第８回　化学センサ研究発表会


April 7-8, 1989
Yokohama National University

プログラム

1
イオン選択性高分子修飾電極の構成

 岡田達弘・杉原秀樹・平谷和久

製品科学研

CHARACTERISTICS OF POLYMER MODIFIED ION-SELECTIVE ELECTRODES

 Tatsuhiro OKADA, Hideki SUGIHARA and Kazuhisa HIRATANI

Industrial Products Research Institute, I. I. T. I.,
Yatabe, Tsukuba, Ibaraki 305, Japan

A new type, polymer modified ion-selective electrodes are proposed which are based on ion exchangers incorporated into electrochemically polymerized pyrrole films on solid electrodes. By use of sulfonated naphthalene derivatives as doping materials into pyrrole films, electrodes sensitive to monovalent cations were prepared. If bis [di-(octylphenyl) phosphonato] calcium was incorporated into the film by selection of solution composition for electro-polymerization, calcium selective electrodes were successfully composed. The present method enabled miniaturized ion-selective electrodes by was of electrochemical procedure.


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2
血清中のNa+測定用NASICON電極の開発

 徳本淳一・民谷栄一*・軽部征夫*

日本特殊陶業・東大先端研*

DEVELOPMENT OF NASICON ELECTRODE FOR MEASUREMENT OF Na+ IN SERA

 Jun-ichi TOKUMOTO, Eiichi TAMIYA* and Isao KARUBE*

NGK SPARK PLUG CO., LTD.
14-18 Takatsuji-cho, Mizuho-ku, Nagoya 467, Japan
*Research Center for Advanced Science and Technology, University of Tokyo
4-6-1 Komaba Meguro-ku, Tokyo 153, Japan

A Na+ electrode based on NASICON was developed for measuring Na+ concentration in sera. This electorde needs no inner electryte solution because NASICON is one of solid electrolyte. Quick and stable response was obtained when this sensor was applied to Na+ solution. Interfering ions such as K+, Li+, NH4+ and Ca2+ had less effects on sensor response where Na+ concentration was over 1×10-2 M. Furthermore, Na+ concentration in controlled sera was determined using the NASICON electrode.


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3
微少薄膜基準電極の新規作成方法およびその電気化学的特性

 山口秀一郎・内田直人・下村　猛・石塚知生*・勝部昭明*

テルモ技術開発部・埼玉大工*

PREPARATION OF A MICRO REFERENCE ELECTRODE CONSTRUCTED WITH MULTI THIN-FILMS, AND ITS ELECTROCHEMICAL PROPERTIES

 S. YAMAGUCHI, N. UCHIDA, T. SHIMOMURA, T. ISHIZUKA, T. KATSUBE

TERUMO Co. Ltd. Tech. R&D

2656-1 Obuchi Fuji-shi, Shizuoka , Japan
Saitama Univ.
255 Shimo-okubo Urawa-shi, Saitama, Japan

It is necessary to develop a micro reference electrode in order to miniaturize whole scale of a sensor. In this report, we propose a new type of micro reference electrode. It is constructed with Ag electrode and thin film coated over the Ag electrode. This thin film is made by (a) a mixture of AgCl and polytetrafuluoroethyrene (PTFE), or (b) and aggregate of them cumulated alternatively. Potential of the mixed film electrode (a) moves in response to chloride concentration in a measurement solution. But the cumulated film electrode (b) has no response to both chloride ion concentration and pH of the solution.


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4
トマトにおける糖の転流測定

 村上　隆・武川征弘・松岡英明

東農工大工

MEASUREMENT OF SUGAR TRANSLOCATION IN TOMATO

 Takashi MURAKAMI, Yukihiro TAKEKAWA and Hideaki MATSUOKA

Department of Industrial Chemistry, Faculty of Technology, Tokyo University of Agriculture and Technology
Nakamachi Koganei, Tokyo 184, Japan

13C-NMR was applied to the measurement of the sugar translocation in tomato. Photosynthesis was performed in a vessel filled with 13CO2 under illumination (15,000 lux) for 4hr. Then 13CO2 was replaced by 12CO2 and photosynthesis was continued for successive 6 hr. At the time of 13CO2 replacement (t= 0), the incorporation rate of 13C (fD) in leaves was 0.12. The fD in leaves decreased gradually and reached 0.09 at t= 6 hr, while the fD in stems increased and reached a steady level of 0.09 around t= 3 hr. Non-destructive measurement of 13C-sugar in a tomato fruit was also demonstrated. The feasibility of plant biosensor system based on the sugar translocation rate as an indicator of metabolic activity of plant is discussed.


