Vol. 7, Supplement B (1991)

Digest of the 13th Chemical Sensor Symposium
October 12-13, 1991
Nagoya Institute of Technology

Abstracts

1
グルコース脱水素酵素、補酵素、メディエーター固定化ポリピロール膜のグルコースセンサ作用

 梶谷芳男・松本　一・米山　宏

阪大工

GLUCOSE-SENSING PROPERTIES OF POLYPYRROLE FILMS CONTAINING IMMOBILIZED GLUCOSE DEHYDROGENASE, NICOTINAMIDE ADENINE DINUCLEOTIDE, AND AN ELECTRON MEDIATOR

 Yoshio KAJIYA, Hajime MATSUMOTO and Hiroshi YONEYAMA

Department of Applied Chemistry, Faculty of Engineering, Osaka University
2-1 Yamada-oka Suita-shi, Osaka 565, Japan

Glucose dehydrogenase, nicotinamide adenine dinucleotide, and β-naphtoquinonesulfonate were immobilized in polypyrrole films prepared by electropolymerization of pyrrole in an aqueous solution containing these substances. The resulting polypyrrole films showed amperometric glucose sensitivities without assistance of any electron mediator in solution. It was found that there is an optimum deposition charge to achieve the highest sensitivity, and the sensitivity is affected by pH of glucose solution, suggesting that the amperometric sensitivities is controlled by the redox activities of naphtoquinonesulfonate incorporated in polypyrrole films.


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2
An Amperometric Sensor with Fructose Dehydrogenase-Entrapped Polypyrrole Interface

 G. F.Khan・E.Kobatake・H.Shinohara・Y.Ikariyama・M.Aizawa

Dept. of Bioeng., Tokyo Inst. Tech.

Direct electron transfer between a PQQ oxidoreductase (fructose dehydrogenase: FDH) and Pt electrode was examined to fabricate an amperometric sensor for fructose. An approach for the smooth electron transfer was proposed by making a molecular interface between the enzyme and the electrode surface. An electron mediator was also incorporated into the molecular interface to shuttle electrons from the analyte to the electrode at less extreme applied potential. Monolayer FDH adsorbed electrochemically exhibited distinct and rapid electron transfer to the electrode at a potential scarcely higher than the redox potential of PQQ {0.06 V (1)} upon the addition of D-fructose. An ultrathin membrane of conductive polypyrrole (PP) was electrochemically polymerized over the FDH-adsorbed electrode to introduce a molecular interface and also to prevent the enzyme from desorption. Due to the molecular writing of the conductive polypyrrole, the current response for D-fructose was increased several times. The current response further magnified by the incorporation of an electron mediator. In both cases, the response current depends linearly of D-fructose concentration in the range from 10 μM to 10 mM.


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3
グルコースオキシダーゼ固定化N-置換ポリピロール薄膜電極の作製 およびそのセンサへの応用（２）

 安澤幹人・松下伸幸・佐竹　弘・金品昌志・椚　　章

徳島大工

FABRICATION OF THIN FILM ELECTRODE IMMOBILIZED GLUCOSE OXIDASE IN N-SUBSTITUTED POLYPYRROLE FILM AND ITS APPLICATION TO GLUCOSE SENSOR (2)

Mikito YASUZAWA, Nobuyuki MATSUSHITA, Hiromu SATAKE, Syouji KANESHINA and Akira KUNUGI

Department of Chemical Science and Technology, Faculty of Engineering, The University of Tokushima
Minamijosanjima-cho, Tokushima 770, Japan

An effective glucose sensor was prepared immobilizing glucose oxidase (GOD) by electropolymerization of N-substituted pyrrole derivatives (1-pyrrole propionic acid; PPA and 1-pyrrole propanol; PPOH). The characterization of GOD/PPPA or PPPOH/Pt electrode was investigated by FIA system. The glucose sensor having good sensitivity and stability was obtained by the copolymerization of PPA and PPOH (1:1).


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4
NADPH酸化酵素とG-6-P脱水素酵素とを利用した酵素電極

 水谷文雄・奥田　篤*・矢吹聡一・曽良達生

繊高研・北海道工試*

AMPEROMETRIC ENZYME ELECTRODE WITH THE USE OF NADPH OXIDASE AND G-6-P DEHYDROGENASE

 Fumio MIZUTANI, Atsushi OKUDA*, Soichi YABUKI and Tatsuo KATSURA

Research Institute for Polymers and Textiles
1-1-4 Higashi Tsukuba, Ibaraki 305, Japan
*Hokkaido Industrial Reserch Institute
19 Kita 11 Nishi, Sapporo 060, Japan

Two kinds of enzyme layers, one contains NADPH oxidase (layer I) and the other contains NADPH oxidase and glucose-6-phosphate (G-6-P) dehydrogenase (layer II), are prepared and are separately combined with Clark oxygen electrodes. The resulting enzyme electrodes are used for the determination of NADPH. The detection limits are 5 μM for the electrode with the layer I and 0.1 μM for that with the layer II in the presence of G-6-P. The amplification of current response through te cyclic enzymatic reactions between NADPH and NADP+ brings about the high sensitivity in the latter system.


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5
金コロイドを用いる集積型バイオセンサの開発

 中島健治*・鈴木正康・民谷栄一・軽部征夫

テクノローグ*・東大先端研

DEVELOPMENT OF INTEGRATED BIOSENSORS USING GOLD COLLOID

 Kenji NAKAJIMA*, Masayasu SUZUKI, Eiichi TAMIYA and Isao KARUBE

*Teknologue co., LTD.,
Choufu-city, Tokyo 182, Japan
Research Center for Advanced Science and Technology, University of Tokyo
Meguro-ku, Tokyo 153, Japan

A selective immobilization of enzymes is strongly required for the construction of an integrated micro-biosensors. We paid attention to gold colloid which has a negative charge and can adsorbed protein. Glucose oxidase and Lactate oxidase were immobilized onto each platinum disk electrode (φ=30 μm) using galvanostatic method (200nA, 90 min). The determination ranges were from 0.9〜5 mM for glucose, and 0.35〜1.2 mM for lactate. Response time was within 100sec. Apparently gold colloid is useful for integration into micro-biosensors.


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6
EEEセンサの非定常応答

 山内　繁・松本　太*・横山崇裕*・矢尾板仁・碇山義人**

国立リハ研・東京理科大理*・東工大生命理工**

TRANSIENT RESPONSE OF EEE SENSOR IN PULSE TECHNIQUES

 Shigeru YAMAUCHI, Futoshi MATSUMOTO*, Takahiro YOKOYAMA*, Masashi YAOITA and Yoshito IKARIYAMA**

Research Institute of National Rehabilitation Center
4-1 Namiki Tokorozawa, Saitama 359, Japan
*Department of Chemistry, Science University of Tokyo
1-3 Kagurazaka Shinjuku-ku, Tokyo 162, Japan
**Dept. of Bioengineering, Tokyo Institute of Technology
4259 Nagatuda Midori-ku, Yokohama 227, Japan

An enzyme embodied electrode (EEE) fabricated by direct immobilization of enzyme on a platinum black electrode was adopted to be used as a working electrode for glucose sensing pulse voltammetric device. A reaction scheme in the micropores of platinum black is proposed, where in hydrogen peroxide produced while the circuit is kept open is oxidized to produce anodic transient current. Based on this scheme a preoxidation pulse technique was developed, which was followed by an open circuit period and the measurement with a potentiostatic pulse. A consecutive pulse technique was also proposed, wherein a sequence of an anodic pulse and an open circuit period is repeatedly given. The transient current was measured at each initial edge of the anodic pulse. The open circuit period plays a central role in this pulse technique. A reproducible sensor response with this technique revealed another advantage that any blank measurement are necessary.


