the fabrication and characterization of tellurite glass waveguides by ion-exchange is necessary. In the present study, the planar waveguides of 12Na2O·10NbO2.5·25WO3·53TeO2+1Er2O3 ([NbWEr]) glasses were prepared by Ag+-Na+ ion-exchange at 320-380°C for 5-30 h. The optical properties of the waveguides were characterized. Waveguiding property was successfully confirmed under all the ion-exchange conditions in this study. The thickness of the waveguides increased with increasing ion-exchange temperature and time. The minimum propagation loss of the waveguides was approximately 0.8 dB/cm at 632.8 nm. This value was the lowest in the tellurite glass waveguides fabricated by the authors’ group until now. Hence, the [NbWEr] glass waveguides were considered to be promising for broadband optical amplifiers.

Figure 1. Refractive index profiles at 632.8 nm for [NbWEr] glass waveguides fabricated by ion- exchange at 360°C for 5-30 h.

Figure 2. Relationship between propagation losses at the wavelength of 632.8 nm and ion-exchange temperatures for [NbWEr], [TiWEr], [AlWEr], [ZrWEr] and [WEr] glass waveguides.

■Key word■ Glass Waveguide, Ion Exchange, Tellurite Glass ■Affiliation■ 1) Graduate School of Environmental Science 2) Assistant Professor, Environmental Management Center 3) Associate Professor, Dept. of Environmental Chemistry and Materials 4) Professor, Dept. of Environmental Chemistry and Materials ■Printing■ IOP Publishing IOP Conf. Series: Materials Science and Engineering 18 (2011) 112018 doi:10.1088/1757-899X/18/11/112018 Peer-reviewed paper, Language: English


Investigation of photocatalytic ozonation treatment of water over WO3 under

visible light irradiation Takayuki Mano1), Shunsuke Nishimoto2), Yoshikazu Kameshima3), Michihiro Miyake4) ■ Summary ■ Water treatment by photocatalytic ozonation over bare WO3 under visible light irradiation (O3/vis/WO3) system was performed under different experimental conditions using a phenol aqueous solution as model wastewater. The effects of parameters such as the initial phenol concentration, water temperature, and initial solution pH on the total organic carbon (TOC) removal efficiency in the O3/vis/WO3 system were investigated. The results suggest that the TOC removal process consists of three stages, and the combined effect of photocatalysis and ozonation, which is important for complete TOC removal, became dominant in the third stage. Furthermore, the TOC removal efficiency increased with increasing water temperature in the O3/vis/WO3 system. Figure. Phenol wastewater treatment using a WO3 photocatalyst combined with ozonation under visible light irradiation. ■ Key word ■ Visible-light-responsive photocatalyst, Tungsten oxide, Ozone, Phenol ■ Affiliation ■ 1) Graduate School of Environmental Science 2) Assistant Professor, Dept. of Environmental Chemistry and Materials 3) Associate Professor, Environmental Management Center 4) Professor, Dept. of Environmental Chemistry and Materials ■Printing■ J. Ceram. Soc. Japan, 119, 822-827 (2011).

Peer-reviewed full paper, Language: English


Effect of Addition of Non-oxides on the Slag Corrosion Resistance of MgO-Al2O3 Refractories K. MORITA1), S. SAKIDA2), Y. BENINO3), T. NANBA4) ■Summary■ In the 1990's dioxins exhausted from waste incineration plants have been a serious social issue in Japan, and reducing the dioxin emissions has been instructed strictly. High temperature melting incineration systems have been developed to prevent the generation of endocrine disrupters such as dioxin. Municipal waste is discharged as aggregated molten slag, which have greatly contributed to the volume reduction of wastes and the improvement of the waste disposal capabilities. In the high temperature melting furnaces, Al2O3-Cr2O3 refractories have been often used because of their high corrosion resistance against the molten slags. However, another issue has been raised, that is, generation of poisonous hexavalent chromium ions by reacting with the molten slag. Therefore the development of chromium free refractories with high corrosion resistance is needed. Then, in the present study, various non-oxides, such as SiC, Si3N4 and AlN were added to MgO-Al2O3 refractory, and the effect on the slag corrosion resistance was investigated. The specimens were prepared by a spark plasma sintering (SPS) method. Slag corrosion tests were carried out using a button method under a reducing atmosphere. Improvement in corrosion resistance was confirmed for the SiC-added specimens, and the addition of nitrides, however, resulted in deterioration. Wettability was also examined, and the compositional dependence was not observed in contact angle. Quantitative relation was not found between contact angle and penetration depth.

