小林 範久

オリゴ(オキシエチレン)側鎖を有するポリメタクリル酸誘導体に,過塩素酸リチウムとホトクロミック化合物であるスピロベンゾピラン(SP)誘導体を複合した固体膜を作製し,色素の光異性北反応とそのときのイオン伝導度変化について検討した。<BR>高分子側鎖末端にヒドロキシル基をもつポリマーとしてメタクリル酸のα-ヒドロオリゴ(オキシエチレン)エステルポリマー[P(MEO)OH]を試料とし,このポリマー中で,紫外線照射によって,SPが無色種からホトメロシアニン体(PMC体)に異性化することを可視吸収スペクトルの変化より確認した。これにともないr固体膜のIRスペクトルにおける,O-H伸縮振動のピーク波数が低波数側にシフトし,高分子側鎖末端のヒドロキシル基-PMC体間に水素結合が存在することが明らかとなった。さらに, 紫外線照射時の水素結合の形成に基づき高分子固体膜のイオン伝導度が低下し,暗所下では,この相互作用の低下に基づきイオン伝導度が増加することから,スピロベンゾピラン誘導体の光異性化反応によりイオン伝導度が剃御できることを見いだした。

The solid film of poly[(ω-methoxy)oligo(oxyethylene) methacrylate] [P(MEO)] doped with malachite green leuco hydroxide (MGLOH) or triphenylmethylalcohol (TPMOH) has been prepared as a new type of solid polymer electrolyte with controllable ionic conductivity upon photoirradiation. The ionic conductivity for P (MEO) film doped with 0.1 mol% MGLOH or 0.05 mol% TPMOH increased with UV irradiation. This suggests that the photogenerated ions act as conductive carrier in the matrix. In particular, for the TPMOH doped film, the effect of TPMOH content on the ionic conductivity change has been analyzed with the change of glass transition temperature (Tg) upon UV irradiation. © 1992 Springer-Verlag.

A polymer containing anthryl groups is prepared as the matrix for a Solid Polymer Electrolyte with controllable ionic conductivity by photoirradiation. The complex composed of the polymer (anthryl group content at 14 mol%) and LiClO4(3 mol%) showed the high ionic conductivity of 6.8 × 10-6 S cm-1 at 25°C in the dark. The conductivity change caused by photodimerization of anthryl groups is revealed to be considerably affected by the anthryl group content and Tg of the matrix. © 1992.

The solid polymer electrolyte composed of poly[(a-hydrooligo(oxyethylene)-&lt o-yl me-thacrylate] [P(MEO)OH], LiC1O4 and a spirobenzopyran derivative (SP) has been prepared, and its photoinduced change in ionic conductivity has been also investigated. SP is a well-known photochromic material. SP is isomerized to photomerocyanine (PMC-form) upon UV irradiation. PMC-form is especially stable in protic solvents. This is attributable to the formation of hydrogen bond between PMC-form and the solvent. In the IR spectra of P(MEO)OH film, the absorption assignable to the O-H stretching vibration shifts from 3501cm-1 to 3480 cm-1 after UV irradiation for 2 h. This also indicates the formation of a hydrogen bond between PMC-form and the hydroxyl group in the polymer side chain. The ionic conductivity of this film decreased upon UV irradiation and subsequently increased in the dark. This is attributed to the formation of hydrogen bond between PMC-form and P(MEO)OH by UV irradiation. Namely, this interaction acts as quasi-crosslinking point and this causes the ionic mobility change. Therefore, it was found that the ionic conductivity can be controlled by photoisomerization of SP in the solid polymer electrolyte upon irradiation. © 1992, The Chemical Society of Japan. All rights reserved.

Effects of lattice energy of the additive salt on ionic species and ion conductivity characteristics were studied in the solid polymer electrolyte. Poly[oligo(oxyethylene) methacrylate] and several lithium salts were used as matrix and additive salt for solid polymer electrolytes, respectively. Salt and salt content deeply affected the ion conductivity characteristics as well as morphology even for amorphous type solid polymer electrolytes. The relationship between ion conductivity at constant reduced temperature (T - T(g) = 90-degrees-C) and lattice energy of the additive salt was evaluated at each salt content. A different relationship was found for each salt content. Multiple ion aggregate formation was considerably affected by the salt, and was revealed to be effective to increase the ion conductivity.