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5
電解重合薄膜修飾電極を用いた電気化学免疫センサ

 辻　一郎・宇野木正憲・安河内一夫*・谷口　功*

化学及血清療法研・熊本大工*

ELECTROCHEMICAL IMMUNOSENSORS BASED ON ELECTROGENERATED POLYMER MODIFIED ELECTRODES

 Ichiro TSUJI, Masanori UNOKI, Kazuo YASUKOUCHI* and Isao TANIGUCHI*

The Chemo-Sero-Therapeutic Research Institute, Kikuchi Laboratories
Kyoku-shi, Kumamoto, 861-15, Japan
*Department of Applied Chemistry, Faculty of Engineering, Kumamoto University
Kurokami, Kumamoto 860, Japan

On the basis of a electrogenerated polytyramine (tyramine= p-(2-aminoethyl)-phenol) modified electrode, prepared from alkaline alcohol solution at a low current density, a simple potentiometric human Chorionic Gonadotropin (hCG) sensor, on which the monoclonal anti-hCG was immobilized, was obtained. The detection limit of hCG was ca. 1 ng/ml. Also, and effective amperometric enzyme immunosensor for human immnoglobulin G (IgG) was prepared based on the polytyramine doubly coated electrode designed to reduce non-specific adsorption of proteins but to be immobilized anti-IgG in enough amounts. By means of the competitive enzyme immunoassay technique using the IgG sensor, IgG was determined in the concentration down to ca. 10 pg/ml.


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6
電気化学ルミネッセンス免疫センサ

 相澤益男・田中　俊*・篠原寛明・碇山義人

TDK開研*・東工大工

ELECTROCHEMICAL LUMINESCENCE-BASED IMMUNOSENSOR

 Masuo AIZAWA, Masaru TANAKA*, Hiroaki SHINOHARA and Yoshihito IKARIYAMA

Department of Bioengineering, Tokyo Institute of Technology
Meguro-ku, Tokyo 152, Japan
*R & D center, TDK Co.,
Ichikawa-shi, Chiba 272, Japan

A new detection device for electrochemiluminescence of luminol has been fabricated for a sensitive homogeneous immunoassay system. The device is a flow-cell type two electrode system for excitation of luminol labeled to an antigen, combined with a photo multiplier for counting of generated photons. Luminol as low as 10-9 mol・dm-3 was determined with the device, and an antibody was also sensitively quantitated with the detection limit of 10-11 g・cm-3. The advantages of sensitive homogenous immunoassay based on the electrochemiluminescence are discussed in details.

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7
グルコースオキシターゼとフェロセンカルボン酸を固定した
ポリピロール膜のグルコースセンサ作用
 梶谷芳男・岩倉千秋*・米山　宏
阪大工・阪府大工*
GLUCOSE SENSOR PROPERTIES OF POLYPYRROLE FILMS IMMOBILIZING BOTH GLUCOSE OXIDASE AND FERROCENECARBOXYLIC ACID

 Yoshio KAJIYA, Chiaki IWAKURA* and Hiroshi YONEYAMA

Department of Applied Chemistry, Faculty of Engineering, Osaka University
Suita, Osaka565, Japan
*Department of Applied Chemistry, college of Engineering, University of Osaka Prefecture

Sakai, Osaka 591, Japan

Polypyrrole films prepared by electropolymerization of pyrrole in aqueous solution containing glucose oxidase and ferrocenecarboxylic acid work as a glucose sensor without using any mediators in solution. Current response of the polypyrrole films to glucose depends on the deposition charge of polypyrrole films and there is an optimum deposition charge beyond which the diffusion of glucose through polypyrrole film becomes rate-limiting.


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8
レドックス活性クレー薄膜/GOx酵素膜被覆に基づく新しいグルコースセンサ

 大坂武男・山口善夫・小山　昇

東農工大工

A NEW AMPEROMETRIC GLUCOSE SENSOR BASED ON BILAYER-FILM COATING OF REDOX-ACTIVE CLAY FILM AND GLUCOSE OXIDASE ENZYME FILM

 Takeo OHSAKA, Yoshio YAMAGUCHI and Noboru OYAMA

Department of Applied Chemistry for Resources, Tokyo University of Agriculture and Technology
Koganei, Tokyo 184, Japan

The electrode characteristics of the immobilized enzyme chemically modified electrode (IECME) based on bilayer-film coating for amperometric determination of glucose were examined. The electrode substrate was coated with two kinds of polymeric films in a bilayer state, that is, at first with montmorillonite clay film into which Ru(NH3)62+ complexes are incorporated electrostatically and then with glucose oxidase enzyme film. In this sensor system for estimation of glucose concentration, the H2O2 production via glucose-glucose oxidase enzyme reaction was monitored by measuring the current of H2O2 reduction eledctrocatalyzed by the clay film where Ru(NH3)62+/3+ complexes function as "electron shuttle".
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特別講演１
植物におけるバイオセンシング

 松岡英明

東農工大工

BIOSENSING SYSTEM USING PLANT

 Hideaki MATSUOKA

Department of Industrial Chemistry, Faculty of Technology, Tokyo University of Agriculture and Technology
Nakamachi Koganei, Tokyo 184, Japan

Concept of biosensing system using plant is presented. Plant may respond to chemical compounds by changing its appearance, shape, electrochemical potential, enzymatic activity, and metabolic activities. Transducers which can detect these responses in vivo or in situ are being developed. Combining a plant with an appropriate transducer, a novel sensor system can be constructed for the detection of air pollutants, odour compounds or allelochemical compounds. Excellent sensitivity and considerable stability of the sensing function are expected.