Table 1. Cross section of the sintered bodies of MgO-Al2O3 after slag corrosion tests under a reducing atmosphere

Table 2. Penetration depth (mm) after slag corrosion tests amount of additive (vol%) additive 0 2 5 10

SiC 0.50 0.36 0.73 0.49 Si3N4 0.50 1.34 0.93 0.71 AlN 0.50 2.74 1.50 1.50

0

10

20

30

40

50

10vol%

5vol%

2vol%

1200 1300 1400 1500

Con

tact

an

gle

/ d

eg

ree

Temperature / ℃

0vol%

Figure 1. Contact angle for molten slag on the sintered-bodies of MgO-Al2O3 including SiC.

■Key word■ Spinel, Non-Oxides, Refractory, Slag Corrosion Resistance ■Affiliation■ 1) Graduate School of Environmental Science 2) Assistant Professor, Environmental Management Center 3) Associate Professor, Dept. of Environmental Chemistry and Materials 4) Professor, Dept. of Environmental Chemistry and Materials ■Printing■ IOP Publishing IOP Conf. Series: Materials Science and Engineering 18 (2011) 222015 doi:10.1088/1757-899X/18/22/222015 Peer-reviewed paper, Language: English


Characterization of Glasses Based on Basicity Tokuro NANBA ■Summary■ Basicity is defined as an electron donating ability of a material, and hence, an oxide material containing oxide ions with high electron density is regarded to be in high basicity. It has been demonstrated that basicity can be evaluated by binding energy of core level electrons, which is measured by X-ray photoelectron spectroscopy. Based on the experimental results obtained from a large number of oxide glasses, correlations among basicity, O1s binding energy, structure and properties of glasses have been investigated. In the present paper, some of the research outcomes are introduced.

528

530

532

534

0.4 0.5 0.6 0.7

B2O

3

SiO2

P2O

5

GeO2

TeO2

Bi2O3

O1

s b

ind

ing

ene

rgy,

EB(O

1s)

/ eV

Optical basicity, Λ(χ) / − Fig. 1. Correlation between experimentally obtained O1s binding energy EB(O1s) and the optical basicity numerically-estimated from electronegativity Λ(χ).

Fig. 3. Absorption linewidth, Δλa at 1.5 μm band of Er3+ ion against O1s binding energy, EB(O1s).

-508 -506 -504 -502 -500

DO

S / -

Energy / eV

Total

Si-O-Si Si-O-B4

O(5)

BO NBO

Fig. 2. Density of states (DOS) of the atomic orbitals obtained from the MO calculations. The vertical lines are the energy levels in sodium silicates. The numbers in the parentheses indicate the site number of the structural model used for the MO calculation.

20

40

60

80

100

120

529530531532533534

TeO2

B2O

3

Bi2O

3

SiO2

GeO2P2O5Al

2O

3Ab

sorp

tio

n lin

ew

idth

, Δλ a

/ n

m

O1s binding energy, EB(O1s) / eV

■Key word■ Glass, Characterization, Structure, Properties, Material design, Basicity ■Affiliation■ Professor, Dept. of Environmental Chemistry and Materials ■Printing■ Journal of the Ceramic Society of Japan, Vol. 119(10), pp. 720-725, 2011.10. (The 65th CerSJ Awards for Academic Achievement in Ceramic Science and Technology)

Peer-reviewed review, Language: English


Phase separation of borosilicate glass containing phosphorus Y. OHTSUKI1), S. SAKIDA2), Y. BENINO3), T. NANBA4) ■Summary■ Iron- and steel-making slags consist of chemical components, such as SiO2, CaO and Al2O3, which are also included in widely-used commercial glasses. We focused on these components and came up with the idea that phase separation of glass, which has been used for the production of porous glasses in glass industry, could be applied to the recovery of phosphorus from iron- and steel-making slags. However, little is known concerning the distribution of phosphorus after phase separation. Then, Sodium borosilicate glasses containing P2O5 and Al2O3 were prepared, and the behavior of phosphorus associated with the phase separation and the effect of Al2O3 addition have been investigated. After the heat treatment, phase separation by spinodal decomposition was observed in the all samples. In the Al2O3-free glasses, phosphorus was preferentially distributed into B2O3-rich glass phase after the phase separation. With increasing Al2O3 content, the amount of phosphorus distributed into SiO2-rich glass phase increased. According to 31P MAS NMR measurements, in the Al2O3-containing glasses, Q4 units free from terminal oxygen atoms were formed. It was suggested that the distribution of phosphorus depend on the PO4 units.