Poly(aniline) and poly(ring-substituted aniline) films showing electrochromic characteristics were obtained by electropolymerization in tetra-n-butylammonium tetrafluoroborte (TBABF4) and 1,2-dichloroethane solution without protic acid. The resulting film was found to exhibit better electrochromic response than that prepared with TBAP. © 1992.

Photoinduced ionic conductivity in poly(ethylene glycol)400 (PEG400)/malachite green leuco hydroxide (MGLOH) was analyzed with photochemical reaction of MGLOH in its matrix. The resonance structure in photogenerated cation lay in the favor of 4,4'-(dimethylamino) triphenylmethylcation (MG+) under UV irradiation. The change in the ionic conductivity was discussed with that in glass transition temperature (Tg) of the matrix on UV irradiation.

All solid state WO3-prussian blue (PB) based ECD is constructed with polymer electrolyte, and their electrochromic mechanism is investigated. From the analyses of cyclic voltammogram for PB or WO3 electrode measured in two or three electrodes system, electrochromic behavior of this ECD is indicated to be controlled by the electrochemical reaction for PB electrode. When alkali metal thiocyanates (MSCN) are used as additive salts for polymer electrolyte, resulting solid state ECD shown good electrochromic characteristics. Weak interaction between cation and surrounding polar environment is revealed to be effective to improve EC characteristics, because the cation should be fully desolvated from ether oxygens of polymer in order to be injected into PB lattice for such a ECD. Their coloring and bleaching mechanisms are discussed with the electrochemical behaviors in this ECD. © 1990.

Poly[(ω-carboxy)-oligo(oxyethylene)methacrylate] alkali metal salts (P(CMEnM)s) are synthesized as solid polymer electrolytes which can transfer only cations. The conductivity of a series of alkali metal ions such as Li+, Na+, K+, Rb+, and Cs+ is measured, and the results are summarized with the reduced temperature (T-Tg:Tg=glass transition temperature) to neutralize the effect of segmental motion on the relative conductivity. They show a linear relation between the logarithm of conductivity at T-Tg=60°C and the logarithm of radius of the carrier cations. The ion-dipole interaction is suggested to be the most effective factor to control the mobility in the solid polymer electrolytes. Cations having larger ionic radius such as Rb+ or Cs+ are suggested to have weaker interaction force with ether oxygens, reflecting the faster ion exchange between possible adjacent sites in the polymer matrix. © 1990.

Azo benzene derivatives are dispersed in a poly(carbonate) or poly(N-vinyl carbazole) matrix, and their photoconductive characteristics are investigated in terms of the structure of azo benzene derivatives and polymer matrix. These azo benzene derivatives are composed of electron donating and accepting parts bridged by azo bonds and are intramolecular charge transfer complexes as determined by UV-Vis spectra and electrochemical measurements. This charge transfer is effective for theincrease of photoconduction in these derivative-dispersed poly(carbonate) films. When poly(N-vinyl carbazole) is used as a polymer matrix, photocurrent increases by one order of magnitude in comparison with that in a poly(carbonate) system. The roles of azo derivatives and polymers for photoconduction are discussed with the action spectrum of the photocurrent in these systems. © 1990 The Society of Polymer Science, Japan.

Electrochromic characteristics of tris-bipicoline rhodium complex, [Rh (bipc.) <SUB>3</SUB>] Cl<SUB>3</SUB>, are invetigated in DMF solution containing some electrolytes. This shows electrochromic characteristics with the color change from pale-yellow to red at reduction state in TBAP/DMF solution. At the presence of LiClO<SUB>4</SUB> in DMF solution, this complex shows neither electrochemical response nor electrochromic characteristics. From the results of DMF solution containing TBAP and LiClO<SUB>4</SUB> with several concentration ratio, electrochromic behavior of Rh (bipc.) <SUB>3</SUB> complex is considerably affected by the interaction between Rh (bipc.) <SUB>3</SUB> complex and cation species. Rh (bipc.) <SUB>3</SUB> complex may interact with lithium cation, resulting in no electrochromic behavior. These interactions and/or the structure of the complex are also revealed to be affected by the electronic characteristics of the solvent.