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9
酵素-メディエーター系によるH2O2の高感度バイオセンシング

 立間　徹・大川祐輔・吉田章一郎・渡辺　正

東大生研

HIGHLY SENSITIVE BIOSENSING OF HYDROGEN PEROXIDE WITH AN ENZYME-MEDIATOR SYSTEM

 Tetsu TATSUMA, Yusuke OKAWA, Shouichiro YOSHIDA and Tadashi WATANABE

Institute of Industrial Science, University of Tokyo
Roppongi, Minato-ku, Tokyo 106, Japan

An enzyme-based biosensor for hydrogen peroxide was developed, employing a horseradish peroxidase (HRP) monolayer covalently attached to a tin oxide electrode and a dissolved electron mediator. The sensor can determine hydrogen peroxide at levels down to 10-8 M. Glucose oxidase (GOD) was chemically immovilized on the HRP-modified electrode. A GOD/HRP bilayer-modified electrode thus obtained exhibits about 10-fold higher sensitivity to glucose than previously reported GOD monolayer-modified electrodes.


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10
L-アスコルビン酸オキシダーゼを用いたL-アスコルビン酸のクーロメトリー

 内山俊一・浜本　修・中村幸夫・鈴木周一

埼玉工大工・三井造船

COULOMETRY OF L-ASCORBATE USING L-ASCORBATE OXIDASE

 Shunichi UCHIYAMA, Osamu HAMAMOTO, Yukio NAKAMURA and Shuichi SUZUKI

Department of Environmental Engineering, Saitama Institute of Technology
Okabe, Saitama 369-02, Japan
Mitsui Engineering & Ship-building Co., Ltd.,
Ichiharashi, Chiba 290, Japan

Selective measurements of L-ascorbate in vitamin C tabulets have been carried out by using controlled potential coulometric cell with porous carbon felt electrode containing ferricyanide ion as a mediator. The sample solution is added to the carbon felt and the total coulomb (Qs) was measured. Next, ascorbate oxidase is added to this sample solution and -ascorbate was converted to dehydroascorbate and the total coulomb of this blank solution (Qb) was also measured. A highly performed by measuring Qs-Qb. The results obtained by coulometry were in fairly good agreement with those obtained by hydrazine method.


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11
パルスボルタンメトリー法によるグルコースセンシングデバイス

 山内　繁・片山明秀**・島田直樹**・吉田泰彦**・矢尾板仁・碇山義人*

国立リハ研・東工大工*・東洋大工**

PULSE VOLTAMMETRIC DEVICE SENSING

 Shigeru YAMAUCHI, Akihide KATAYAMA**, Naoki SHIMADA**, Yasuhiko YOSHIDA**, Masashi YAOITA and Yoshihito IKARIYAMA*

Research Institute of National Rehabilitation Center
4-1 Namiki Tokorozawa, Saitama 359, Japan
*Dept. of Bioengineering, Tokyo Institute of Technology
2-12-1 O-okayama Meguro-ku, Tokyo 152, Japan
**Dept. of Applied Chemistry, Faculty of Engineering, Toyo University
2100 Kujirai Kawagoe, Saitama 350, Japan

We have already reported that a EEE sensor can be utilized for rapid determination of glucose concentration by a pulse voltammetric technique starting from a open circuit. For detailed studies of electrode processes, potential step measurement starting from a rest potential is required and we have found a systematic dependence of a rest potential on the glucose concentration. Current response to potential step from respective rest potential yielded dependence on glucose concentration from 0.1 to 10 mM, which is compared with the earlier result.


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12
アンペロメトリー方式マルチ酵素センサの試作

 山内　繁・矢尾板仁・長井律子**・吉田泰彦**・碇山義人*

国立リハ研・東工大工*・東洋大工**

AMPEROMETRIC MULTIBIOSENSING DEVICE WITH EEE

 Shigeru YAMAUCHI, Masashi YAOITA, Ritsuko NAGAI**, Yasuhiko YOSHIDA** and Yoshihito IKARIYAMA*

Research Institute of National Rehabilitation Center
4-1 Namiki Tokorozawa, Saitama 359, Japan
*Dept. of Bioengineering, Tokyo Institute of Technology
2-12-1 O-okayama Meguro-ku, Tokyo 152, Japan
**Dept. of Applied Chemistry, Faculty of Engineering, Toyo University
2100 Kujirai Kawagoe, Saitama 350, Japan

We have already shown that EEE works for glucose sensing with fast response and wide dynamic range. In this paper we demonstrate that application of EEE sensor is not limited to glucose, but can be extended to choresterol. EEE sensor with immobilized choresterol oxidase yielded anodic current of oxidation of hydrogen peroxide depending on the choresterol concentration from 0.5 g/l to 2.5 g/l.
The choresterol sensing and glucose sensing EEE were combined to a multifunctional biosensing device. The glucose sensing EEE did not give any response to choresterol, although little response of choresterol sensing EEE was observed to glucose.
We consider that a biosensing device of both glucose and choresterol can be developed with some more improvements.


