Vol. 7, Supplement A (1991)
Digest of the 12th Chemical Sensor Symposium
April 5-6, 1991
Science University of Tokyo
Abstracts
1
オゾンのクーロメトリックセンサの開発
内山俊一・鈴木周一・笠間 要*・石川陽一**・金子光範**・梅沢 彰*
埼玉工大・新日鐵化学**・エイブル**
DEVELOPEMENT OF COULOMETRIC OZONE SENSOR
Shunichi UCHIYAMA, Shuichi SUZUKI, Kaname KASAMA*, Youichi ISHIKAWA**, Mitsunori KANEKO** and Akira UMEZAWA**
Department of Environmental Engineering, Saitama Institute of Technology
Okabe, Saitama 369-02, Japan
*Nippon Steel Chemical Co. Ltd.
Chuou-ku, Tokyo 104, Japan
**Able co.
Shinjuku-ku, Tokyo 162, Japan
A coulometric ozone sensor using a porous carbon felt as electrode, and using an electrolyte consists of iodine redox mediator was investigated to get a simple and low-costed sensor. At first, the experimental was carried out using iodine solution as the sample, and we obtained that the current efficiency decreased apparently when the iodine concentration was lower than 0.0001 [N]. So, we compensated the results using the current efficiency when we measured the ozone water, and we obtained the good relation between the indigo method from 0.1 ppm to 2.0 ppm. Another sensor, an amperometric ozone sensor using the carbon felt and redox mediator, that the applied sensor of the coulometric sensor was investigated, too. In this sensor, current was good relation between the indigo method from 0.1 ppm to 1.5 ppm.
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2
溶液中の低濃度オゾン測定用センサの開発
内山俊一・鵤木孝夫・鈴木周一・笠間 要*・石川陽一**・金子光範**・梅沢 彰*
埼玉工大・新日鐵化学**・エイブル**
FABRICATION OF AMPEROMETRIC SENSOR FOR LOW CONCENTRATION OZONE IN AQUEOUS SOLUTION
Shunichi UCHIYAMA, Takao IKARUGI, Shuichi SUZUKI, Kaname KASAMA*, Youichi ISHIKAWA**, Mitsunori KANEKO** and Akira UMEZAWA**
Department of Environmental Engineering, Saitama Institute of Technology
Okabe, Saitama 369-02, Japan
*Nippon Steel Chemical Co. Ltd.
Chuou-ku, Tokyo 104, Japan
**Able co.
Shinjuku-ku, Tokyo 162, Japan
An amperometric ozone sensor using porous was fabricated to measure 1-1000 ppb level dissolved ozone, and the response characteristics were investigated. This sensor consists of carbon felt working electrode, Ag wire counter electrode, electrolyte (IN-KCL) and PTFE membrane. The currents obtained by the reduction of ozone were in proportion to analytical data obtained by indigo method in the very wide concentration range from 5 ppb to 800 ppb within 10% of relative standard deviation and the detection limit was determined to be about 1 ppb. The response time of this sensor is 5-15 minutes. The current response of ozone is not decreased for at least 5 months and the present device would be useful one as an on-line sensor for monitoring in a variety of scientific fields.
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3
プレーナ型酸素電極の開発
荒井真人・遠藤英樹・中嶋 聡・滝沢耕一
オムロンライフサイエンス研
DEVELOPMENT OF A PLANER-TYPE OSYGEN ELECTRODE
Masato ARAI, Hideki ENDO, Satoshi NAKAJIMA and Koichi TAKIZAWA
OMRON INSTITUTE OF LIFE SCIENCE
17 Chudoji Minami-machi Shimogyo-ku, Kyoto 600, Japan
A planer-type oxygen electrode simulated Clark-type was developed and its charactristics were investigated and compared with Clark-type oxygen electrode. In applied potential -0.6 v (vs. Ag/AgCl) , 90% response time was about 15 sec. And linearity was obtained from saturated oxygen solution to 20% oxygen solution at 25℃.