Table 1. Nominal and analytical compositions (mol%), Tg and Tx (°C) of the samples. No. Na2O B2O3 SiO2 P2O5 Al2O3 Tg Tx 1 10 (8.2) 40 (36.9) 50 (54.9) - - 469 - 2 10 (8.8) 40 (37.8) 47 (50.6) 3 (2.8) - 450 - 3 8 (7.1) 40 (36.9) 47 (50.9) 3 (2.9) 2 (2.3) 444 - 4 7 (5.9) 40 (36.7) 47 (51.0) 3 (3.0) 3 (3.4) 433 533 5 6 (4.8) 40 (36.0) 47 (51.7) 3 (3.0) 4 (4.5) 423 535

Figure 1. SEM photograph of the surface of the glass No. 3 heated at 600 °C for 16 h.

Table 2. Analytical composition of the glass phases after phase separation (a) SiO2-rich phase (mol%)

No. Na2O B2O3 SiO2 P2O5 Al2O32 0.0 4.2 95.7 0.1 - 3 2.1 0.4 93.1 1.1 3.3 5 2.6 0.6 87.9 3.5 5.5

(b) B2O3-rich phase (mol%) No. Na2O B2O3 SiO2 P2O5 Al2O32 18.1 73.1 2.8 6.0 - 3 10.6 81.7 2.3 5.3 0.0 5 7.0 89.1 1.7 2.2 0.0

■Key word■ Phase Separation, Borosilicate Glass, Distribution of Elements ■Affiliation■ 1) Graduate School of Environmental Science, 2) Assistant Professor, Environmental Management Center, 3) Associate Professor, Dept. of Environmental Chemistry and Materials 4) Professor, Dept. of Environmental Chemistry and Materials ■Printing■ IOP Publishing IOP Conf. Series: Materials Science and Engineering 18 (2011) 112022 doi:10.1088/1757-899X/18/11/112022 Peer-reviewed paper, Language: English


Fabrication of layered double hydroxide/photoresponsive dendron nanocomposite

multilayer film by electrostatic layer-by-layer assembly Toshiyuki Tanaka1), Shunsuke Nishimoto2), Yoshikazu Kameshima3), Michihiro Miyake4) ■ Summary ■

A novel inorganic-organic nanoscopic multilayer film consisting of exfoliated MgAl-type layered double hydroxide (LDH) nanosheets and anthryl dendrons [i.e., poly(amidoamine) dendrons with an anthracene chromophore group at the focal point] was fabricated using an electrostatic layer-by-layer (LbL) assembly. UV-vis spectroscopy and X-ray diffraction analysis indicated the successful LbL growth of dendron/LDH multilayer films. Furthermore, fluorescence spectroscopic analysis indicated that the dendrons are present as a monolayer between LDH nanosheets in the film.

Figure. Schematic image of the LDH/(AD/LDH)n multilayer film. ■ Key word ■ Layered double hydroxide, Dendron, Layer-by-layer assembly, Multilayer structure, Nanocomposites, Photophysical properties ■ Affiliation ■ 1) Graduate School of Environmental Science 2) Assistant Professor, Dept. of Environmental Chemistry and Materials 3) Associate Professor, Environmental Management Center 4) Professor, Dept. of Environmental Chemistry and Materials ■Printing■ Mater. Lett., 65, 2315-2318 (2011).

Peer-reviewed communication, Language: English


Micro-flowers of poly(p-phenylene pyromelliteimide) crystals Kanji Wakabayashi1), Tetsuya Uchida2), Shinichi Yamazaki3), Kunio Kimura4) ■Summary■

Morphology control of poly(p-phenylene pyromelliteimide) (PPPI) crystals was examined using reaction-induced crystallization of oligomers during solution polymerization of self-polymerizable N-(4'-aminophenyl)-3-carboxyl-4-alkoxycarbonylPhthalimide. Micro-flowers of the PPP1 needle-like crystals were formed in which the needle-like crystals grew radially from the center part as petals. The molecules aligned regularly along the long axis of the needle-like crystal. The structure of alkoxy group in the monomer and the monomer concentration influenced the size of the needle-like crystals, and their average length and width were changeable from 640 nm to 1.69 μm and from 110 nm to 210 nm, respectively. The average thickness was 20 nm. The obtained micro-flowers possessed high crystallinity and exhibited excellent thermal stability.