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13
酵素センサシステムによるスクロース、グルコースの逐次測定

 水谷文雄・浅井道彦

繊高研

DETERMINATION OF SUCROSE AND GLUCOSE WITH AN ENZYME SENSOR SYSTEM

 Fumio MIZUTANI and Michihiko ASAI

Research Institute for Polymers and Textiles
1-1-4 Higashi Tsukuba, Ibaraki 305, Japan

Simultaneous determination of sucrose and glucose in one sample has been achieved by a flow injection system that consisted of a glucose-sensing enzyme electrode and an invertase/mutarotase-packed column. Up to 20 samples containing both sucrose and glucose were measured with high precision, when the ratio of glucose concentration to sucrose concentration in the sample was below 10.


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14
ハイブリッド型小型L-リジンセンサの開発

 鈴木博章・小嶋尚美・菅間明夫・武井文雄・池上佳住・民谷栄一*・軽部征夫*

富士通研・東大先端研*

DEVELOPMENT OF A HYBRID MINIATURE L-LYSINE SENSOR

 Hiroaki SUZUKI, Naomi KOJIMA, Akio SUGAMA, Fumio TAKEI, Kasumi IKEGAMI, Eiichi TAMIYA* and Isao KARUBE*

FUJITSU LABORATORIES, LTD.,
Atsugi, Kanagawa 243-01, Japan
*Research Center for Advanced Science and Technology, University of Tokyo
Meguro-ku, Tokyo 153, Japan

A disposable hybrid L-lysine sensor was developed by combining a miniature oxygen electrode, CO2 utilizing autotrophic bacteria, and L-lysine decarboxylase. Optimum temperature and pH were 33℃ and 6.0 respectively. A linear relationship was obtained between the L-lysine concentration and the current decrease. The sensor showed and excellent selectivity to various amino acids.


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15
in vivo 測定用超微少電極の作製

 板橋武之・阿部孝之・末永智一・内田　勇

東北大工

FABRICATION OF ULTRAMICROELECTRODES FOR IN-VIVO MEASUREMENTS

 Takeyuki ITABASHI, Takayuki ABE, Tomokazu MATSUE and Isamu UCHIDA

Department of Molecular Chemistry and Technology, Faculty of Engineering, Tohoku University
Sendai-shi, Miyagi 980, Japan

A fabrication method of ultramicroelectrodes with tip diameters less than 1 μm is reported. The ultrasmall dimension of these electrodes makes it possible to measure the electrochemical behavior in ultrasmall. Like in-vivo, environments. These electrodes were prepared by electroless plating of silver of glass micropipettes. The surface of silver was very flat and smooth. The condition of electroless plating including pre- and past-treatments of the electrodes are discussed. The sigmoidal voltammograms, which are typical for ultramicroelectrodes, were obtained in the reduction of 0.5 mM Hydroxyethylviologen in 0.1 N KNO3.


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16
酵素固定化マイクロアレー電極の酵素スイッチ特性（III）
酵素固定化膜の作製法に関する検討

 鳴海　学・末永智一・内田　勇

東北大工

SWITCHING CHARACTERISTICS OF MICROELECTRODE ARRAYS MODIFIED WITH CONDUCTING POLYMER ENTRAPPING ENZYME

 Manabu NARUMI, Tomokazu MATSUE and Isamu UCHIDA

Department of Moleculer Vhemistry and Engineering, Faculty of Engineering, Tohoku University
Aramaki Aoba, Sendai 980, Japan

An enzyme switch, sensitive to a substrate (NADH), was fabricated and its characteristic was investigated. This switch consisted of three Au microband electrode arrays modified with the electro-porimerized polypyrrole entrapping diaphorase. This device turned off only when the substrate was present in a solution.


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17
マルチチャンネル電気化学検出器の試作と評価

 末永智一・青木　純・安藤英児・内田　勇

東北大工

A MULTI-CHANNEL ELECTROCHEMICAL DETECTOR FOR FLOW SYSTEMS

 Tomokazu MATSUE, Atusushi AOKI, Eiji ANDO and Isamu UCHIDA

Department of Molecular Chemistry and Engineering, Faculty of Engineering, Tohoku University
Aramaki Aoba, Sendai 980, Japan

A multi-channel electrochemical flow-through detector for FIA and HPLC was fabricated and its applicability was investigated. The detector has a parallel microelectrode array consisting of 16 microband electrodes. The potential of each microband was independently applied and the current was collected in a computer. The measurements were usually conducted with 80 channel detection by 5-times stepping of the potential applied to 16 band electrodes in order to obtain high potential resolution. This detector was used to detect uric acid in a blood serum.