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4
交互型マイクロアレイ電極を用いた対流下における高感度測定
青木 純・長谷川哲也・末永智一・内田 勇
東北大工
AMPEROMETRIC ANALYSES AT INTERDIGITATED MICROELECTRODE ARRAYS IN FLOWING STREAMS
Atsushi AOKI, Tetsuya HASEGAWA, Tomokazu MATSUE and Isamu UCHIDA
Department of Molecular Chemistry &Engineering, Faculty of Engineering, Tohoku University
Aramaki-Aoba Aoba-ku, Sendai 980, Japan
Electrochemical behavior at interdigitated microelectrode arrays (IDA) were investigated in two configurations: series and parallel with respect to the flow axis. Anodic current response at IDA in series configuration was amplified 4 times compared to that of a dual rectangular electrode (DRE) by redox cycling. Amperometric responses at these electrodes were in good agreement with those of theoretical prediction and dependent on the cubic root of the flow rate. Anodic currents were proportional to the concentration of (ferrocenylmethyl) trimethyl ammonium ion (FA+) from 10-8 to 10-5 M. Current response at IDA in parallel configuration showed the steady-state current by redox cycling between the adjacent electrodes and was independent to the flow rate.
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5
P E G修飾酵素／フェロセン固定化カーボンペースト電極によるグルコース測定
水谷文雄・奥田 篤*・矢吹聡一・曽良達生
繊高研・北海道立工試*
GLUCOSE-SENSING ELECTRODE BASED ON CARBON PASTE CONTAINING PEG-ATTACHED ENZYME AND FERROCENE
Fumio MIZUTANI, Atsushi OKUDA*, So-ichi YABUKI and Tatsuo KATSURA
Research Institute for Polymers and Textiles
1-1-4 Higashi Tsukuba, Ibaraki 305, Japan
*Hokkaido Industrial Research Institute
19 Kita 11 Nishi, Sapporo 060, Japan
An Amperometric glucose-sensing electrode is constructed by the use of a carbon paste containing a polyethylene glycol-attached glucose oxidase and 1,1'-dimethyl ferrocene. The polymer-modified enzyme is soluble in organic solvents (e.g., n-hexane) as well as in water, and exhibits much higher activity than native enzyme on the surface of hydrophobic carbon paste electrode. The higher enzyme activity results in an enhanced electrode response: the current response for glucose on the modified enzyme-based electrode is 3-4 times as large as that obtained on a native enzyme-based electrode. A linear relationship between the current response and the glucose concentration is obtained in the range of 0.1-10 mM on the modified enzyme-based electrode.
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6
酸化チタン型針状グルコースセンサの調整について
菱田裕子・池田章一郎・伊藤 要
名大工
PREPARATION OF THE NEEDLE TYPE TITANIUM OXIDEGLUCOSE SENSOR
Yuko HISHIDA, Shoichiro IKEDA and Kaname ITO
Department of Applied Chemistry, Nagoya Institute of Technology
Gokiso-cho Showa-ku, Nagoya 466, Japan
The needle type titanium oxide glucose sensor has already developed. However, the property of the base oxygen electrode was insufficient. The surface of the base electrode has been modified with platinum to improve the performance. It has been suggested that the oxygen reduction reaction preferentially proceeded on the platinum site. The applied potential for the oxygen electrode system became nobler than the former type. The glucose sensor based on the platinum modified titanium oxide electrode responded to the glucose concentration up to about 0.5 g dm-3 within 30 seconds. The response property of the sensor was almost constant for 10 days.
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7
ゲート感応膜にLaF3を用いたMOS型グルコースセンサ
久保田智樹・清水正章・原 正史・勝部昭明・三浦則雄*・山添 f*
埼玉大工・九大総合理工*
MOS-TYPE GLUCOSE SENSOR WITH SPUTTERED LaF3 FILM
Tomoki KUBOTA, Masaki SHIMIZU, Masashi HARA, Teruaki KATSUBE, Norio MIURA* and Noboru YAMAZOE*
Faculty of Engineering, Saitama University
255 Shimo-Okubo Urawa, Saitama 338, Japan
*Department of Materials Science and Technology, Graduate School of Engineering Science, Kyushu University
Kasuga-shi, Fukuoka 816, Japan
A new MOS-type micro glucose sensor using a sputtered LaF3 (solid electrolyte) film was developed. The sensor, having a structure of immobilized film/Pt/LaF3/SiO2/Si/Al multiple layers, needs no external reference electrode. A stable responce was obtained in the glucose concentration range from 2×10-4 to 2×10-2 M in a phosphate buffer solution (pH= 6.9), with also found to respond to H2O2 in the buffer.