Kawaden Co., Ltd has developed an automatic mold lofting, an indispensable process for steel bridge manufacturing. Consequently, a computer-aided backup system for bridge manufacturing works has been established, which enables the works a continuous operation from design stage to mold lofting process. The characteristics of this system are as follows: special shaped end section of the girder which is frequently dealt with is covered; mutual interference of bridge members can be automatically detected; output form of mold lofting documents can be easily arranged in accordance with the clients' requests; and man-hour-per-ton necessary for a bridge mold lofting is similar to those calculated by conventional calculation centers in Japan, but can be reduced to nearly 65% of that for manual lofting.

Alkali-metal salts of (ω-carboxy)oligo(oxyethylene) methacrylate (CMEnM, M = Li, Na, or K) have been synthesized and polymerized to prepare polymeric solid electrolytes. These polymers have a flexible main chain, an oligo(oxyethylene) side chain for ion conduction, and a carrier ion source in the repeating unit. The conductivity of CME7K homopolymer, 1.1 X 10-7S/cm at 30 °C, is the highest value reported for a polyelectrolyte “homopolymer” without any additives. This conductivity is attributed to the oligo(oxyethylene) side chain, which facilitates the dissociation of the alkali-metal carboxylate. The temperature dependence of ionic conductivity is not linear, suggesting that conduction occurs by the WLF mechanism. Vogel-Tam-mann-Fulcher plots are linear when the standard temperature is defined as Tg- 50 °C. The differences in conductivity of P(CME7M) with different cations at the same ΔT from Tgare attributed to differences in ion-dipole interaction forces and in dissociation energy of the electrolyte. WLF plots of the conductivity of P(CMEnM) are independent of cation species and show a standard curved line, suggesting that carrier ions do not migrate naked but are bound to polymer segments through ion-dipole interaction forces. It is suggested that ion migration is controlled primarily by segmental motion of the polymer rather than by the interaction between cation and ether oxygen. © 1989, American Chemical Society. All rights reserved.

Alkali-metal salts of (ω-carboxy)oligo(oxyethylene) methacrylate (CMEnM, M = Li, Na, or K) have been synthesized and polymerized to prepare polymeric solid electrolytes. These polymers have a flexible main chain, an oligo(oxyethylene) side chain for ion conduction, and a carrier ion source in the repeating unit. The conductivity of CME7K homopolymer, 1.1 × 10-7 S/cm at 30°C, is the highest value reported for a polyelectrolyte ″homopolymer″ without any additives. This conductivity is attributed to the oligo(oxyethylene) side chain, which facilitates the dissociation of the alkali-metal carboxylate.

Aminophenanthroline derivatives are investigated as the unique monomer of organic polymeric material showing electrochromic behavior, because they have large π-electron conjugated system and hetero atoms in their unit structures. Electropolymerization technique is applied to preparing electroactive thin film on the electrode with these monomers. Especially, from (5-aminophenanthroline) ruthenium complex, electroactive yellow thin film is obtained on Pt or ITO electrode. This film shows electrochromic behavior of which yellow thin film is decolorized by applying the oxidative potential to the film. This behavior is considered to be arisen from the changes in the electronic structure of Ru-aminophenanthroline complex, which are caused by the redox between Ru<SUP>2+</SUP> and Ru<SUP>3+</SUP>.

Thin films of poly[(oligo(oxyethylene) methacrylate)-co-(alkali-metal methacrylates)] were prepared from methanol solutions of oligo(oxyethylene) methacrylate and alkali-metal methacrylates by casting and polymerization on a Teflon plate under nitrogen. The ionic conductivity of the films depends on the electrolyte content, the dissociation energy of the alkali-metal methacrylate, and the degree of motion of polymer segments surrounding the ions in the polymer matrix. The ionic conductivity of the polymeric Li and K salts is 10-6 S/cm at 80 °C. The transient ionic current after reversing the dc bias polarity shows one sharp peak corresponding to cation migration, indicating that the polymer is a cationic single-ion conductor. The temperature dependence of conductivity was determined. The Williams-Landel-Ferry parameters, calculated from the temperature dependence of conductivity, agreed reasonably well with theoretical values, confirming the influence of polymer segmental motion on conductivity. Additional confirmation was obtained from a Vogel-Tammann-Fulcher plot. © 1988, American Chemical Society. All rights reserved.