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18
SnO2系ガスセンサ上に吸着した酸素のESRスペクトル

 床田裕美・岩切豊志・八尋秀典・岩本正和・松浦吉展*・高畠　敬*

宮崎大工・フィガロ技研*

ESR STUDY OF OXYGEN ADSORBATES ON SnO2 GAS SENSORS

 Hiromi TOKODA, Toyoshi IWAKIRI, Hidenori YAHIRO, Masakazu IWAMOTO, Yoshinobu MATSUURA* and Kei TAKAHATA*

Faculty of Engineering, Miyazaki University
Miyazaki-shi, Miyazaki 889-21, Japan
*Figaro Engineering Inc.,
Minoo-shi, Osaka 562, Japan

The adsorption state of oxygen on SnO2 gas sensors and its reactivity were investgated by using an electron spin resonance technique. Four kinds of ESR signals have been found. One is O2-adsorbed on a Sn atom. The assignment of remaining three signals have been tried by applying simulation and N2O-adsorption. They are tentatively attributed to O- ion coordinating two Sn atoms, electron trapped near the surface, and electron with relatively high mobility. The O2- and O- species were desorbed at 100-150℃ and 200-350℃, respectively, which are well corresponding with the results of temperature programmed desorption experiments. It was further clarified that the reactivity of O2- to hydrogen is greater than that of O- at room temperature.


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19
半導体ガスセンサの過渡応答とガス識別

 若林淳右・大嶋幸一郎・白江公輔

阪大基礎工

GAS RECOGNITION USING TRANSIENT RESPONSE OF SEMICONDUCTOR GAS SENSOR

 Kiyosuke WAKABAYASHI, Koichiro OSHIMA and Kimisuke SHIRAE

Department of Control Engineering, Faculty of Engineering Sciences, Osaka University
Toyonaka-shi, Osaka 560, Japan

When the gas concentration is changed, the transient response propaty of a sensor is depend on kind of gas and concentration. This propaty can by used a recognition parameter for kind of gas. In order to change the gas concentration, a measuring apparatus of sensor dynamic response that modeled respiration function is made. On this apparatus, sensor dynamic responses of TGS-812 and 813 are measured in atmosphere of H2, CO and C2H5OH, because of that the necessary characteristics pick out for gas recognition.
From the locus of Lissajous figure between each sensors, useful results for gas recognition can be obtained at lower concentration.


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20
鉄酸化物スパッタ膜のガス検出特性とその要因

 吉川修一・辻本浩章・白江公輔

阪大基礎工

GAS DETECTION PROPERTIES AND DETECTING FACTORS OF IRON OXIDE SPUTTERING FILM

 Shuichi YOSHIKAWA, Hiroaki TSUJIMOTO and Kimisuke SHIRAE

Department of Control Engineering, Faculty of Engineering Science, Osaka University
Toyonaka-shi, Osaka 560, Japan

The iron oxides have various structures, and they are also presented as gas sensors. This paper is concerned with the relation between gas sensitive properties and structures of iron oxide thin films by RF reactive sputtering. By analyzing the structures of iron oxide sputtering thin films, it was estimated that these films were mainly composed of γ-Fe2O3 and Fe3O4. As the experimental result that H2 gas detection property depended on their thickness, we suggested the thin film model depending on thickness.


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21
薄膜半導体センサを用いた水中のオゾンの連続測定法

 青木豊明・大黒広司・原田健治*・塩沢浩明**・高田　義**

阪府大工・富士電機総研*・新コスモス電機**

CONTINUOUS FLOW DETERMINATION OF RESIDUAL AQUEOUS OZONE WITH MEMBRANE SEPARATION-THIN FILM SEMICONDUCTOR

 Toyoaki AOKI, Hiroshi OGURA, Kenji HARADA*, Hiroaki SHIOZAWA** and Tadashi TAKADA**

Laboratory of Environmental Chemistry, College of Engineering, University of Osaka Prefecture
Mozu-umemachi, Sakai 591, Japan
*Fuji electric Corporate Research and development, Ltd.
**New Cosmos Electric Co., Ltd.

A method without any reagent for the determination of ultratrace aqueous ozone utilizing a membrane-separation process and a thin film semiconductor is proposed. A double-tube system, with an inner tube of microporous PTFE and an outer tube of PTFE, is used as the separator to transfer aqueous ozone into a gas phase. Air bubbling was used to enhance the separation. Ozone permeates through microporous PTFE tube and dissolves into clean air flowing in the tube. The inner air flows onto the thin film semiconductor. Signals produced from the semiconductor were proportional to concentration of aqueous ozone more than 5 ppb. Detection limit (S/N=3) was 0.1 ppb. The relative standard deviation (n=4) was 4.8% at 0.15 ppm. The time it took from stating the sample flow until the signal to reach a stable level was 4.0 min. The interference from inorganic ions, amino acids, protein, humic acid, ammonia and chloramines such as monochloramine and dichloramine were completely eliminated. The sensitivity of ozone were ranging from 30 to 130 times greater than those of hypochlorite and chlorine dioxide.