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8
ペルオキシダーゼモデル電極（４）
イミダゾール誘導体の計測
立間 徹・福岡 実・渡辺 正
東大生研
PEROXIDASE MODEL ELECTRODES-IV.
APPLICATION TO SENSING OF IMIDAZOLE DERIVATIVES
Tetsu TATSUMA, Minoru FUKUOKA and Tadashi WATANABE
Institute of Industrial Science, University of Tokyo
Roppongi Minato-ku, Tokyo 106, Japan
A heme peptide-modified electrode was investigated as an interference-based amperometric sensor for imidazole derivatives. Heme nonapeptide as a peroxidase model was covalently immobilized on a tin (IV) oxide electrode to obtain a peroxidase model electrode, which catalyzed electrochemical reduction of H2O2 without mediator at +150 mV vs. Ag/AgCl. The current for H2O2 reduction is inhibited by a strong ligand for heme. Such ligands, either charged or neutral, can thus be sensed amperometrically in the presence of H2O2. The response was completed in a few seconds. This electrode exhibited a selectivity sequence Im ≧ 1-MeIm > 4-MeIm ≧ histamine > histidine > SCN- > I- ≧ salicylate ≧ NO2- ≧ ClO4-, and did not respond to 2-MeIm, Br-, Cl-, MeOH and EtOH.
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特別講演１
においセンシングシステム
中本高道・福田 敦・森泉豊栄
東工大工
ODOR SENSING SYSTEM
T. NAKAMOTO, A. FUKUDA and Toyosaka MORIIZUMI
Department of Electrical and Electronic Engineering, Faculty of Engineering , Tokyo Inastitute of Technology
2-12-1 Ookayama Meguro-ku, Tokyo 152, Japan
Mimicking the olfactory mechanism, authors' group have been developing an odor sensing system, utilizing quartz resonator gas sensors and neutral-network pattern recognition algorithms. The recent achievements in our system and the possibility of replacing human sensory tests performed in food and drink industries will be described.
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9
アスコルビン酸共存下での神経伝達物質のカーボンファイバー微小電極における応答特性
徐 海涛・北村房男・大坂武男・徳田耕一
東工大総合理工
ELECTROCHEMICAL DETECTION OF NEUROTRANSMITTERS IN THE PRESENCE OF ASCORBIC ACID BY CARBON FIBER MICRO-CYLINDER ELECTRODES
Hai-Tao XU, Fusao KITAMURA, Takeo OHSAKA and Koichi TOKUDA
Department of Electronic Chemistry, Graduate School at Nagatsuta, Tokyo Institute of Technology
Voltammetric behavior of dopamine (DA) at carbon fiber electrodes has been investigated in the presence of ascorbic acid (AA) in saline buffer (pH 7.2). Two different electrochemical pretreatments (ECP), "mild" and "strong" ones, were employed. The "mild" ECP (four potential sweep cycles between -0.3 and 2.0 ) made it possible to show clearly the differential pulse wave of 1μM DA in the presence of 0.1 mM AA. DA has been found to adsorb strongly to the carbon fiber electrodes with "strong" ECP (four potential seep cycles between -0.3 and 2.5 V) and it was shown that AA affects little either on the differential pulse voltammograms or on the chronochoulograms for adsorbed DA.
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10
ディスポーザブルヒポキサンチンセンサの開発
大熊廣一・鈴木 宗*・赤星亮一*・高橋仁志・谷澤誠一・関向修一
新日本無線研・東洋大工*
DISPOSABLE BIOSENSOR FOR HYPOXANTHINE
Hirokazu OKUMA, Hajime SUZUKI*, Ryoichi AKAHOSHI*, Hitoshi TAKAHASHI, Seiichi YAZAWA and Shuichi SEKIMUKAI
Research and Development Laboratory, New Japan Radio Co. Ltd.,
Kamifukuoka-shi, Saitama 356, Japan
*The Faculty of Engineering, Toyo University
Kawagoe-shi, Saitama 360, Japan
A disposable hypoxanthine sensor by pulse voltammetric technique was investigated. The technique is a direct measurement method without resorting to dilution of sample and stirring. The hypoxanthine concentration can be determined with trace droplet of a sample (5μl) on the electrode. The sensor was fabricated by coating gold electrodes with a carboxymethyl cellulose containing a xanthine oxidase and potassium ferricyanide as an electron transfer mediator. The relative standard deviation is 8.5% (n= 8) and the response is linear up to 1×10-3M.