Polymeric solid electrolyte having high ionic conductivity about 10<SUP>-5</SUP> S/cm is applied to construct all solid state WO<SUB>3</SUB>-PB based electrochromic device (ECD). Poly [oligo (oxyethylene) methacrylate]/LiClO<SUB>4</SUB> hybrid thin film is prepared and sandwiched between WO<SUB>3</SUB> and PB coated ITO glass electrodes in a dry argon atmosphere. The increase of the applied voltage from 1 to 3 V results in the increase of an optical density change in coloring and bleaching processes for this ECD. Optical density change is about 50% larger than that for WO<SUB>3</SUB> based ECD. Furthermore, the charges can be injected 3 times more than that for WO<SUB>3</SUB> based ECD. The optical density at 800nm for this ECD is proportional to the injected charges. These results suggest that PB electrode acts as effective cation supplying or accepting electrode for WO<SUB>3</SUB> as well as coloring layer, because it shows opposite redox behavior against WO<SUB>3</SUB>. Cycling of coloring and bleaching is carried out for more than several hundred times without any decay in the activity and efficiency.

Coloring mechanism of tris-1, 10-phenanthroline nickel complex was evaluated with spectro-electrochemical methods. Tris-1, 10-phenanthroline nickel complex colored violet by applying cathodic voltage in the tetrabutylammonium perchlorate/DMF solution. The coloring rate of tris-1, 10-phenanthroline nickel complex was determined by the diffusion of this complex near the cathode. On the other hand, 1, 10-phenanthroline was also revealed to exhibit electrochromic phenomena similar to tris-1, 10-phenanthroline nickel complex. Supporting electrolyte concentration dependence was found in the electrochromism of 1, 10-phenanthroline. However, this tendency was not observed in the electrochromism of tris-1, 10-phenanthroline nickel complex. These suggest that 1, 10-phenanthroline colors as the result of interaction with tetrabutylammonium perchlorate. 1, 10-Phenanthroline was revealed not to color in itself but in the interaction with supporting electrolyte or metal ions under reduction. Namely, in tris-1, 10-phenanthroline nickel complex system, 1, 10-phenanthroline interacted with nickel ion stronger than with tetrabutylammonium perchlorate. Therefore, tris-1, 10-phenanthroline nickel complex showed higher electrochromic efficiency at lower applied voltage than 1, 10-phenanthroline system.

A series of benzoxazole derivatives are revealed to exhibit electrochromic phenomena, and the three primary colors such as red, green and blue are obtained by means of changing the structure of the benzoxazole derivatives. The coloring mechanism of these derivatives is evaluated with electrochemical and spectroscopical measurements. Phase-selective second-harmonic AC voltammetry is applied to obtain the reversible half-wave potential (<I>E</I><SUP>γ</SUP><SUB>1/2</SUB>) of benzoxazole derivatives. This measurement enables to evaluate <I>E</I><SUP>γ</SUP><SUB>1/2</SUB> more correctly than ordinary cyclic voltammetry under the system including the follow-up chemical reaction. From the results obtained with these methods, the coloration is probably caused by the interaction between the benzoxazole derivatives and supporting electrolyte and/or solvent. Benzoxazole derivatives containing thiophene ring exhibit clectrochromic behavior with low eletrochemical energy than that containing phenyl ring. This is attributed to a difference of resonance energy between thiophene ring and phenyl ring. Relation between electrochemical and spectroscopical data is also discussed.