■Key word■ crystallization, morphology, polyimide

■Affiliation■ 1) Graduate School of Environmental Science 2) Graduate School of Natural Science and Technology 3) Associate professor, Dept. of Environmental Chemistry and Materials 4) Professor, Dept. of Environmental Chemistry and Materials ■Printing■ Polymer Vol. 52, No. 3, pp. 837-843, 2011. DOI: 10.1016/j.polymer.2010.12.022



Preparation of Poly(p-phenylenepyromelliteimide) Microspheres with Rugged

Surfaces Using Crystallization During Isothermal Polymerization Kanji Wakabayashi1), Tetsuya Uchida2), Shinichi Yamazaki3), Kunio Kimura4) ■Summary■

Preparation of discrete PPPI microspheres was examined using the crystallization of oligomers during isothermal polymerization of PMDA and p-phenylene diisocyanate, and that of pyromellitic dithioanhydride and PPDA in poor solvents. In contrast to PPPI microspheres with smooth surfaces that were previously prepared by phase-separation during the polymerization of PPDA and PMDA, the microspheres obtained here consisted of flake-like lamellae with rugged surfaces. The diameters of the microspheres ranged from 0.5 to 6.7 μm. They exhibited excellent thermal stability depending on the monomers. These results provide a new preparative procedure of the PPPI microsphere with a rugged surface.

■Key word■ heteroatom-containing polymers, high-performance polymers, microspheres, morphology

■Affiliation■ 1) Graduate School of Environmental Science 2) Graduate School of Natural Science and Technology 2) Associate professor, Dept. of Environmental Chemistry and Materials 3) Professor, Dept. of Environmental Chemistry and Materials ■Printing■ Macromolecular Chemistry and Physics Vol. 212, No. 2, pp. 159-167, 2011. DOI: 10.1002/macp.201000510


Figure. PPPI precipitates prepared in (a) at a conc. of 0.5% in LPF from PMDA and PPDI, (b) at a conc.of 2% in DBT from PMDA and PPDI, (c) in LPF at 240oC from PMTA and PPDA, (d) in LPF at 330oC from PMTA and PPDA, (e) in DBT at 240oC from PMTA and PPDA, (f) in DBT at 330oC from PMTA and PPDA and (g) at a conc. of 0.5% in LPF from PMDA and PPDA.

２０１０年度環境物質工学科

卒業論文リスト

セラミックス材料学研究室 (指導教員：難波徳郎・紅野安彦・崎田真一）１．Na2O-CaO-B2O3-SiO2系ガラスの分相に伴う遷移金属元素の分配挙動２．無機系廃棄物のケミカルリサイクルにおける微量成分の挙動３．逆モンテカルロ法による重元素含有ホウ酸塩ガラスのモデル構築４．ビスマスホウ酸塩ガラスの結晶化と非線形光学機能発現５．ガラスの分相促進剤として用いるホウ素の循環再利用プロセスの開発６．湿式ボールミル法による希土類含有廃棄物からの希土類元素の回収７．下水処理汚泥からのリンの回収プロセスの開発８．耐火物と溶融スラグの反応性に及ぼす塩基度の影響

無機機能材料化学研究室（指導教員：三宅通博・亀島欣一・西本俊介）１．CuFe2O4可視光応答型光触媒を用いた促進酸化法による水質浄化２．微弱紫外光下での TiO2膜の超親水化に対する過酸化水素水の添加効果３．ハイドロタルサイトへのアセチルサリチル酸のインターカレーション挙動４．異種元素ドープをした配向性 ZnO 熱電変換材料の開発５．Ni 担持 SrTiO3によるエタノールスチームリフォーミング反応６．超音波を用いた超微粒子/活性炭複合材料の開発７．改質バイオガスを燃料とする固体酸化物燃料電池用燃料極の開発

有機機能材料学研究室（指導教員：高口豊・田嶋智之）１．1,10-ビス(デシロキシ)デカンをコアに持つデンドリマーを用いた単層カーボンナノチ

ューブ/炭酸カルシウム複合体調製

２. 2,3,9,10 位にシアノビフェニル基を有するヘキサチアペンタセン誘導体の合成と性質

３．フラーレンの新規なフェニルセレノ基導入法の検討４．ヘキサチアペンタセン誘導体合成法の改良と材料応用５．テトラエチレンオキシド鎖を有する新規 terthiophene 誘導体の合成と性質６．ピセン硫化反応の検討７. 単層カーボンナノチューブ/フラロデンドロン/Pt ナノハイブリットを利用した光水素