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11
フロー分析法におけるEEEセンサの応答特性の検討
矢尾板仁・長井律子*・吉田泰彦*・碇山義人**・山内 繁
国立リハ研・東洋大工*・東工大工**
THE RESPONSE OF EEE SENSOR IN FLOW ANALYSIS
Masashi YAOITA, Ritsuko NAGAI*, Yasuhiko YOSHIDA*, Yoshihito IKARIYAMA** and Shigeru YAMAUCHI
Research Institute of National Rehabilitation Center
4-1 Namiki Tokorozawa, Saitama 359, Japan
*Dept. of Applied Chemistry, Faculty of Engineering, Toyo University
2100 Kujirai Kawagoe, Saitama 350, Japan
**Dept. of Bioengineering, Tokyo Institute of Technology
2-12-1 O-okayama Meguro-ku, Tokyo152, Japan
It has been already reported that the peak current of EEE sensor in a flow injection analyzer decreases with an increase in the flow rate, although the peak current normally increases by an electrochemical detector, Steady response of EEE sensor was measured in a steady flow of a glucose solution to elucidate this peculiar phenomenon. It was found that the steady current was almost independent of the flow rate and the decrease of the peak current was interpreted as a result of a decrease in a contact time of the injected sample solution with the electrode. Simulated experiment of cathodic reduction of potassium ferricyanide on a platinum black electrode in a flow cell was carried out and little dependence was found for the steady cathodic current on the flow rate. It has been concluded that boundary layer diffusion does not limit the steady current by EEE sensor because of the geometric structure of the platinum black electrode.
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12
酵素包括ポリピロール誘導体を用いた酵素スイッチの開発
西澤松彦・澤口隆博・末永智一・内田 勇
東北大工
AN ENZYME SWITCH SENSITIVE TO NADH
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 switching device based on enzyme was investigated as an approach to fabrication of novel biosensors. A microarray electrode coated with pyrrole/N-methylpyrrole copolymer containing diaphorase shows clear "off" responses upon addition of NADH due to reduction of the polymer by NADH from conductive to insulating state through catalytic reaction of diaphorase.
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13
ガス透過性膜で被覆した導電性ADH膜電極アルコールセンサ
石塚俊博*・小畠英理・碇山義人・相澤益男
オリエンタル電気*・東工大生命理工
ALCOHOL GAS SENSING USING ELECTROCONDUCTIVE ADH ELECTRODE COVERED WITH GAS PERMEABLE MEMBRANE
Toshihiro ISHIZUKA*, Eiri KOBATAKE, Yoshihito IKARIYAMA and Masuo AIZAWA
Department of Bioengineering, Faculty of Bioscience and Biotechnology, Tokyo Institute of Technology
4259 Nagatuda-chou Midori-ku Yokohama-shi, Kanagawa 227, Japan
*Oriental Electric Co., Ltd.
3-9-7 Nobidome Niiza-shi, Saitama 352, Japan
A new gas sensor for alcohol based on electroconductive ADH (alcohol dehydrogenase) membrane coated electrode was developed. This sensor was fabricated by co-immobilizing ADH, and an electron mediator (Meldola blue) in a conductive polymer, and by covering the sensor with a gas permeable membrane (Fig.1). Alcohol was determined by the oxidation current of the mediator in the ADH-NAD-mediator electron transferring system of the conductive polymer. The alcohol sensor was applied for the detection of not only liquid phase alcohol but also gaseous alcohol by employing a gas permeable membrane. In this research, we showed the fabrication technique of the alcohol gas sensor by employing the electron transferring system covered with a gas permeable membrane, and the its characteristics.