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7
酵素単分子層・二分子層修飾電極の定常応答解析

 立間　徹・渡辺　正

東大生研

STEADY-STATE RESPONSE ANALYSIS OF THE ENZYME MONOLAYER- AND BILAYER-MODIFIED ELECTRODES

 Tetsu TATSUMA and Tadashi WATANABE

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

The steady-state sensor responses of enzyme monolayer- and heterobilayer-modified electrodes were theoretically analyzed. The sensor response was divided into three factors; the efficiencies of substrate and mediator supply to enzyme, the enzyme/electrode charge transfer efficiency, and the potential rate of enzymatic reaction where the supply efficiencies are unity. Contributions of the parameters to these factors or the total sensor response were examined. The experimental observations are successfully interpreted in terms of these theoretical results.


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8
酵素固定化TCNQ錯体薄膜を用いたグルコースセンサ

 岸本芳久・横田佳子・高野哲雄

住友金属工業ハイクォリティライフ研

THIN FILM ELECTRODE BASED ON TCNQ COMPLEX AND IMMOBILIZED ENZYME FOR GLUCOSE SENSOR

 Yoshihisa KISHIMOTO, Yoshiko YOKOTA and Tetsuo TAKANO

Sumitomo Metal Industries, Ltd. High Quality Life Research Laboratories
1-8 Fusocho Amagasaki, Hyogo 660, Japan

Thin film of TCNQ (tetracyanoquinodimethane) complex and immobilized glucose oxidase (GOD) was prepared and the applicability of this new type of enzyme electrode for an amperometric glucose sensor was evaluated.
This enzyme electrode is coated with two layers. The inner layer of the TCNQ charge transfer complex was electrolyzed spontaneously on the surface of Cu of Ag substrate in TCNQ solution. In the outer layer there are incorporated GOD and an electron mediator uniformly in the polymer matrix.
Electron transfer is assumed to occur across the two layers by the aid of the mediator and conducting complex. Our sensing system shows rapid current response and stabilization against the fluctuation of dissolved oxygen concentration.
Results thus obtained are also useful for the glucose sensor to simplify its fabrication process.


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9
ヌクレオシドオキシダーゼ電極、ヌクレオシド酸化による還元電流応答

 池田篤治・磯野義員*・千田　貢

京大農・大塚食品*

A NUCLEOSIDE OXIDASE-MODIFIED ELECTRODE. CATHODIC CURRENT RESPONSE TO NUCLEOSIDES

 Tokuji IKEDA, Yoshikazu ISONO* and Mitsugi SENDA

Department of Agricultural Chemistry, Kyoto University
Sakyo-ku, Kyoto 606, Japan
*Biwako Research Institute, Otsuka Foods Co., Ltd.
Karasaki Otsu, Shiga 520-01, Japan

The cathodic current for the reduction of benzoquinone at a glassy carbon electrode was increased in the presence of nucleoside oxidase and inosine. This was attributed to the regeneration of benzoquinone from hydroquinone by the laccaselike reaction of the enzyme, the rate of which depended on the concentration of inosine in the solution. Accordingly, an enzyme electrode for nucleosides was constructed by immobilizing nucleoside oxidase behind a dialysis membrane on a carbon paste electrode containing p-benzoquinone of hyroquinone. The current response of the electrode to nucleosides was studied. The nucleoside oxidase-modified electrode was tested as an amperometric enzyme electrode for nucleosides.


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10
プロトン導電性固体電解質を用いた電流検出型グルコースセンサ

 又吉直子・三浦則雄・山添　f

九大総合理工

AN AMPEROMETRIC GLUCOSE SENSOR USING PROTON-CONDUCTIVE SOLID ELECTROLYTE

 Naoko MATAYOSHI, Norio MIURA and Noboru YAMAZOE

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

A new solid-state sensor using proton-conductor thick-film was examined for the amperometric detection of glucose. The sensor element had a planar-type structure which is convenient for fabrication of miniaturized or integrated sensors. The antimonic-acid thick-film was formed on a porous alumina substrate by a spin-coating method. A sensing Pt electrode, a counter Au electrode and a reference Ag electrode were deposited on the surface of the thick-film by RF sputtering method. Glucose oxidase (GOD) was immobilized by applying it together with carbon paste on the sensing Pt electrode. At an applied voltage of +0.7 V, the sensing current of glucose increased linearly with an increase in glucose concentration from 0 to 7×10-3 M, with the 90% response time of ca. 2min. A new sensing mode using short-circuit current response was also examined.


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特別講演１
プロトン導電性セラミックスを用いた水素及び水蒸気センサ

岩原弘育

名大工

HYDROGEN AND STEAM SENSORS USING PROTON CONDUCTING CERAMICS

 Hiroyasu IWAHARA

Synthetic Crystal Research Laboratory, School of Engineering, Nagoya University
Furo-cho Chikusa-ku, Nagoya 464-01, Japan

Using proton conducting ceramics based on perovskite-type oxides as a solid electrolyte, galvanic-cell-type, high temperature hydrogen and steam sensors cam be constructed. Here, the principle, the advantages and the characteristics of these sensors are reviewed citing experiments made in our laboratory.


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11
ISFET型アセチルコリンセンサによる酵素活性阻害物質の測定

 坂井宏光・金木則明・原　　弘

室蘭工大

DETERMINATION OF CHEMICALS BY ACETYLCHOLINE SENSOR USING ISFET

 Hiromitsu SAKAI, Noriaki KANEKI and Hiroshi HARA

Department of Computer Science and Systems Engineering, Faculty of Engineering, Muroran Institute of Technology
27-1 Mizumoto-cho, Muroran 050, Japan

Acetylcholine sensor based on ISFET as a pH sensor, using the immobilized acetylcholine esterase (AChE) in the BSA membrane are reported for the characteristics and for measuring chemicals. The detection range of acetylcholine using the AChE-ISFET sensor was 5×10-5-10-2 M. The response of the enzyme sensor was depended on pH (optimal pH 8.0) and the concentration of the buffer solution. The analysis of chemicals are reported using the present acetylcholine sensor based on the inhibition of the immobilized AChE. Reactivation of immobilized AChE after inhibition with irreversible inhibitor, is carried out using a mixture of acetylcholine and pyridine-2-aldoxime methiodide (PAM). The detection for DEP and methomyl are found to be in the range 5×10-5-10-1 M and 10-2-5×10-1 M respectively.