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22
SnO2系ガスセンサにおけるアルコール検知特性の制御

 前川知輝・松嶋茂憲・玉置　純・三浦則雄・山添　f

九大総合理工

CONTROL OF ALCOHOL SENSING CHARACTERISTICS OF SnO2-BASED ELEMENT

 Tomoki MAEKAWA, Shigenori MATSUSHIMA, Jun TAMAKI, Norio MIURA and Noboru YAMAZOE

Department of Materials Science and Technology, Graduate School of Engineering Sciences, Kyushu University
Kasuga-shi, Fukuoka 816, Japan

Influences of various oxide additives and noble metals on C2H5OH sensing properties of an SnO2-based element were examined. The sensitivity and selectivity of the elements could be markedly promoted with the addition of basic oxides represented by La2O3. The promoting effect was estimated to be related with selectivity in oxidation reaction of C2H5OH. Furthermore, noble metal doping was effective to shorten the response time at lower temperature region as well as to elevate the sensitivity at lower C2H5OH concentration.


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23
スピネル型酸化物半導体の酸素センサ機能の発現機構

 江頭　誠・清水康博・高尾雄二・桑山博行・田中克之*

長崎大工・長崎大海洋生産科学*

SENSING MECHANISM OF SPINEL TYPE OXIDES AS AIR/FUEL STOICHIOMETRIC OXYGEN SENSORS

 Makoto EGASHIRA, Yasuhiro SHIMIZU, Yuji TAKAO, Hiroyuki KUWAYAMA and Katsuyuki TANAKA*

Department of Materials Science and Engineering, Faculty of Engineering
*Graduate School of Marine Science and Engineering
Nagasaki University
1-14 Bunkyo-machi, Nagasaki 852, Japan

Oxygen-sensing properties of spinel type oxides as air/fuel stoichiometric oxygen sensors has been investigated based on catalytic activities for complete oxidation of methane and point defect structures of the oxides. The catalytic activities were sell correlated with response times of oxygen-sensing, suggesting that the rate of charge transfer between gaseous oxygen and chemisorbed oxygen at the surface as well as the mobility of oxide ions in the bulk are important for the rapid oxygen-sensing. In addition, it was suggested that concentration of oxide ion vacancies markedly affected both the response times and the sensitivity at the stoichiometric point.


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24
原子価制御法による各種酸化物半導体のトリメチルアミンガス検出特性の改良

 高尾雄二・宮　順孝・清水康博・江頭　誠

長崎大工

IMPROVEMENT IN SENSITIVITY TO TRIMETHYLAMINE OF SEMICONDUCTOR GAS SENSORS BY VALENCY CONTROL

 Yuji TAKAO, Yoritaka MIYA, Yasuhiro SHIMIZU and Makoto EGASHIRA

Department of Materials Science and Engineering, Faculty of Engineering, Nagasaki University
1-14 Bunkyo-machi, Nagasaki 852, Japan

To develop a new type of semiconductor gas sensor capable to detect freshness of fishes, attempts were made to enhance the trimethylamine sensitivity of metal oxides by employing the valency control. The sensitivities were improved by the partial substitution of Ti4+ for Cr3+ in Cr2O3 as well as by that of Mg2+ for In3+ in In2O3, suggesting that the sensitivity can be enhanced by reducing carrier concentration of the oxides. It was revealed that the sensitivity of the In2O3 doped with 5 mol% Mg was comparable to that of TiO2.


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25
光脱離反応を用いる酸素センサの開発

 小林健吉郎・波多野博憲・岡田元次

愛媛大工

OXYGEN SENSOR OF ZnO-SiO2-Au BY USING PHOTODESORPTION OF OXYGEN

 Kenkichiro KOBAYASHI, Hironori HATANO and Genji OKADA

Department of Resources Chemistry, Ehime University
Matsuyama-shi, Ehime 790, Japan

The ZnO-SiO2-Au device was fabricated by means of RF magnetron sputtering technique. In the dark, the device exhibites good rectification characteristic and has no sensitivity to the change in the oxygen partial pressure. After uv illumination the rectification characteristic is drastically broken. The recovery rate of rectification characteristic depends on the ambient oxygen partial pressure. Complex impedance plots of the device indicate that the drastic current change caused by uv illumination is ascribed to the barrier height change. The reduction of the barrier height can be explained by photodesorption of oxygen on the ZnO surface.