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14
微生物センサを用いた亜硫酸イオン計測
鈴木正康・藤井圭子*・蟻川芳子*・久保いづみ**・金川貴博***・三上栄一***・軽部征夫
東大先端研・日女大家政*・創価大工**・微工研***
DETERMINATION OF SULFITE ION BY USING MICROBIAL SENSOR
Masayasu SUZUKI, Keiko FUJII*, Yoshiko ARIKAWA*, Izumi KUBO**, Takahiro KANAGAWA***, Eiichi MIKAMI*** and Isao KARUBE
Research Center for Advanced Science and Technology, University of Tokyo
*Faculty of Domestic Science, Japan Women's University
**Faculty of Engineering, Soka University
***Fermentation Research Institute, Agency of Industrial Sciencd, MITI.
Chemoautotrophic and aerobic bacterium Thiobacillus thioparus TK-m, which has sulfite oxidation pathways, was used for the development of sulfite ion sensor. The sensor consists of an oxygen electrode and T. thioparus immobilized between two nitrocellulose membranes. Since T. thioparus could not be cultivated in the medium containing sulfite as sulfur source, T. thioparus grown in the thiosulfate containing medium was used for the experiment. The selectivity for sulfite was gradually increased during the use as sulfite sensor. After 6 days, the response to thiosulfate became approximately 10% of that of sulfite.
When the sensor was applied to the sulfite determination in batch system, calibration curve showed the linearity in the concentration range between 4μM and 280μM.
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15
フローインジェクションカロリメトリーによるコバルト(II)イオンのバイオセンシング
佐藤生男・渡辺啓治
神奈川工科大工
FLOW-INJECTION CALORIMETRIC BIOSENSING OF COBALT (II) IONS
Ikuo SATOH and Keiji WATANABE
Department of Chemical Technology, Faculty of Engineering, Kanagawa Institute of Technology
1030 Shimo-Ogino Atsugi-shi, Kanagawa-ken 243-02, Japan
A novel biosensing with use of an immobilized apoenzyme is proposed for flow-injection calorimetric determination of cobalt (II) ions. The system was assembled with a column containing immobilized alkaline phosphatase beads and a thermistor device for monitoring the enzymatic activity. Cobalt (II) ions were calorimetrically determined in the range of 0.04 to 1.0 mM through its activation of the immobilized metal-free alkaline phosphatase (apoenzyme) column. The activity of the column was assessed by injecting a 0.1 mL of 100 mM p-nitrophenyl phosphate solution and then the heat evolved in the hydrolytic reaction was miasured. The column was regenerated by pumping 40 mM 2, 6-pyridine dicarboxylate solution (pH 6.0).
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16
Pt-Ir合金触媒薄膜を付加した水晶振動子を用いる新接触燃焼式ガスセンサ
酒井 剛・三浦則雄・山添 f
九大総合理工
PIEZOELECTRIC QUARTZ CRYSTAL BASED NEW TYPE CALORIMETRIC GAS SENSOR FITTED WITH Pt-It ALLY CATALYST FILM
Go SAKAI, Norio MIURA and Noboru YAMAZOE
Department of Materials Science, Graduate School of Engineering Sciences, Kyushu University
Kasuga-shi, Fukuoka 816, Japan
A new type piezoelectric crystal sensor coated with a sputtered noble metal catalyst film was developed for the detection of inflammable gases in the temperature range 100-400℃. Among the various coating films tested, sputtered Pt-Ir alloy film (Ir content: 27-36 at%) gave the best sensing performance with high gas sensitivity and high resistance to interference by coexisting water vapor. The replacement of an AT-cut quartz crystal by a Y-cut crystal having larger temperature coefficients of resonant frequency was found to be quite effective to increase the gas sensitivity of the sensor.
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17
酸化物コンデンサのCO2検知特性とその機構
米谷和浩・石原達己・水原由加子・滝田祐作
大分大工
CO2 SENSING CHARACTERISTICS AND DETECTION MECHANISM OF MIXED OXIDE CAPACTOR
Kazuhiro KOMETANI, Tatsumi ISHIHARA, Yukako MIZUHARA and Yusaku TAKITA
Department of Environmental Chemistry and Engineering, Faculty of Engineering, Oita University
Oita 870-11, Japan
Oxide capacitor consisting of BaTiO3 and an oxide is studied as a new type CO2 sensor based on the capacitance change. In our previous study, it is found that CuO-BaTiO3 is highly sensitive to CO2. The optimum operating temperature on CuO-BaTiO3 is 729 K, and the eighty percent response time to 2% CO2 is within 25 seconds. The equimolar mixture of CuO and BaTiO3 can distinguish the CO2 concentration from 100 to 60000 ppm. Carbonation of CuO in element elevates the height of potential barrier. The capacitance increase of CuO-BaTiO3 by exposure to CO2 seems to result from the elevated height of potential barrier at the grain boundary between CuO and BaTiO3.