Polymeric solid electrolyte with high ionic conductivity of about 10-<SUP>5</SUP>S/cm is prepared to construct all solid state WO<SUB>3</SUB>-based electrochromic display device (ECD). Poly [oligo (oxyethylene) methacrylate]/LiClO<SUB>4</SUB> hybrid thin film is cast on both ITO glass electrode and WO<SUB>3</SUB> coated ITO glass electrode. These are contacted with the polymeric solid electrolyte film-coated sides under dry argon atmosphere. The increase in the applied voltage resulted in the increase of the differential optical density change between coloring and bleaching processes for this ECD. The optical density at 800 nm for the coloring of WO<SUB>3</SUB> is proportional to the injected charges. The coloring state of this ECD has been maintained for several weeks under open circuit, deeply depending on the anion migration in polymeric solid. electrolyte. From the time dependence of the current passing through the cell in coloring and bleaching processes, the coloring and bleaching mechanisms for this ECD are interpreted to be the same as those for ordinary ECD composed of electrolyte solution system. Cycling of coloring and bleaching is carried out for more than several hundred times without any decay in the activity and efficiency.

Triethylbutadiynylsilane was polymerized selectively at the 1, 2-position by a Ziegler-Natta catalyst. The polymer obtained was soluble in non-polar organic solvents, and the average molecular weight of 4600 was found by vapor pressure osmometry. It showed an electrical conductivity of 32. 2 multiplied by 10**31 **1**1 S cm** minus **1 and 6. 0 multiplied by 10**31 **5 S cm** minus **1 without and with I//2 doping, respectively. Bulky silyl groups on the polymer were eliminated by tetrabutylammonium fluoride treatment to give poly(ethynyl acetylene). The conductivity of poly(ethynyl acetylene) was 6. 4 multiplied by 10** minus **8 S cm** minus **1 without doping. It was considerably improved by heat-treatment at temperatures higher than 600 degree C. Heat-treatment at 800 degree C for 2 h attained to provide 7. 8 multiplied by 10** minus **1 without doping. A partial acene structure was suggested in the heat-treated poly(ethynyl acetylene).

Since the first commercial SCR system was delivered in 1976, many SCR systems have been supplied by MHI for coal, gas and oil fired flue gases, exhausted from utility and industrial boilers, etc. Successful results have been obtained. In addition to the above, new type SCR systems, based on the most up-to-date technology, for large capacity utility boilers, respectively fired with coal, coal and oil, coal-oil mixtures (COM) and on the combined gas turbine cycle plants have recently started. This paper describes the points to be considered when planning systems of this type and the operating results.

7,7,8,8-Tetracyanoquinodimethane (TCNQ) was complexed with alkylated heterocyclic compound to evaluate the conductivity and melting point. Pyridine, quinoline, iso-quinoline, acridine, picoline and 3-methyl quinoline were quaternized by n-alkyl iodide to prepare electron-donating compounds. Among a series of complex salts, hexylpyridinium- and butyl-iso-quinolinium-TCNQ complex salts showed high conductivity of 4.3 × 10-1 and 2.2 × 10-2 S cm-1, respectively. There was a large temperature difference between melting point and decomposition point of about 50°C for these complex salts. These conductive complex salts were strongly suggested as potential candidates for the basic material to construct an effective capacitor. All solid-state capacitor (5 mm φ × 10 mm h) composed of Al/TCNQ complex salt/Al2O3 insulator/Al showed an electric capacity of 7-8 μF. © 1987.

Inherently conductive metallophalocyanine crystals were syntheesized by electrolysis. Potassium dicyanocobalt(III)phthalocyanine was electrolyzed at +1.1 V vs. AgAgCl reference electrode in acetonitrile solution without any supporting electrolytes. After several hours, single crystals (&gt 4mm) were grown on the anode surface. Elementary analysis and infrared measurement revealed that these crystals were composed of only cyanocobalt(III)phthalocyanine. The molecular arrangement was estimated by X-ray diffraction analyses. This compound crystallized in the triclinic space group P1, with a = 7.65(3), b = 9.85(4), c = 9.82(3) A ̊ α = 90.8(3), β = 107.3(3), γ = 107.2(3)° Fw = 597.5, V = 670.35 A ̊3, Z = 1, Dx = 1.46, Dm = 1.46 Mg/m3 (by flotation). It turned out that one phthalocyanine molecule is overlapped with adjacent six phthalocyanines, suggesting the three-dimensional overlapping of π-orbitals. The conductivity of this crystals was 5.7 × 101 S/cm at room temperature with the activation energy of 0.04 eV. No decay was found after keeping it under atmosphere for several months. Remarkably high concentration of spin at g = 2.008 was observed without temperature dependence, and thermoelectric power of about +40μV/K indicated holes as carrier. The three-dimensional conductive paths might be the reason of high conductivity. © 1987.