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12
ISFET型グルコースセンサによる血清サンプルの無希釈連続測定

 齋藤　敦・塩野谷紀聖子*・木村　純・栗山敏秀**

日本電気　資源研・分析評価センタ*、マイクロ研**

CONTINUOUS NON-DILUTED SERUM SAMPLE MEASUREMENT WITH AN ISFET GLUCOSE SENSOR

 Atsushi SAITO, Kiseko SHIONOYA, Jun KIMURA and Toshihide KURIYAMA

Resources & Environment Protection Research Laboratories
Analysis & Evaluation Technology Center
Microelectronics Research Laboratories
NEC Corporation

Kawasaki, Kanagawa 216, Japan

A continuous serum glucose measurement system using an ion-sensitive field-effect transistor (ISFET) glucose sensor is developed and evaluated. The sensor is composed of an ISFET, a glucose oxidase immobilized membrane and an external membrane. The external membrane, which is albumin highly crosslinked by glutaraldehyde, restricts glucose diffusion, to expand the calibration curve linear range. This sensor is used to measure glucose concentration in NaCl solution (0.15 M). A good linearity, up to 400 mg/dl glucose, is achieved, so that this sensor is considered capable of accurate measurement without a pH buffer solution. This sensor is connected to a flow cell, into which serum samples and air alternately flow. The output shows a good linear relationship with up to 300 mg/dl glucose and correlates well with a conventional glucose analyzer. This result indicates that continuous measurement of glucose in serum without a pH buffer solution is successfully accomplished.


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13
メタンフェタミンの高感度検出用としての免疫反応利用型水晶振動式センサ

 三浦則雄・肥後橋弘喜・武安　明*・宇田泰三**・山添　f

九大総合理工・宇部興産*・広島県立大**

PIEZOELECTRIC CRYSTAL IMMUNOSENSOR FOR SENSITIVE DETECTION OF METHAMPHETAMINE

 Norio MIURA, Hiroki HIGOBASHI, Akira TAKEYASU*, Taizo UDA** and Noboru YAMAZOE

Department of Materials Science, Graduate School of Engineering Sciences, Kyushu University
Kasuga-shi, Fukuoka 816, Japan
*Central Research Laboratory, UBE Industries Ltd.,
Ube-shi, Yamaguchi 755, Japan
**Hiroshima Prefectural University, School of Bioresources
Shoubara, Hiroshima 727, Japan

A sensitive piezoelectric crystal immunosensor for methamphetamine (MA) has been proposed. Pt-black was electrodeposited on top of the Au electrode on an AT-cut quartz crystal. MA-albumin conjugate (MA-BSA) was adsorbed on the surface of the crystal. On contact to a solution of monoclonal antibody against MA (antigen), the resonant frequency of the crystal decreased to a level well correlated with the antibody concentration. At a fixed antibody concentration, the frequency response (僥) was found to be attenuated by the coexistence of MA in the antibody solution. Based on this principle, it was possible to detect 0.02-10 ppm MA, with a 90% response time of about 5 min.


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14
免疫反応を利用した爆発物検出機の開発

 中山　浩・杉原宏和・高橋系子・宮崎仁誠・光亦忠泰

松下電器中研

THE DEVELOPMENT OF SENSOR FOR EXPLOSIVES USING IMMUNE REACTION

 Hiroshi NAKAYAMA, Hirokazu SUGIHARA, Keiko TAKAHASHI, Jinsei MIYAZAKI and Tadayasu MITSUMATA

Matsushita Electric Industrial Co., Ltd. Central Research Lab.
Moriguchi, Osaka 570, Japan

We have developed a technique for measuring trace amounts (10-9 M) of trinitrotoluene (TNT-a low molecular weight organic compound used explosives) in water solutions within 1 minute, using biological methods.
We combined the original detection method, called Fluorescence Quenching, with a basic immunoassay and increase the assay speed 300-fikd without sacrificing the high sensitivity and selectivity of the immnoassay.


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15
CCD素子を用いた培養肝細胞の観察

 大橋昭王・宮本重幸・木村　純・戸辺成四郎*・赤池敏宏**

日本電気資源環境研・神奈川科学技術アカデミー*・東工大生命理工**

OBSERVATION OF CULTURED HEPATOCYTES BASED ON A CCD

 Akio OHASHI, Sigeyuki MIYAMOTO, Jun KIMURA, Seishiro TOBE* and Toshihiro AKAIKE**

Resources & Environment Protection Research Laboratories, NEC Corporation
Kawasaki, Kanagawa, Japan
*Kanagawa Academy of Science and Technology
Kawasaki, Kanagawa Japan
**Faculty of Bioscience and Biotechnology, Tokyo Institute of Technology
Yokohama, Kanagawa 227,Japan

When cultured hepatocytes are observed continuously, culture conditions for the hepatocytes have to be kept constant. These conditions include temperature, humidity and carbon dioxide (CO2) concentration. For observation of cultured hepatocytes, a large optical microscope is utilized with a camera or video system. However, it is difficult to maintain constant culture conditions with such a microscope. Thus, observation equipment for cultured hepatocyte is developed.
Using this equipment, primary cultured primary rat hepatocytes were observed continuously. This equipment has capability being used as a toxic sensing system with cultured hepatocytes.


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16
固定化酵素-化学発光系を用いるリン酸の高感度測定

 鈴木正康・山本弘之*・戸松千秋*・大池高保*・西田亮子**・蟻川芳子**・久保いづみ***軽部征夫

東大先端研・鶴見精機*・日女大家政**・創価大工***

HIGHLY SENSITIVE DETERMINATION OF PHOSPHATE IONS BASED ON THE IMMOBILIZED ENZYME-CHEMILUMINESCENCE SYSTEM

 Masayasu SUZUKI, Hiroyuki YAMAMOTO*, Chiaki TOMATSU*, Takayasu OOIKE*, Ryoko NISHIDA**, Yoshiko ARIKAWA**, Izumi KUBO*** and Isao KARUBE

Research Center for Advanced Science and Technology, University of Tokyo
Meguro-ku, Tokyo 153, Japan
*The Tsurumi-seiki Co., Ltd.,
Tsurumi, Yokohama 230, Japan
**Faculty of Domestic Science, Japan Women's University
Mejirodai Bunkyo-ku, Tokyo, Japan
***Faculty of Engineering, Soka University
Hachioji, Tokyo, Japan

Phosphate ion sensor was constructed utilizing the immobilized pyruvate oxidase and luminol-p-iodophenol-chemiluminescence system. Since pyruvate oxidase (POP; from Pediococcus sp., EC 1.2.3.3) requires phosphate ions when it oxidizes pyruvate, phosphate ions might be determined utilizing POP reaction. Hydrogen peroxide produced by POP reaction was determined by the use of peroxidase-luminol-p-iodophenol chemiluminescence reaction. Response time for phosphate ion was 90s. Optimal composition of the reaction solution was 2 mM pyruvete, 0.6 mM Thiamine pyrophosphate (TPP) and 0.1 μM Flavin dinucleotide (FAD). Phosphate ions could be determined in the concentration range between 0.05 ppm and 5 ppm. Components of lake water did not affect the sensor response.