の発生環境高分子材料学研究室（指導教員：木村邦生・山崎慎一）１．重合相変化を利用したフッ素含有芳香族ポリエ－テルオキサジアゾールの高次構造形

成２．特異な形態を有する芳香族ポリエステルイミド結晶の調製３．多重水素結合性官能基を末端に有するポリエステルの核生成４．バイオマスを原料としたスーパーエンプラの開発５．結晶格子中でらせん形態をとる環状高分子の核生成と結晶成長６．エステル結合間の長さの異なる脂肪族ポリエステルの流動場結晶化におけるエステル

交換反応を介した絡み合い解消の役割７．ホウ酸触媒を用いた直接脱水重縮合による AA-BB 型芳香族ポリエステルの調製

「「２０１１年３月および９月認定の卒業論文」

環境プロセス工学研究室（指導教員：木村幸敬・小野努）１．ポリアスパラギン酸誘導体を用いた新規水性二相系の創製２．混合溶媒系を用いた水溶性物質内封ポリ乳酸ナノ粒子の調製３．亜臨界水を利用した中国産山核桃の殻からの有用成分の抽出４．過熱水蒸気を用いたバイオマスの減量および有用成分の抽出５．ハイドロゲルをコアとした水内包マイクロカプセルの調製６．単分散アガロースゲル粒子内での微生物溶菌技術の構築７．マイクロ流路を用いた単分散液滴内における晶析挙動８．亜臨界水でのスクロース分解に及ぼす高 pH の影響

環境反応工学研究室（指導教員：加藤嘉英・アズハウッディン）１．太陽電池セル内シリコンリサイクルのためのケミカルエッチングと評価手法２．製鋼スラグの pH 試験方法の基礎検討３．水モデルを用いた RH 真空脱ガス装置の反応速度向上方法の検討４．鉄－硫化鉄混合粉による地下水中トリクロロエチレンの分解除去５．農業廃棄物からのバイオチャーの調製６．ガス吹き込み撹拌時の液-液間物質移動速度におよぼす操作要因の影響７．木質バイオマスのガス化で生じるタールの分解用鉄-セリウム系触媒の開発

２０１０年度環境物質工学科

卒業論文報告

1．特異な形態を有する芳香族ポリエステルイミド結晶の調製, 大西拓也 2．ビスマス亜鉛ホウ酸塩ガラスの結晶化と非線形光学機能発現, 金西啓太 3．ガラスの分相促進剤として用いるホウ素の循環再利用プロセスの開発, 畑雄大


特異な形態を有する芳香族ポリエステルイミド結晶の調製 Preparation of aromatic poly(ester imide) crystals having unique morphology 大西拓也 Takuya Ohnishi ■ 概要 ■ [緒言] 全芳香族ポリエステルイミドは、ポリエステルとポリイミドの性質を併せもち耐熱性や力学特性に優れた高性能高分子材料として期待される。これまでに、モノマーにイミド結合を内包する N-(4-カルボキシフェニル)-4-アセトキシフタルイミド(CAP)を 280oC から 330oC で重合すると、らせん状のポリエステルイミド結晶が生成することを見出した。また、らせんピッチは重合温度に依存し、重合温度の

上昇に伴って 300 nm から 1.3 μm まで増大した。そこで、本研究では、モノマー濃度がポリエステルイミド結晶の形態に及ぼす影響を明らかにするとともに、先端部にのみらせん形態を有する針状結晶が生

成することを見いだしたので報告する。 [実験] 重合管にジベンジルトルエン混合物、ならびに所定量の CAP を仕込み、窒素雰囲気下で 280oCまで加熱した。モノマーが完全に溶解したら撹拌を停止し、280oC で 4 時間重合した。析出した生成物は熱時濾過により回収し、n-ヘキサンとアセトンにより洗浄した。 [結果と考察] 重合温度を 280oC にし、モノマー濃度を 0.5 %から 5.0 %まで変化させて重合を行ったところ、モノマー濃度の増大とともに収率は 14 %から 86 %まで増加した。モノマー濃度 0.5 %の条件ではスラブ状結晶や不明瞭な結晶も生成したが、モノマー濃度が高くなるにつれてらせん状結晶や針状結晶