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26
CaZrO3系プロトン導電性セラミックを用いた水素および水蒸気センサ

 岩原弘育・内田裕之・長野　貴・小椋敏明

鳥取大工

HYDROGEN AND STEAM SENSORS USING PROTON-CONDUCTING CERAMIC BASED ON CaZrO3

 Hiroyasu IWAHARA, Hiroyuki UCHIDA, Takashi NAGANO and Toshiaki OGURA

Department of Environment Chemistry and Technology, Faculty of Engineering, Tottori University
Koyama-cho, Tottori 680, Japan

Using a proton-conducting oxide ceramic based on CaZrO3, Nernstian hydrogen and steam sensors were constructed. Similar to the proton conductors based on SrCeO3 or BaCeO3, In-doped CaZrO3 functioned stably as a solid electrolyte for such sensors at high temperature. When CO2-blocker (CaCO3) was smeared on the sensing electrode, the sensor detected the equilibrated hydrogen partial pressure selectively in H2O-O2-CO2 gas mixture. The sensor has a potential use for combustion control in combination with zirconia-oxygen sensor.


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27
アルカリ金属硫酸塩を母体とした小型SO2センサプローブ

 今中信人・今井寿雄・足立吟也・塩川二朗*

阪大工・近畿大理工*

A COMPACT SO2 SENSOR PROBE BASED ON ALKALINE SULFATES

 Nobuhito IMANAKA, Hisao IMAI, Gin-ya ADACHI and Jiro SHIOKAWA*

Department of Applied Chemistry, Faculty of Engineering, Osaka University
2-1 Yamadaoka Suita, Osaka 565, Japan
*Department of Applied Chemistry, Faculty of Science and Engineering, Kinki University
3-4-1 Kowakae Higashiosaka, Osaka 577, Japan

A compact SO2 gas sensor probe was fabricated by using the Na2SO4-Li2SO4-Y2 (SO4) 3-V2O5-SiO2 system and the NiSO4-NiO system as a solid electrolyte and a solid reference electrode, respectively. Vanadium pentoxide was mixed into the electrolyte so as to promote SO2 oxidation to SO3. SO2 sensing characteristics were investigated by the probe insertion in a SO2-Air gas mixed atmosphere. The measured EMF was in good accordance with the calculated EMF from the Nernst's equation. The SO2 sensor probe was found to be a handy detector for the SO2 gas.


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28
ペロブスカイト型酸化物電極による固体電解質型酸素センサの低温作動化

 井上高教・関　則彰・江口浩一・荒井弘通

九大総合理工

LOW TEMPERATURE OPERATION OF SOLID OXIDE OXYGEN SENSORS USING PEROVSKITE-TYPE OXIDE ELECTRODES

 Takanori INOUE, Noriaki SEKI, Koichi EGUCHI and Hiromichi ARAI

Department of Materials Science and Technology, Graduate School of Engineering Science, Kyushu University
Kasuga-shi, Fukuoka 816, Japan

The lowest limit of operation temperature for ceria-based solid electrolyte oxygen sensor was significantly reduced with a use of perovskite-type oxide electrodes. In particular, the sensor with La0.6Sr0.4Co0.98Ni0.02O3 exhibited theoretical emf even at 200 C. The cathodic overpotential, which was measured by current interruption method, was low for an electrode operative at low temperature. And, the oxygen ions in perovskite-type oxide, being weakly bonded to metal cation, are expected to be active at low temperatures.


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29
ペロブスカイト型酸化物電極を用いたLaF3酸素センサ

 Jerzy P.Lukaszewicz・三浦則雄・山添　f

九大総合理工

LaF3-BASED OXYGEN SENSOR USING PEROVSKITE-TYPE OXIDE ELECTRODE

 Jerzy P. LUKASZEWICZ*, Norio MIURA and Noboru YAMAZOE

Department of Materials Science and Technology, Graduate School of Engineering Sciences, Kyushu University
Kasuga-shi, Fukuoka 816, Japan
*Institute of Chemistry, N. Copermicus University
87-100 Torun, Poland

LaF3-based oxygen sensors were constructed by using six perovskite-type oxides for the sensing electrode. It was found that oxygen sensing characteristics of the oxide electrodes, i.e., sensitivity to a change in oxygen partial pressure and response time, were greatly dependent on the oxide used, the dependence being closely related with the activity of the oxides for the electrochemical reduction of oxygen in solution. Among the oxides tested, LaCrO3, LaCoO3 and LaMnO3 were found to give a sensing electrode with higher sensitivity and shorter response time than Pt sensing electrode.