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18
絶縁油中のアセチレンガス測定用センサの開発
石地 徹*'**・打越祥一**・高橋勝緒***
埼玉大工*・理研計器**・理化学研究所***
ELECTROCHEMICAL SENSOR FOR ACETYLENE GAS IN ISOLATION OIL
Toru ISHIJI, Shoichi UCHIKOSHI and Katsuo TAKAHASHI
*Saitama University
225 Shimo-ohkubo urawa-shi, Saitama 338, Japan
**RIKEN KEIKI Co. Ltd.
2-7-6 Azusawa Itabashi-ku, Tokyo 174, Japan
***RIKEN Institute of Physical and Chemical Research
2-1 Hirosawa Wako-shi, Saitama 351-01, Japan
The detection of C2H2 gas is attracting attention as a judgment for the condition of isolation oil used in a transformer or a power cable. An useful electrochemical sensor was studied and the optimum condition was discussed. The sensor used is based on the measurement of the current when C2H2 is electrochemically oxidized at gas diffusion electrodes. The sensor using a gold working electrode shows better selectivity of C2H2 than a platinum one. Under optimum condition, the influence of H2, CO and C2H4 on C2H2 determination were less than 0.6%. Good linear relationship was obtained between the oxidation current and the concentration of C2H2 in low concentration region.
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19
ポリ(N,N-ジメチルアミノエチルメタクリレート)の伝導度に及ぼす酢酸蒸気の影響
斎藤達巳・松口正信・定岡芳彦・酒井義郎
愛媛大工
EFFECT OF ACETIC ACID VAPOR ON THE ELECTRICAL CONDUCTIVITY OF POLY (N,N-DIMETHYLAMINOETHYLMETHACRYLATE
Tatsumi SAITO, Masanobu MATSUGUCHI, Yoshihiko SAKAOKA and Yoshirou SAKAI
Department of Industrical Chemistry, Faculty of Engineering, Ehime University
Matsuyama, Ehime 790, Japan
Effect of acetic acid vapor on the electrical conductivity of poly (N,N-dimethylaminoethylmethacrylate) (P-DMAEM) films was investigated. Linear relationship was obtained between the change on conductivity and the vapor concentration of acetic acid. At low concentration of acetic acid vapor, Henry's law can be applied, while at high concentration Freundlich type sorption is applicable. In addition, the change of conductivity became larger when water vapor coexists with acetic acid vapor because of the increment of dissociation constant of acetic acid by the sorption of water in P-DMAEM.
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20
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（III）
平山和子・松口正信・定岡芳彦・酒井義郎
愛媛大工
WATER RESISTIVE HUMIDITY SENSOR COMPOSED OF INTERPENETRATING POLYMER NETWORKS. (III)
Kazuko HIRAYAMA, Masanobu MATSUGUCHI, Yoshihiko SADAOKA and Yoshiro SAKAI
Department of Industrial Chemistry, Faculty of Engineering, Ehime University
Matsuyama-shi, Ehime 790, Japan
An interpenetrating polymer networks (IPNs) film composed of hydrophilic HMPTAC polymer and hydrophobic EGDMA polymer was prepared on the alumina substrate with interdigitated gold electrodes to fabricate a humidity sensor. The impedance of this sensor changed about 5 orders of magnitude in the whole humidity range and the sensitivity was almost the same as that of HMPTAC homopolymer sensor. This sensor was more water resistive than those using melamine resin or HEMA polymer as a hydrophobic polymer which were reported previously.
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21
リン酸塩皮膜を用いた湿度センサ
石倉和弘・盛屋喜夫
日本パーカライジング総研
HUMIDITY SENSOR WITH USE OF PHOSPHATE COATING.
Kazuhiro ISHIKURA and Yoshio MORIYA
Central Research Laboratories, Nihon Parkerizing CO., LTD.,
2784 Ohgami Hiratuka, Kanagawa 254, Japan
Phosphate coating is widely used as paint base for automobile and for lubrication of cold forming. We found that the phosphate coating has a good humidity sensitivity. The characteristic of humidity sensor can be changed by its coating weight . The thin coating shows the humidity-typed characteristic, and its impedance in common logarithm decreases linealy to the relative humidity. While the thick coating shows the dew-typed characteristic. The conduction mechanism of this sensor will be caused by diffusion of proton in absorbed water.