1,3‐Butadiyne was epitaxially polymerized on the graphite basal plane by chemical vapor deposition to form a homogeneous thin film. The film thickness varied from 100 to 3000 Å depending on the polymerization condition. The films on the graphite showed a variety of interference colors such as blue, purple, or gold depending on the film thickness. Raman spectra revealed that the polymerized film was mainly composed of CCbonds. Electron diffraction pattern and the ESCA spectrum of the film were quite similar to those of graphite, suggesting that butadiyne was polymerized in an epitaxial manner. Copyright © 1987 John Wiley & Sons, Inc.

低いガラス転移点を持つポリ (メタクリル酸オリゴオキシエチレン) に, 無機アルカリ金属塩を複合させて得られる高分子固体電解質のイオン伝導挙動に関する知見を整理した. 複合膜は100～300μmの膜厚を有し, 20℃でイオン歩導度10<SUP>-6</SUP>～10<SUP>-5</SUP>S/cmを示した. 添加塩の解離エネルギーとイオン伝導度の相関あるいはイオン伝導度の温度特性の検討から, イオン伝導度は添加塩の解離エネルギーとマトリクスの分子運動に大きく影響されることが明らかにされた. この高分子固体電解質を利用して, 試作した全固体エレクトロクロミック表示素子は, 印加電圧に対応して良好な吸光度変化を示した. また, 複合膜の膜厚調節は高い応答性と大きな吸光度変化を与える条件を支配する.

catena-μ-Ethynylene-phthalocyaninatocobalt(III) was synthesized by the reaction of dichlorophthalocyaninatocobalt(III) with bis(bromomagnesio)acetylene. This polymer was regarded as a novel type of an one-dimensional polymer, consisting of phthalocyanine radical species. The one-dimensional structure of this polymer was confirmed by IR spectrum and X-ray analysis. The conductivity of this polymer was found to be 3×10<SUP>-4</SUP> S/cm at room temperature without doping. This conductivity was explained by an increase of the carriers induced by the radical phthalocyanine rings.

catena-μ-Ethynylene-phthalocyaninatocobalt(III) was synthesized by the reaction of diehloro-phthalocyaninatocobalt(III) with bis(bromomagnesio)aeetylene. This polymer was regarded as a novel type of an one-dimensional polymer, consisting of phthalocyanine radical species. The one-dimensional structure of this polymer was confirmed by IR spectrum and X-ray analysis. The conductivity of this polymer was found to be 3×l0-4S/cm at room temperature without doping. This conductivity was explained by an increase of the carriers induced by the radical phthalocyanine rings. © 1986, The Chemical Society of Japan. All rights reserved.

Potassium dicyanocobalt(III) phthalocyanine was electrolysed at +1.1 V versus an AgAgCl reference electrode in acetonitrile without any supporting electrolyte for several hours at 25°C. Many plate-like crystals grew on the platinum point electrode. Elemental analysis and infrared spectroscopic measurements revealed that these were composed of cyanocobalt(III) phthalocyanine. The unit structure of the crystal was analysed by X-ray diffraction. This showed that one phthalocyanine was overlapped with six adjacent phthalocyanine planes, suggesting the three-dimensional overlapping of π-orbitals. The conductivity of the crystals was 5.7 × 101 S cm-1 with an activation energy of 0.04 eV. © 1986.

Poly[oligo(oxyethylene) methacrylate-co-sodium methacrylate was prepared as a polymeric solid electrolyte which enables sodium single ionic conduction. A methanol solution of the mixture of oligo(oxyethylene) methacrylate and sodium methacrylate was cast and polymerized on a Teflon® plate. The film obtained showed a conductivity of 4.0×10−7 S cm−1 at 80°C. The conductivity of the films depended on the sodium methacrylate content. Temperature dependence of the conductivity was analyzed as WLF-type behaviour. The ionic conduction mechanism of this film was found to be deeply affected by the segmental motion of the matrix polymer. This was also confirmed by the Vogel–Tammann–Fulcher plot for ionic conductivity. © 1986 The Society of Polymer Science, Japan.