が多く見られた。Fig. 2 に示すように、モノマー濃度 0.5 %の条件ではらせんピッチは 328 nm であったが、1.0 %では 417 nm、3.0%では 614 nm と増大することが分かった。らせん状結晶の幅は濃度の増大に従って 147 nm から 156 nm へと僅かに増大したが、大きな変化は見られなかった。しかし、モノマー濃度を 5.0%まで増大させると、らせんピッチは急激に減少し、らせん状結晶の幅は増大した。また、モノマー濃度 3.0%までは規則的であったらせんピッチは、モノマー濃度 5.0%では先端にいくほど短くなった。また、モノマー濃度 5.0%では繊維状結晶の先端部のみがらせん形態となっている針状結晶も見られた。このようにモノマー濃度 5.0%の条件では特異的形態を有する結晶が得られるなど、重合濃度3.0%以下の重合とは全く異なる傾向が見られたので、形態的変化を経時的に調べた。重合時間 20 分では先端のみにらせん状形態を有する針状結晶は見られなかったが、重合時間 40 分からは先端のみにらせん状形態を有する針状結晶の生成が見られた。そこで、溶液中の溶けているオリゴマーを回収し、

MALDI-TOF MS によりオリゴマーの重合度を調べた。重合時間 20 分のオリゴマー中には 2 量体までのオリゴマーしか検出されず、重合時間 40 分のオリゴマー中には 3 量体までのオリゴマーが検出された。よって、重合開始 20 分までは主に 3 量体が析出するのに対して、40 分後からは析出オリゴマーの分子量が増大し 4 量体が析出するようになったと推察できる。濃度 5.0%で重合した場合、重合初期では析出オリゴマーの分子量が低く、bent-core 型のオリゴマーが生成しなかったために針状結晶が生成する。重合の進行に従って液相中のオリゴマー濃度が減少し、オリゴマーの析出限界分子量が増大する。よっ

て重合中期から 4 量体オリゴマーが析出し始めたために針状結晶の先端にらせん状結晶が生成し、特異的な形態が発現したと考えられた。 ■卒論指導教員■ 環境物質工学科・木村邦生, 環境物質工学科・山崎慎一

■キーワード■ ポリエステルイミド，らせん形態，重合結晶化

■ 所属 ■ 大学院環境学研究科博士前期課程資源循環学専攻 ■ 掲載先 ■ 第 60 回高分子学会高分子討論会 2011 年 9 月 28－30 日岡山大学津島キャンパス


ビスマス亜鉛ホウ酸塩ガラスの結晶化と非線形光学機能発現 Crystallization of Bismuth Zinc Borate Glasses and Nonlinear Optical Property 金西啓太

Keita KANENISHI

■ 概要 ■ レーザー光からより短波長の光を得るのに用いられる波長変換材料には、高い非線形光学機能に加え

て透明性等の光学的品質の観点から単結晶が選択される。一方、結晶化ガラスは単結晶に比べて製造コ

ストを大幅に削減できる利点が挙げられるが、波長変換機能を有する結晶相と残留ガラス相との境界に

起因する光散乱が事実上問題となる。結晶化ガラスの光学的品質向上を目的とし、光散乱に関係する結

晶析出形態を制御することにより透明性維持が可能であれば、単結晶育成の困難な結晶に関して結晶化

ガラスの優位性は向上するものと考えられる。Bi2ZnB2O7 (BZB)結晶は高い非線形光学特性を有することが報告されている。そこで本研究では、Bi2O3-ZnO-B2O3系ガラスから Bi2ZnB2O7相を結晶化により析出させることを試みた。ガラスの基礎物性、結晶化挙動および結晶化ガラスの非線形光学特性を調査した。

10 20 30 40 50

BZB powder

430℃

440℃

◇BZB crystal◆Unknown

◆◆

◆

2θ(deg)

Inte

nsity

(a.u

.)

◇

◇ ◇

◇◇

◇

◇◇

◇◆ ◆ ◆

Fig. 1. 12 h 熱処理した結晶化ガラスの XRD パターン

10 20 30 40 50

◇ BZB crystal◆ Unknown

BZB powder

410℃

400℃◆

◆◆

◆◆

◆◇ ◇◇ ◇ ◇ ◇

Inte

nsity

(a.u

.)