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30
相互侵入網目構造を有するポリマーアロイを用いた耐水性湿度センサ

 酒井義郎・松口正信・定岡芳彦・平松　勲

愛媛大工

WATER RESISTIVE HUMIDITY SENSOR COMPOSED OF INTERPENETRATING POLYMER NETWORKS

 Yoshiro SAKAI, Masanobu MATSUGUCHI, Yoshihiko SADAOKA and Isao HIRAMATSU

Department of Industrial Chemistry, Faculty of Engineering, Ehime University
Matsuyama-shi, Ehime 790, Japan

A water resistive humidity sensor was produced by forming the film of a interpenetrating polymer networks (IPN) between the crosslinked poly (2-hydroxy-3-methacryloxypropyl trimethylammonium chloride) HMPTAC and the crosslinked melamine resin. The value of impedance was the same as that of the HMPTAC homopolymer in the whole humidity range. The activation energy for the resistance has a maximum value at 40% relative humidity. In the low humidity range, chloride ion is the majority carrier and its apparent ionic radius increases due to the hydration as the humidity increases up to 40% r.h. On the other hand, in the high humidity range, the conduction by protons becomes predominant and the activation energy decreases as the amount of sorbed water increases. The sensor composed of HMPTAC and melamine IPN film showed excellent water resistivity.


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31
４級アンモニウム基を有するポリマーをグラフト重合した多孔質ポリエチレンフィルムを用いた湿度センサ

 松口正信・酒井義郎・定岡芳彦・神垣　守

愛媛大工

HUMIDITY SENSOR USING POROUS POLYETHYLENE GRAFTED WITH POLYELECTROLYTES

 Masanobu MATSUGUCHI, Yoshiro SAKAI, Yoshihiko SADAOKA and Mamoru KAMIGAKI

Department of Industrial Chemistry, Faculty of Engineering, Ehime University
Matsuyama-shi, Ehime 790, Japan

2-hydroxy-3methacryloxypropyl trimethylammonium chloride was grafted on the pore wall of the microporous polyethylene film by a γ-ray pre-irradiation method. A humidity sensor was prepared by depositing the gold electrodes on both surfaces of the grafted film. The impedance decreased exponentially as the humidity decreased and the response by changing the humidity was fast. The sensor was stable even in water for more than 2 hours and in an ordinary atmosphere for a long time . The heat resistivity was improved because polyethylene film was crosslinked by γ-ray pre-irradiation.


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32
CO2センサの開発

 片山晋一・岩切芳和・八尋秀典・岩本正和

宮崎大工

DEVELOPMENT OF CO2 GAS SENSOR USING ZEROLITES AS SENSOR MATERIALS

 Shin-ichi KATAYAMA, Yoshikazu IWAKIRI, Hidenori YAHIRO and Masakazu IWAMOTO

Faculty of Engineering. Miyazaki University
Miyazaki-shi, Miyazaki 899-21, Japan

This study have been devoted to develop a new type of CO2 sensor by using various zeolites. Platinum coil which was connected in a Wheatstone Bridge circuit was covered by the zeolites and the property for sensing CO2 was examined. Ca2+ ion-exchanged mordenite-type zeolites showed the highest sensitivity. The sensing abilities of zeolites have been examined as a function of the zeolite structure, silica alumina molar ratio, kind of cation and its exchange level, and the amount of CO2 adsorbed at 623 K. It follows that the sensitivity is dependent on the CO2-adsorbability.


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33
電気化学センサによるハロゲン化炭化水素の検知 ― 第２報

 小宮弘隆・木村伸一

バイオニクス機器

FREON AND HALOGENATED HYDROCARBON DETECTION WITH ELECTROCHEMICAL SENSORS

 Hirotaka KOMIYA and Shiichi KIMURA

Bionics Instrument Co., Ltd.
6-1254-2 Shimizu, Higashiyamato, Tokyo 189, Japan

A new method was introduced for continuously detecting freons and chlorinated hydrocarbons by combining electrochemical sensors and a hot filament. An HCl sensor, which does not require external applied voltage, was selected to detect electrochemical active gases after pyrolysis over a heated filament. However, it was not able to detect CF4 and C2F6 which are chemically and thermally very stable. It is confirmed that an acid gas sensor which responds to all acid gases can be used to detect CF4 and C2F6. In spite of its high sensitivity, the response was very slow. It was found that a Cl2 sensor showed excellent performance for detection of CBrF3 and CH3Br. But this Cl2 sensor was not suitable for detection of TLV level of CCl4.


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特別講演２
セラミック酸素センサの材料とその特性

 荒井弘通

九大総合理工

MATERIALS AND CHARACTERISTICS OF VARIOUS CERAMIC OXYGEN SENSORS

 Hiromichi ARAI

Department of Materials Science and Technology, Graduate School of Engineering Sciences, Kyushu University
Kasuga-shi, Fukuoka 816, Japan

Various ceramic oxygen sensors developed for lots of fields are reviewed. These oxygen sensors are classified into three types, (1) concentration cell, (2) oxide semiconductor and (3) electrochemical pump (limiting current). The properties of these materials are discussed and their performance characteristics are compared. Finally, recent progress in lean fuel-air ratio control sensor is discussed.


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To Record of Chemical Sensor Symposium (Japanese)
To Record of Chemical Sensor Symposium (English)