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17
半導体加工技術を利用した酵素フロー分析用化学発光検出器

 須田正之・村松　宏・作原寿彦・中村秀明*・村上裕二**・鈴木正康**・民谷栄一**・内山俊一*・鈴木周一*・軽部征夫**

セイコー電子工業・埼玉工大工*・東大先端研**

CHEMILUMINESCENCE DETECTOR FOR ENZYMATIC FIA PREPARED BY MICROMACHINING

 Masayasu SUDA, Hiroshi MURAMATSU, Toshihiko SAKUHARA, Hideaki NAKAMURA, Yuji MURAKAMI, Masayasu SUZUKI, Eiichi TAMIYA, Shunichi UCHIYAMA, Syuuichi SUZUKI and Isao KARUBE

Seiko Instruments Inc.,
563 Takatsuka-shinden Matsudo-shi, Chiba 271, Japan
Saitama Institute of Technology
1690 Ohaza Fuzaiji Okabemachi, Ohosato-gun, Saitama 369-02, Japan
Research Center for Advanced Science and Technology, University of Tokyo
4-6-1 Komaba Meguro-ku, Tokyo 153, Japan

A micro chemiluminescence detector for enzymatic FIA was fabricated with micromachining techniques. An enzymatic reaction column, a mixing chamber, a spiral flow-through cell were formed on a silicon substrate (n type, 500 μm thick) by anisotropic etching, and PYREXR glass plate (1 mm thick) was anodically bonded on it. The whole size of the detector is 15×20 mm. Incase of the H2O2 determination with lucigenin chemiluminescence reaction, a linear calibration curve was obtained in the range from 100 μM to 15 mM. The detector was also applied to the determination of glucose concentration with immobilized glucose oxidase (GOD).


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18
流速影響のない溶存酸素測定法 (1) ミクロホール内でのパルス電解

 斎藤幸司・清水義浩*・森田健一

桐蔭学園横浜大・東レ基研*

FLOW-RATE-INSENSITIVE OXYGEN SENSOR (1).
PULSE ELECTROLYSIS WITHIN A MICROHOLE.

Koji SAITO, Yoshihiro SHIMIZU and Ken-ichi MORITA

Department of Materials Science and Technology, TOIN University of Yokohama
Kurogane-cho Midori-ku, Yokohama 225, Japan
*Basic Research Laboratories, TORAY IND. INC.,
Tebiro, Kamakura 248, Japan

An amperometric flow-rate-insensitive oxygen sensor was investigated. An amperometric oxygen sensor widely used today can not give correct results of measurements when the solution to be detected is in the stationary states or in the slowly stirred states because the sensor is flow-rate-sensitive. It was found that the flow-rate becomes insensitive when a Microhole Array Electrode is employed and an amperometric electrolysis of oxygen is performed within a microhole by the use of a normal pulse polarographic technique.


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19
流速影響のない溶存酸素測定法 (2) パルス電解の隔膜センサへの応用

 降谷悦雄*・山里昌春*・森田健一

東亜電波工業*・桐蔭学園横浜大

FLOW-RATE-INSENSITIVE OXYGEN SENSOR (2)
APPLICATION OF PULSE ELECTROLYSIS TO A MEMBRANE SENSOR

 Etsuo FURUYA*, Masaharu YAMASATO* and Ken-ichi MORITA

*Department of analytical Technology, TOA Electronics Ltd.,
Kitairiso, Sayama-shi 613, Japan
Department of Materials Science and Technology, Toin University of Yokohama
Kurogane-cho Midori-ku, Yokohama 215, Japan

Since amperometric membrane oxygen sensors now available are flow-rate-sensitive, it is needed to stir a sample for correct measurements. It was found that the menbrane oxygen sensor became flow-rate-insensitive by the use of the polous membrane and the pulse electrolysis. The method will be applied to other oxidizable and reducible gasses like chloline or hydrogen.


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20
マイクロマシン技術による小型ガラス電極の作製

 鈴木博章・小嶋尚美・菅間明夫

富士通研

FABRICATION OF A MINIATURE GLASS ELECTRODE BY MICROMACHINING TECHNIQUES

 Hiroaki SUZUKI, Naomi KOJIMA and Akio SUGAMA

FUJITSU LABORATORIES LTD.
Atsugi-shi, Kanagawa 243-01, Japan

A miniature glass electrode was fabricated by micromachining techniques. A Ag/AgCl reference electrode was formed on a 7740 glass substrate. The container for the electrolyte solution was made by anisotropically etching a (100) silicon substrate where a 20-μm-thick 7740 glass membrane was also formed. The glass and silicon substrates were bonded by field-assisted bonding. To make the membrane more sensitive to pH change, a 500-nm-thick Na-Ca glass thin film layer was formed on the glass membrane. The 90% response time was 10 seconds. The glass electrode potential varied against pH with a gradient of about -50 mV/pH at 25℃.


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21
ポリピロール被覆マイクロアレイ電極のpH感応素子への応用

 西澤松彦・澤口隆博・末永智一・内田　勇

東北大工

pH SENSITIVE POLYPYRROLE-BASED ELECTROCHEMICAL DEVICE

 Matsuhiko NISHIZAWA, Takahiro SAWAGUCHI, Tomokazu MATSUE and Isamu UCHIDA

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

A pH sensitive electrochemical device was fabricated by electropolymerization of polypyrrole at a microarray electrode using the finding that the electrical conductivity of polypyrrole prepared on our microarray electrode system reversibly responds to pH changes. The pH sensitive device coated with a penicillinase membrane worked as a penicillin sensor, since the enzyme reaction yields an acidic product which increases the conductivity of polypyrrole.


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22
Li系副電極とNa+導電体を用いたCO2センサ

 姚　勝・清水陽一・三浦則雄・二田穂積*・山添　f

九大総合理工・矢崎計器*

SOLID ELECTROLYTE CO2 SENSOR USING NASICON AND Li-BASED CARBONATE ELECTRODE

 Sheng YAO, Youichi SHIMIZU, Norio MIURA, Hozumi FUTATA* and Noboru YAMAZOE

Department of Materials Science and Technology, Graduate School of Engineering Sciences, Kyushu University
Kasuga, Fukuoka 816, Japan
Yazaki Meter Co. Ltd.,
Hamakita, Shizuoka 434, Japan

New type CO2 sensor was developed by combining NASICON and Li2CO3-CaCO3 electrode. It responded to CO2 quickly and reversibly at 500℃, following a Nernst equation excellently in the CO2 concentration range 102-105 ppm even under humid condition. The sensor EMF was hardly affected by the coexistence of CO (90 ppm), NO (100 ppm) and NO2 (50 ppm), while SO2 (50 ppm) interfered somewhat with the EMF response. The electrode was found to be quite stable to deliquescence even when exposed to the air nearly saturated with water vapor at 30℃ for more than 700 h.