2θ(deg)

Fig. 2. UST 後熱処理した結晶化ガラスの XRD パターン

Fig. 3. 650°C で 10min 熱処理した結晶化ガラス

-40 -20 0 20 40angle of incidence (deg)

SH in

tens

ity(a

.u.)

crystallized glassY-cut quartz

Fig. 4. 結晶化ガラスの Maker フリンジパターン

■卒論指導教員■ 環境物質工学科・紅野安彦，難波徳郎，環境管理センター・崎田真一

■キーワード■ 結晶化ガラス，超音波処理，光機能性材料，非線形光学特性 ■ 所属 ■ 大学院環境学研究科博士前期課程資源循環学専攻 ■ 掲載先 ■ 学会発表：日本ｾﾗﾐｯｸｽ協会ﾔﾝｸﾞｾﾗﾐｽﾄﾐｰﾃｨﾝｸﾞ in 中四国, 愛媛(2010). 日本ｾﾗﾐｯｸｽ協会年会, 静岡(2011). 28th Japan-Korea International Seminar on Ceramics, 岡山(2011).


ガラスの分相促進剤として用いるホウ素の循環再利用プロセスの開発 Recovery and Recycling of Boron Used as Promotion Agent for Phase Separation of Glasses 畑雄大

Yudai HATA

■ 概要 ■ 近年、ガラスの相分離現象を利用した無機性廃棄物のリサイクルや放射性廃棄物からの元素回収が検討され、有価元素の回収プロセスの開発が行われている。相分離現象を利用する手法では、シリカ成分を含む無機物質に分相促進剤として B2O3 を加え溶融急冷法にてガラスを作製し、ガラス転移温度以上の温度で熱処理することによりガラスを分相させ、酸処理によりボレートリッチ相を酸に溶出させシリカリッチ相の固体での回収に成功している。また、このとき共に回収された溶液中には廃棄物由来の元素と分相促進剤として利用したホウ素が溶出することになる。このプロセスを実用化するには処理コストを抑制する必要があり、我々の研究グループでは分相促進剤として添加したホウ素を分離回収し循環再利用するプロセスの開発も行っている。試薬から調整した模擬スラグでは添加したホウ素の 75%を回収することができたが、実際の都市ごみ溶融スラグでは 60%程度しか回収することができず、最初の酸処理の段階でのホウ素回収率が異なることが明らかとなった。そこで本研究では、廃棄物の組成がホウ素の回収率に与える影響を調べるために、ガラス瓶等の汎用性の高いガラスを用いて実験を行った。実験手順に従って得られた各溶液に含有される元素量を ICP 測定により求め、原料バッチ中の量に対する残存率として Fig. 1 に示した。これより廃ガラス中の主成分のうち Si は最初の酸処理で沈殿として回収され、Al と Fe は次の凝集沈殿処理で沈殿として回収され、Na と Ca は最後のイオン交換により除去されたことが確認される。B はいずれの処理でも減少がほとんど見られず、三次溶液においても 90%以上の残存が確認できる。模擬スラグや都市ごみ溶融スラグを用いた実験では、一次溶液以降の処理でもホウ素の残存率は 20%程度減少しており、今回はすべての処理工程でロスを大幅に削減できた。

0

20

40

60

80

100

120

B Si Al Fe Na Ca

cｶｦ(%)

一次溶液二次溶液三次溶液

Fig. 1. 各溶液中に残存する元素の割合

10 20 30 40 50 60 70 80

Intensity (a.u.)

Angle, 2? (degree)

H3BO3

三次固体

HBO2NH4Cl

Fig. 2. 三次固体の XRD パターン

■卒論指導教員■ 環境物質工学科・難波徳郎，紅野安彦，環境管理センター・崎田真一

■キーワード■ 廃ガラス，ケミカルリサイクル，相分離，循環再利用 ■ 所属 ■ 大学院環境学研究科博士前期課程資源循環学専攻 ■ 掲載先 ■ 学会発表：日本ｾﾗﾐｯｸｽ協会ﾔﾝｸﾞｾﾗﾐｽﾄﾐｰﾃｨﾝｸﾞ in 中四国, 愛媛(2010). 日本ｾﾗﾐｯｸｽ協会年会, 静岡(2011). 28th Japan-Korea International Seminar on Ceramics, 岡山(2011).

2011年度 環境物質工学科...

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2011年度環境物質工学科...