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22
固体電解質を用いた単一らせん電極素子(SMED)のガスセンシング機能
森 和代・矢嶋 保・岩原弘育
名大工
GAS SENSING FUNCTION OF SPIRAL MONOELECTRODE DEVICE (SMED) USING SOLID ELECTROLYTES
Kazuyo MORI, Tamotsu YAJIMA and Hiroyasu IWAHARA
Synthetic Crystal Research Laboratory, School of Engineering, Nagoya University
Furo-cho Chikusa-ku, Nagoya 464-01, Japan
New type of gas sensing device called Spiral Monoelectrode Device (SMED) was developed using YSZ or Bi2O3-based oxides as a solid electrolyte and its gas sensing function was investigated under various conditions. When dc current was sent to SMED at high temperature and the test gas was changed, its terminal voltage changed in response to the partial pressure of oxygen in the gas. When a test gas was injected to a carrier gas which flowed over SMED, it gave rise to change in its terminal voltage. Linear relation was observed between peak height of terminal voltage and logarithm of Po2 of injected gas.
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23
フロン134a用半導体ガスセンサの開発
野村 徹・瀬戸口泰弘・松浦吉展・松浦俊二
フィガロ技研
DEVELOPMENT OF SEMICONDUCTOR R-134a GAS SENSOR
Tohru NOMURA, Yasuhiro SETOGUCHI, Yoshinobu MATSUURA and Shunji MATSUURA
Figaro Engineering Inc.,
Minoo City, Osaka 562, Japan
The conventional type of semiconductor gas sensors show only small gas sensitivity to 1,1,1,2,-tetrafulorethane (R-134a). In order to improve the sensitivity, modifying the gas sensing material (SnO2) was studied by adding other elements. For additives, Pd and sulfur were found to be effective. The optimum amounts of Pd and sulfur were 0.3wt% and 1.0 mol% to SnO2, respectively. The improved sensor showed the excellent sensitivity to R-134a. It was found that the sensor could even detect gas leakage as low as 5 ppm.
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24
固体電解質を用いたマイクロCOセンサ
藤岡 透・草薙繁量・山鹿範行・渡部祥文・土井謙之・井上孝啓
松下電工中研
MICROELECTROCHEMICAL, CO SENSOR USING SOLIED ELECTROLYTE
Toru FUJIOKA, Shigekazu KUSANAGI, Noriyuki YAMAGA, Yoshihumi WATABE, Kenji DOI and Takahiro INOUE
Central Research Laboratory, Matsushita Electric Works, Ltd.
1048 Kadoma, Osaka 571, Japan
Planar-type electrochemical CO sensors have been fabricated. The sensor is comprised of three electrodes: working (Pt), counter (Pt) and reference (Au). These electrodes are covered with solution casted Nafion film. The highest CO sensitivity of the sensor using alumina substrate was 0.05 nA/ppm. In order to get higher CO sensitivity, three-dimensional electrodes which have regularly arranged "micro walls" (width: 2000μm, thickness: 3μm, height: 10-45μm) were fabricated on Si substrate. The CO sensitivity of the three-dimensional electrode sensor was attained over 0.7 nA/ppm. The greater area of the thin Nafion layer on "micro walls" contributed to its higher sensitivity.
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25
固体電解質CO2センサにおける２成分系炭酸塩電極の特性
姚 勝・清水陽一・三浦則雄・山添 f
九大総合理工
CHARACTERISTICS OF BINARY-CARBONATE ELECTRODES FOR SOLID ELECTROLYTE CO2 SENSOR
Sheng YAO, Youichi SHIMIZU, Norio MIURA and Noboru YAMAZOE
Department of Materials Science and Technology, Graduate School of Engineering Sciences, Kyushu University
Kasuga-shi, Fukuoka 816, Japan
The sensing properties and characteristics of the binary-carbonate electrodes for solid electrolyte CO2 sensor were investigated. For BaCO3-Na2CO3 electrode system, it was found that interference of the coexistent water vapor on the EMF response became less significant with increasing Ba content and disappeared ca. 45 at% Ba in the electrode. XRD analysis revealed that this behavior corresponded very well with the decrease and disappearance free-Na2CO3 phase with increasing Ba content. SEM observation revealed that electrode had texture composed of two types of regions, i.e., a region occupied by a large plate (containing Ba only) and another by porous bundles of their needles (containing Ba and Na). Other binary systems, such as CaCO3-Na2CO3 and SrCO3-Na2CO3, were shown to give similar stability against water vapor at optimized composition.