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23
Na5YSi4O12セラミックスの導電性と炭酸ガスセンサへの応用

 小松原一雄・松口正信・定岡芳彦・酒井義郎

愛媛大工

CONDUCTIVITY OF Na5YSi4O12 CERAMICS AND APPLICATION TO CO2 GAS SENSOR

 Kazuo KOMATSUBARA, Masanobu MATSUGUCHI, Yoshihiko SADAOKA and Yoshiro SAKAI

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

The conductivity of Na5YSi4O12 doped Na2O-Y2O3-SiO2 (6.69 : 1.00 : 9.25) glass has been measured. The conductivity of Na5YSi4O12 was enhanced by an adding of the glass. The CO2 sensing characteristics of all solid electrochemical cell with the electrolyte were examined. The cell arrangement cam be represented as,
O2, Pt | Na ion conductor | Pt, Na2CO3, CO2, O2
The number of electron for the electrochemical reaction was slightly higher than 2. The coexisting of the water vapour lowered the e.m.f.value. The changes of response characteristics were almost recovered after cut off the water vapour.


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24
固体電解質を用いた単一らせん電極素子 (SMED) のガスセンシング特性とその機構

 森　和代・矢嶋　保・岩原弘育

名大工

GAS SENSING CHARACTERISTICS OF SPIRAL MONOELECTRODE DEVICE (SMED) USING SOLID ELECTROLYTES AND ITS SENSING MECHANISM

 Kazuyo MORI, Tamotsu YAJIMA and Hiroyasu IWAHARA

Synthetic Crystal Research Laboratory, School of Engineering, Nagoya University
Furo-cho Chikusa-ku, Nagoya, 464-01, Japan

Gas sensing characteristics of Spiral Monoelectrode Device (SMED) using YSZ was investigated under various conditions. When dc current was sent to SMED at high temperature and the test gas was changed, its terminal voltage increased with decreasing PO2. The rate determining step for its electrode reactions changed from a charge-transfer process to a mass-transfer process as PO2 in the gas was lowered.


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25
固体電解質を用いたマイクロCOセンサ (II)

 山鹿範行・藤岡　透・渡部祥文・土井謙之・井上孝啓・草薙繁量

松下電工中研

MICROELECTROCHEMICAL CO SENSOR USING SOLID ELECTROLYTE (II)

Noriyuki YAMAGA, Toru FUJIOKA, Yoshihumi WATABE, Kinji DOI, Takahiro INOUE and Shigekazu KUSANAGI

Central Research Laboratory, Matsushita Electric Works, Ltd.
1048 Kadoma, Osaka 571, Japan

It was reported that the high sensitive CO sensor was realized by using three-dimensional electrodes fabricated on Si substrat. In this paper, the important characteristics for practical use including gas sensitivity, selectivity, humidity dependence and long-term stability, etc. were evaluated. Furthermore, it was found that the sensor response was greatly improved by applying an alumina filter, water reservoir and hydrophobic protective membrane.


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26
NAFION膜を用いた酸素センサの作製と塗膜における酸素透過の評価への応用

 高　云智・渡辺幸雄*・島謙一郎*・喜多秀明

北大理・日産自動車*

NAFION MATRIX OXYGEN SENSOR AND EVALUATION OF OXYGEN PENETRATION IN PAINT FILMS

 Yunzhi GAO, Yukio WATANABE*, Kenichirou SIMA* and Hideaki KITA

Department of Chemistry, Faculty of Science Hokkaido University
Sapporo 060, Japan
*Materials Research Laboratory, Central Engineering Laboratories of NISSAN MOTOR CO., LTD
Yokosuka 237, Japan

A small and simple oxygen sensor has been developed. Its matrix is Nafion. Its sensing electrode and counter electrode were made by depositing Pt on Nafion by means of RF sputtering. The dependence of the limiting current on oxygen partial pressure is linear except at zero pressure. This sensor enables us to estimate the oxygen penetration in paint films at working conditions.


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27
電気化学的律速手法を用いた限界電流式酸素センサ

 兼安一成・中原　毅・武内　隆

徳山曹達

LIMITING CURRENT TYPE OXYGEN SENSOR WITH SOLID ELECTROLYTE RATE-DETERMINING LAYER

 Kazunari KANEYASU, Takeshi NAKAHARA and Takashi TAKEUCHI

TOKUYAMA SODA CO., LTD
2051 Endo Fujisawa-city, Kanagawa 252, Japan

A limiting current type oxygen sensor in which an inflow of oxygen is controlled by electrochemical method has been developed. A solid electrolyte (CaO doped CeO2) disk with two electrodes formed on the both surfaces and short-circuited was used as the layer for controlling the inflow of oxygen. The oxygen sensor exhibited good limiting current characteristics for oxygen concentrations from 1 to 95% at 600℃. The limiting current of the sensor depended on the resistance of the layer for controlling the inflow of oxygen. The 90% response time of the sensor was about 7 sec.


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28
CaZrO3系プロトン導電体を用いた溶融アルミニウム用起電力式水素センサ

 矢嶋　保・風岡勇人・岩原弘育・小出邦博*

名大工・TYK研*

NERNSTIAN-TYPE HYDROGEN SENSOR FOR MOLTEN ALUMINUM USING CaZrO3-BASED PROTON CONDUCTOR

 Tamotsu YAJIMA, Hayato KAZEOKA, Hiroshi IWAHARA and Kunihiro KOIDE*

Synthetic Crystal Research Laboratory, School of Engineering, Nagoya University
Furo-cho Chikusa-ku, Nagoya 464-01, Japan
*TYK Corporation, Research and Development Center
Ohbata-cho Tjimi, Gifu 507, Japan

In order to carry out in-situ measurement of hydrogen content in molten aluminum, galvanic cell type hydrogen sensor was constructed using CaZr0.9In0.1O3-α as a solid electrolyte. This sensor exhibited stable electromotive force (emf) corresponding to hydrogen content in molten aluminum. The values of hydrogen content determined with this sensor showed similar values with Telegas method.


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29
パルス駆動方式半導体ガスセンサ

 天本太郎・山口隆司・天野正弘・松浦吉展・梶山裕久

フィガロ技研

PULSE DRIVE SEMICONDUCTOR GAS SENSOR

 Taro AMAMOTO, Takashi YAMAGUCHI, Masahiro AMANO, Yoshinobu MATSUURA and Yoshihisa KAJIYAMA

Figaro Engineering INC.
Minoo-shi, Osaka 562, Japan

A pulse drive semiconductor gas sensor was investigated to lower power consumption and give higher selectivity to various gases. The sensor mainly consisted of a sensor element, a switching transistor and a microcomputer which generated pulse signals and processed sensor output signals. The sensor element had a multilayer structure which was formed by a printing process on an aluminum substrate. The SnO2 layer was heated by the RuO2 heater pulsatively. In case of a duty ratio of 8/1000 every 1 sec., the effective power consumption was about 14 mW. The sensor showed good sensitivity and response to CO and hydrogen gases.