We have been studying two-step syntheses from butadiynes, i. e. , the formation of intermediate polymer with pendant ethynyl group and the cyclization of the ethyl group to the polyacene structure. Key problems in this approach must be, first, how to cause selective 1,2-polymerization, and second, how to control the stereoregulatory. This article is concerned with the successful 1,2-polymerization of butadiyne by introducing the bulky and eliminable triethysilyl group at the 4-position, and the desilylation reaction from the polymer.

チオシアン酸アルカリ金属侮を分散させたポリメタクリル酸オリゴ(オキシエチレン)複合膜のイオン伝導度はK＞Na＞Liの順になることを観測した。イオン半径が大きいのにKSCN分散系で高いイオン伝導度(σ<SUB>1</SUB>=3.3×10<SUP>-5</SUP>S/cm, 25℃) を示す理由は, 塩の解離エネルギーが小さく, 同じ雰囲気での比較ではキャリヤーイオン生成に有利なためと考えられる。また, イオン伝導は伝導経路の粘性の影響も強く受けるため, 添加塩濃度増大にともない伝導度は極大値をとおって減少する。σ<SUB>1</SUB>の減少は複合膜のガラス転移温度の変化に影響され, T<SUB>g</SUB>の上昇がσ<SUB>1</SUB>低下を引き起こすことが明らかとなった。

Polymeric solid electrolytes with both high ionic conductivity and processibility were prepared from poly[methacryloyloligo(oxyethylene)] and inorganic lithium salts such as LiClO4 or LiPF6. An ac conductivity as high as 2.2 × 10-5 S/cm at 25°C was observed for this hybrid film when the composition of poly(methacrylate) and LiClO4 was 70/30 wt %. © 1985 American Chemical Society.

Poly[lithium methacrylate-co-oligo(oxyethylene)methacrylate] film was prepared as a polymeric solid electrolyte which showed lithium ionic conductivity of 2×10-7(S/cm). This film contained no organic plasticizer nor low molecular weight lithium salts and shown to be a single-ion conductor in solid state. Li+ ionic conductivity was deeply influenced by the glass transition temperature and lithium methacrylate content of this film. A rechargeable battery composed of metallic lithium/this film/graphite showed better characteristics than any previously reported systems using polymeric solid electrolytes. © 1985.

Polymeric solid electrolytes were prepared from inorganic lithium salts, endo-acetylated oligo(ethylene oxide) and polyanions with perfluoro(ethylene) main chain. High ionic conductivity was found when these ternary hybrids took micro-segregated structures with continuous cylindrical conduction columns of lithium salt-oligo(ethylene oxide) in the sea of perfluoro-poly(electrolytes). The ionic conductivity of more than 10-5 S/cm was established at room temperature without affecting the processibility and flexibility of resulting hybrid films. © 1984.

The development of a dry NOx removal process for boiler flue gases is described with emphasis on controlling the performance of commercial reduction NOx reduction catalysts. An integrated evaluation system is introduced covering the whole life of a catalyst from manufacture to replacement. Examples are given to illustrate the practical application of the system.

Polymeric solid electrolytes were prepared by dispersing homogeneously lithium perchlorate in a hydrogen-bonding type intermacromolecular complex of poly(methacrylic acid)-poly(ethylene oxide). They showed ionic conductivity of more than 10-6 (S/cm) at room temperature. The conductivity depended on the molecular weight of the poly(ethylene oxide), the proportion of poly(ethylene oxide) and lithium perchlorate, and so on. Poly(ethylene oxide) with average molecular weights ranging from 400 to 2 × 104 were used to clarify the effect of chain length on the conductivity. The conductivity increased and the flexibility of the films improved with increasing the content of poly(ethylene oxide) with average molecular weight of 400. The maximum conductivity of 1.3 × 10-5 (S/cm) at 60°C was obtained for the flexible film when the composition of poly(methacrylic acid)/poly(ethylene oxide)/lithium perchlorate was in the ratio of 17.0/ 68.0/15.0 in unit mol%. © 1983.