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30
酸化スズ薄膜ガスセンサの動作機構

 大西久男・佐々木博一・松本　毅・一本松正道

大阪ガス基盤研

SENSING MECHANISM OF SnO2 THIN FILM FLAMMABLE GAS SENSORS

 Hisao OHNISHI, Hirokazu SASAKI, Takeshi MATSUMOTO and Masamichi IPPOMMATSU

Fundamental Research Laboratories, Osaka Gas Co., Ltd.
Konohana-ku, Osaka 554, Japan

The mechanisms of electric conduction and surface reaction on the SnO2 thin film gas sensors were resolved, and a quantiative model on the sensing mechanism was proposed. Electric conductivity of SnO2 is determined by only carrier electron density. Further, the carrier electron density is determined by the balance between the rate of the reaction producing electrons and the rate of the reaction consuming electrons. Both of transient response properties and steady-state properties of the SnO2 thin film gas sensors were expressed by a quantiative sensing mechanism model we proposed.


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31
多孔質ニッケルフェライトのガスセンサ特性

 平塚信之・村石賢介・原　正史*・勝部昭明*

埼玉大理工・埼玉大工*

GAS SENSING PROPERTIES OF POROUS NICKEL FERRITE

 Nobuyuki HIRATSUKA, Kensuke MURAISHI, Masashi HARA* and Teruaki KATSUBE*

Graduate School of Sci. and Eng., Saitama Univ.,
Urawa, Saitama, Japan
*Saitama Univ. Faculty of Engineering
Urawa, Saitama, Japan

New combustible gas sensor was developed using Ni ferrite composed of porous structure. The porous structure was prepared by sintering Ni ferrite powder mixed with camphor. By finding the appropriate sintering temperature (1200℃) and mixing ratio (1: 1) of camphor and Ni ferrite powder, considerable sensitivity was obtained for the detection of hydrogen and several hydrocarbon gases. Various Ni ferrite structures composed of different atomic ratios of Ni and Fe were also investigated to attain selective detection of different combustible gases.


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32
各種貴金属を担持したIn2O3-MgO素子のニオイ成分検出特性

 田崎博之・高尾雄二・清水康博・江頭　誠

長崎大工

GAS-SENSING CHARACTERISTICS OF In2O3-MgO SENSORS LOADED WITH NOBLE METALS TO SEVERAL ODOR COMPONENTS

 Hiroyuki TASAKI, Yuji TAKAO, Yasuhiro SHIMIZU and Makoto EGASHIRA

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

Gas sensitivity of In2O3 doped with 5 mol% MgO to several odor components such as trimethylamine, dimethylamine, monomethylamine, acetaldehyde and ammonia has been investigated as a function of the kind of noble metals to be loaded on the oxide. A significant increase in sensitivity to every odor components could be achieved with Au addition. In contrast, the sensitivity was markedly decreased by the addition of Pd or Pt, especially in the temperature range higher than 350℃.


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33
WO3を用いた高感度半導体NOxセンサ

 秋山守人・玉置　純・三浦則雄・山添　f

九大総合理工

HIGHLY SENSITIVE NOX SENSOR USING SEMICONDUCTIVE WO3

 Morito AKIYAMA, 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

The electrical resistance of a sintered body of WO3 was found to be very sensitive to NO and NO2 existing in air at low levels. The sensitivity of the sensor was as high as 33 and 188 to 200 ppm NO and 80 ppm NO2, respectively, with the 90% response time shorter than 20 s at 300℃. Almost linear relationship was observed between the sensitivity and concentration in the range of 0-200 ppm NO and 0-150 ppm NO2. The sensitivity to 80 ppm NO2 was independent of the concentration of O2. On the other hand, that to 200 ppm NO decreased only gradually with decreasing O2 down to ca. 1%, below which it decreased drastically. The sensitivity to inflammable gases such as CO, H2, CH4, i-C4H10 was far lower than to NOx. Water vapor hardly interfered with NOx sensing.


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34
Pt/TiO2粒状金属を用いたガスセンサ

 竹口圭吾・小野　洋・森崎　弘・矢澤一彦

電通大

Pt/TiO2 GRANULAR-METAL GAS SENSOR

 Keigo TAKEGUCHI, Hiroshi ONO, Hiroshi MORISAKI and Kazuhiko YAZAWA

The University of Electro-communications
Chofu-shi, Tokyo182, Japan

The electrical resistance of a granular metal film composed of fine Pt particles dispersed in a TiO2 matrix is found to be influenced by ambient nitrogen atmosphere containing small amounts of oxygen, hydrogen and ammonia. It has been found that appa-rent in-plane resistance of Pt/TiO2 composite films as well as the sensitivities to oxygen, hydrogen and ammonia are strongly influenced by the sputtering pressure for the film deposition.


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35
ヘテロ接合をもったLn2CuO4/SnO2（Ln:希土類元素) 素子のガスセンサ能

 槇本　理・荒川　剛

近畿大九州工

SENSING PROPERTIES OF Ln2CuO4/SnO2 (Ln=RARE EARTH) HAVING THE HETEROJUNCTION

 Osamu MAKIMOTO and Tsuyoshi ARAKAWA

Department of Industrial Chemistry, Faculty of Engineering, Kinki University in Kyushu
Iizuka, Fukuoka 820, Japan

I-V characteristics and sensing properties were investigated for Ln2CuO4/SnO2 (Ln=La, Nd, Sm) elements prepared by mechanically contacting both sintered pellets. In I-V characteristics, the direct current of electricity in these elements was decreasing with elevating temperatures beyond a ceratin temperature. Moreover, the alcohol detecting characteristics of Ln2CuO4/SnO2 elements were examined. The two peaks in temperature-sensitivity curves were obtained. The peak in higher temperature range would seem to be the reason for an oxygen deficient composition. The sequence of the activity was La2CuO4 > Nd2CuO4 > Sm2CuO4.


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36
CuO/ZnO薄膜開接合にによるガス検知

 潮嘉次郎*・石崎豊暁・中村吉伸・宮山　勝・柳田博明

ニコン*・東大先端研

GAS DETECTION OF CuO/ZnO THIN FILM OPEN-JUNCTION

 Yoshijiro USHIO*, Toyoaki ISHIZAKI, Yoshinobu NAKAMURA, Masaru MIYAYAMA and Hiroaki YANAGIDA

*NIKON Corp, Shinagawa-ku, Tokyo 140, Japan
Research Center for Advanced Science and Technology, University of Tokyo
Meguro-ku, Tokyo 153, Japan

Gas sensing properties of CuO/ZuO open-junctions fabricated by thin film formation and photolithography patterning process were investigated in the atmosphere of inflammable gas CO and H2 (〜4000 ppm in Air). In the temperature range from 100 to 250℃ , the increase of currents were seen at forward bias 0.5 V or 1.0 V for both gases. And at near 150℃, noticeable differences between sensitivities of CO and H2 were observed. While, at room temperature, the increase of currents occurred at higher forward bias 2.0 V. Little changes were shown at reversed bias in any case. After raising the temperature to 250℃, the characteristics as sensors changed and sensitivities decreased mainly because of the change of ZnO film properties. Adsorbed or contained oxygens of ZnO layer was suggested to influence sensing.


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37
TiO2-Nb2O5系半導体酸素センサに関する研究

 彭　　軍・大瀧倫卓・江口浩一・荒井弘通

九大総合理工

A STUDY ON TiO2-Nb2O5 SEMICONDUCTORS AS OXYGEN SENSOR MATERIALS

 Jun PENG, Michitaka OHTAKI, Koichi EGUCHI and Hiromichi ARAI

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

Oxygen sensing properties of TiO2-Nb2O5 binary semiconductors are investigated. The compositions of TiO2:Nb2O5 = 5:95 and 80:20 in molar ratio lead to higher sensitivities and temperature stabilities than those of each Nb2O5 and TiO2 as stoichiometric A/F sensor materials. These compositions correspond to a solid solution of TiO2 and Nb2O5, and the mixture of that with TiNb2O7, respectively. Effects of the compositional change of the binary materials on oxygen sensing properties are discussed.


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特別講演２
知能化センシングシステムにおけるセンサ情報の統合と融合

山崎弘郎

東大工

INTEGRATION AND FUSION OF MULTI SENSOR DATA IN INTELLIGENT SENSING SYSTEMS

 Hiro YAMASAKI

Department of Mathematical Engineering and Information Physics
Hongo Bunkyo-ku, Tokyo 113, Japan

Advanced intelligent functions of sensing systems can not be realized by simple data source from single sensor. It is realized by combining multiple data from multiple or various kind of sensors just like human sensory systems. Consequently efficient information processing of multiple data sources is indispensable in the intelligent sensing systems. Integration and fusion of multiple sensor data are concepts of procedures for advanced information processing in this intelligent sensing system. In this paper, background, fundamental structure and simple examples of integration and fusion are described. Especially contribution of knowledge to the integration and fusion is stressed.


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38
アルキルアミン系色素-高分子複合膜を用いた酢酸センサ

 斎藤達巳・松口正信・定岡芳彦・酒井義郎

愛媛大工

ACETIC ACID SENSOR USING ALKYL AMINE DYE-POLYMER COMPOSITE FILMS

 Tatsumi SAITO, Masanobu MATSUGUCHI, Yoshihiko SADAOKA and Yoshiro SAKAI

Department of Applied Chemistry, Faculty of Engineering, Ehime University
Matsuyama, Ehime 790, Japan

Acetic acid gas sensor using dye dispersed polymer thin film coated on quartz oscillating element has been studied.
The sensitivity of poly ethylene oxide thin film doped with malachite green is higher than that of the film doped with crystal violet.
Further more, the characteristics of cellulose acetate film with crystal violet are comparable to those of poly ethylene oxide film with crystal violet. For an optimized film, the amount of sorbed acetic acid in proportional to that concentration up to 80 ppm. The response time of the composite film was within 10 min and the good reproducibility and stability were confirmed.


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39
フタロシアニンNO2センサの膜構造に関する検討

 守家浩二・榎本　量・中村裕司

大阪ガス開発研

INVESTIGATION OF FILM STRUCTURES OF PHTHALOCYANINE-NO2 SENSORS

 Koji MORIYA, Hakaru ENOMOTO and Yuji NAKAMURA

Research and Development Center, Osaka Gas Co., Ltd.
6-19-9 Torishima Konohana-ku, Osaka 554, Japan

Film structures and characteristics of the phthalocyanine-NO2 sensors, with film adhered to the silica substrate, were investigated. Film thickness of the sensor increased according to the source temperature and the adhesion time. However film structures were mainly dependent on the substrate temperature. Thinner films (low adhesion rate) showed faster response and recovery. Column-structured films (low substrate temperature) changed its resistivity to the concentration of NO2, while highly crystallized films (high substrate temperature) showed no sensitivity.


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40
可燃性ガスによる金超微粒子担持 NiO 薄膜の可視吸光度変化特性

 安藤昌儀・小林哲彦・春田正毅

阪工試

CHANGE IN VISIBLE-LIGHT ABSORPTION OF GOLD-SUPPORTED NICKEL OXIDE THIN FILM BY EXPOSURE TO COMBUSTIBLE GAS

 Masanori ANDO, Tetsuhiko KOBAYASHI and Masatake HARUTA

Government Industrial Research Institute of Osaka
1 Midorigaoka Ikeda, Osaka 563, Japan

The effect of gold deposition on the visible-light adsorption properties of NiO film was investigated at temperatures ranging from 100℃ to 250℃. The deposition of highly dispersed gold on NiO film enhanced the absorption change by CO in air and the response rate. This effect on absorbance change becomes more pronounced at lower temperatures. Therefore, the Au/NiO film can provide a good candidate for the optical detection of combustible gases near room temperature.


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41
吸着ルミネッセンス化学センサII −発光の温度スペクトルによるガスの識別と定量−

 中川益生・宇都宮晃・近森真司*・松浦保彰*・富山　毅*・山本　勲*・和田倶典**・山下信彦**・山下敬彦**

岡山理大理・岡山理大工*・岡山大理**

ADSORPTION LUMINESCENCE CHEMICAL SENSOR II
THE MEASUREMENT OF CONCENTRATION AND DISCRIMINATION OF GASES UTILIZING TEMPERATURE SPECTRA OF GLOW CURVES

 Masuo NAKAGAWA, Kou UTSUNOMIYA, , Shinji CHIKAMORI*, Yasuaki MATSUURA*, Tsuyoshi TOMIYAMA*, Isao YAMAMOTO*, Tomonori WADA**, Nobuyuki YAMASHITA** and Yoshihiko YAMASHITA**

Faculty of Science, Okayama University of Science
1-1, Ridai-cho, okayama 700, Japan
*Faculty of Engineering, Okayama University of Science
1-1 Ridai-cho, Okayama 700, Japan
**Faculty of Science, Okayama University
3-1-1 Tsushimanaka, Okayama 700, Japan

In the previous report, we proposed a new gas sensor utilizing adsorption luminescence whose spectrum and intensity depend on the species and concentration of combustible gases in air. This sensor can measure continuously the concentration of gases of the order of ppm. However, a spectrometric photo detector and analyzer is required to discriminate gas species, so that this sensor system costs much for practical use.
We found that adsorption luminescence appears during heating alumina powder after adsorption of combustible gases (ethanol or acetone) at room temperature, the profile of the glow curve depends on the adsorbed gas species, and the amount of total emitted lignt depends on the concentration of the gas. The experimental results for a gas sensor utilizing this phenomenon are reported, and a model to interpret this phenomenon is proposed.


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42
銀添加 CuO-BaTiO3 系酸化物における CO2 センサ特性

 米谷和浩・石原達己・水原由加子・瀧田祐作

大分大工

EFFECTS OF Ag ADDITIVES ON CO2 SENSING CHARACTERISTICS OF CuO-BaTiO3 CAPACITOR

 Kazuhiro KOMETANI, Tataumi ISHIHARA, Yukako MIZUHARA and Yusaku TAKITA

Department of Environmental Chemistry and Engineering, Faculty of Engineering, Oita University
Oita 870-11, Japan

During our study on BaTiO3 system mixed oxides, it was found that the capacitance of CuO-BaTiO3 depended strongly on CO2 concentrations. Effects of Ag addition on CO2 sensing characteristics were examined in this study. Adding 1 wt% Ag to CuO-BaTiO3 increased the sensitivity to carbon dioxide by an order of magnitude. Ag added CuO-BaTiO3 can distinguish between CO2 concentrations of 30 ppm to 100000 ppm.


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43
蒸着重合ポリイミド膜を用いたシリコンダイオードの感湿特性

 中込真二・山本達夫

石巻専修大理工

HUMIDITY SENSING CHARACTERISTICS OF SILICON DIODE CONTAINING A VAPOUR-DEPOSITION-POLYMERIZED POLYIMIDE THIN FILM

 Shinji NAKAGOMI and Tatsuo YAMAMOTO

Faculty of Science and Technology, Ishinomaki Senshu University
Minamisakai Ishinomaki-shi, Miyagi 986, Japan

A humidity- and hydrogen-gas-sensitive diode which is composed of metal-polyimide-silicon junction structure has been fabricated. The following characteristics have been found. A direct current pass through the polyimide layer of 30〜300 nm thickness which is prepared by vapour deposition polymerization. An increase in relative humidity causes an increase of both a forward and a backward current. While an exposure to hydrogen gas atmosphere results in an enhanced forward current and a deteriorated backward current when the n-type Si substrates are used. Moreover, when the device is dipped in a liquid solution, a change in the current can be observed possibly according with its pH values.


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44
三次元架橋構造をもつポリイミド樹脂を用いた容量型湿度センサ

 松口正信・定岡芳彦・酒井義郎・黒岩孝朗*・伊藤昭彦*

愛媛大工・山武ハネウェル*

A CAPACITIVE-TYPE HUMIDITY SENSOR USING ACETYLENE-TERMINATED POLYIMIDE RESINS

 Masanobu MATSUGUCHI, Yoshihiko SADAOKA, Yoshiro SAKAI, Takaaki KUROIWA and Akihiko ITOU

Department of Applied Chemistry, Faculty of Engineering, Ehime University
Matsuyama, Ehime 790, Japan
Fujisawa Factory, Yamatake-Honeywell Co., Ltd.,
Fujisawa, Kanagawa 251, Japan

Acetylene-terminated polyisoimide resin was used to fabricate a capacitive-type humidity sensor. The composite of different molecular weight polyisoimide, IP-603 and IP-600, was preferable to crosslink sufficiently and to prepare the rigid thin film. The sensitivity, C90/C0, was about 1.185 for the 1:1 composite and the hysteresis and the temperature coefficient was very small. The sensor response was a little affected by exposing acetone vapor at high humidity but recovered initial value immediately after removing the acetone vapor.


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45
Y2O3-Pr6O11系酸化物を用いた湿度センサの特性

 吉田昭吾・芝　賢一・東　正志・田村英雄・川崎吉包

阪工大工

HUMIDITY SENSORS USING ANNEALED Y2O3-Pr6O11 OXIDE

 Shougo YOSHIDA, Ken-ichi SHIBA, Masashi AZUMA, Hideo TAMURA and Yoshikane KAWASAKI

Department of Applied Chemistry, Osaka Institute of Technology
Asahiku, Osaka 535, Japan

Sintered composed of Y2O3-Pr6O11 (50:50 w%) humidity sensor was prepared and humidity-impedance characteristics and long term durability were investigated. This element was identified as a mixture of crystalline Y2O3 and Pr6O11 by X-ray diffraction analysis. The impedance of the element is approximately 106 ohm in dry condition. The impedance decreases monotonously about three orders from 106 (0% R.H.) to 103 ohm (93% R.H.). Long term durability, in wet air (93% R.H.) for 100 days, the impedance of an Y2O3 sensor increases remarkably, while that of Y2O3-Pr6O11 sensor does not change so much. It seems that the difference of hydroxyl concentration and/or the electronic conductivity of Pr6O11 cause the difference between Y2O3 and Y2O3-Pr6O11 sensors.


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46
塗布熱分解法によるTiO2-V2O5系湿度センサの作成

 小浦延幸・伊藤　滋・友常茂宏

東理大理工

PREPARATION OF TiO2-V2O5 HUMIDITY SENSOR BY DIPPING-PYROLYSIS PROCESS

 Nobuyuki KOURA, Shigeru ITO and Shigehiro TOMOTSUNE

Department of Industrial Chemistry, Faculty of Science and Technology, Science University of Tokyo
Noda-shi, Chiba 278, Japan

The thin film of TiO2-V2O5 was prepared by a humidity sensor. The film with the composition of Ti/V; 99/1 was obtained by heating the dipped TiO2 substrate at 800℃ for 20 min using the dipping-pyrolysis process, in which titanium tetraisopropoxide and vanadium naphthenate were used as starting materials. The impedance of the film, which was measured at 25℃ applying 50 Hz of a.c., decreased from 108 Ω to 105 Ω with an increase in relative humidity. When the relative humidity was switched quickly from 0.8% to 80%, the impedance of the film reached to 80% of the net change in 10 sec.
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47
色素-ナフィオン複合膜を用いたオプティカル湿度センサ

 村田雄貴・松口正信・定岡芳彦・酒井義郎

愛媛大工

OPTICAL HUMIDITY SENSOR USING NAFION-DYE COMPOSITE THIN FILMS

 Yu-uki MURATA, Masanobu MATSUGUCHI, Yoshihiko SADAOKA and Yoshiro SAKAI

Department of Applied Chemistry, Faculty of Engineering, Ehime University
Matsuyama, Ehime 790, Japan

By using composite films of hydrolyzed nafion and dyes having cyanine or triphenyl structures and with a terminal N-phenyl group, an optical humidity sensor has been fabricated. In the reflection mode, the optical intensity of the absorption peaks which depend on the used dyes decreases with relative humidity. The raising and recovery times are less than 1 min. In dry air, the alkyl amine group reacted with SO3H of hydrolyzed nafion and formed a proton additive. Sorption of water molecules induces the deprotonation of the quaternized ammonium group.


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48
限界電流式平面型酸素センサを利用した高温水蒸気センサ

 八木秀明・市川圭一

日本特殊陶業総研

HUMIDITY SENSOR FOR HIGH TEMPERATURE USING THE LIMITING CURRENT TYPE PLANE OXYGEN SENSOR

 Hideaki YAGI and Keiichi ICHIKAWA

Research & Development Center, NGK SPARK PLUG CO., LTD.,
2808 Iwasaki Komaki-shi, Aichi 485, Japan

A limiting current type plane oxygen sensor with an epoch-making stracture has been developed. The new sensor has cathode and anode electrodes made of Pt on the same plane of ZrO2 electrolyte and the cathode also serves as a hole to limit gas diffusion. This sensor detects humidity lineary proportional to a water vapor pressure of 0〜500 mmHg in a wide range of operation temperature from 20℃ to 300℃. It endured 10,000 hours of use in a life test without showing any deterioration.

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