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26
高温高圧水用pH測定システムの開発（I）
橘 孝二・服部昭宏・横井正顕*
東京理科大理・東仲工業*
DEVELOPEMENT OF A pH MEASURING SYSTEM FOR HIGH TEMPERATURE AQUEOUS SOLUTIONS (I)
Koji TACHIBANA, Akihiro HATTORI and Masaaki YOKOI
Department of Chemistry, Science University of Tokyo
Shinjuku-ku, Tokyo 162, Japan
*Technical Design Div., Toshin Kogyo Co., Ltd.
Shinagawa-ku, Tokyo 140, Japan
An in-situ pH measuring system for high temperature aqueous solutions was developed with YSZ membrane tubes and a new pressure balanced regulator system. Air was filled inside the tube, the pressure of which being balanced with that of high temperature aqueous side by the regulator system. The Pt coated inside surface functioned as an oxygen electrode. Owing to the regulator system and some improvement in the shape of the tube and its cooling position, the damage of the full stabilized membrane tubes was almost prevented. In the temperature range from 150 to 275℃, the potential of the YSZ tube electrode was confirmed to show the one correlation to the potential of the Pt oxygen electrode in air saturated aqueous solutions, The pH measurement by the YSZ tube was also confirmed not to be affected by other redox couples contained in solutions.
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27
PdをTiO2(001)及び(100)面に蒸着したショットキー型ダイオードの水素感知機構の違い
岸本和之・小林 光・中戸義禮・坪村 宏
阪大基礎工
CRYSTAL-FACE DEPENDENCE OF HYDROGEN SENSING MECHANISM FOR Pd/TiO2 SCHOTTKY DIODES
Kazuyuki KISHIMOTO, Hikaru KOBAYASHI, Yoshihiro NAKATO and Hiroshi TSUBOMURA
Laboratory for Chemical Energy Conversion and Department of Chemistry, Faculty of Engineering Science, Osaka University
Toyonaka, Osaka 560, Japan
Hydrogen sensing mechanism of the Pd/TiO2 (001) and (100) diodes has been investigated by measuring the current-voltage and capacitance-voltage characteristics and the work function change. The magnitude of the barrier height lowering caused by hydrogen is nearly proportional to the square of the work function change for the case of the TiO2 (001) diodes. This behavior is attributed to the removal of preadsorbed oxygen atoms by hydrogen atoms. In the case of the TiO2 (100) diodes, the amount of the barrier height lowering is proportional to the square of the work function change only when the hydrogen concentration is low, and becomes almost linear for high hydrogen concentration, which is attributed to the adsorption of hydrogen on the bare Pd sites.
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28
SnO2ガスセンサの過渡応答の測定
清水慶一・若林淳右・白江公輔
阪大基礎工
MEASUREMENT OF TRANSITIONAL RESPONSE OF TIN-OXIDE SEMICONDUCTOR-GAS-SENSOR
Keiichi SHIMIZU, Kiyosuke WAKABAYASHI and Kimisuke SHIRAE
Department of Control Engineering, Faculty of Engineering Science, Osaka University
Toyonaka-shi, Osaka 560, Japan
Using information both from static specifics and from dynamic specifics are advantageous to gas recognition. Transitional responses of tin-oxide semiconductor-gas-sensor were measured with a system of imitating respiration faculty, are possible to extract characteristics. Moreover, this sensor is controlled at regular temperature by PI-controller. As a result of comparing an amplitude of sensor response with a time lag, the relation between the amplitude and the time lag is inverse proportion.
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29
ZnO厚膜型センサによる悪臭成分ガスの測定
鈴木健吾・酒井 才・高田 義・中根正典
新コスモス電機
DETECTION OF OFFENSIVE ODOR USING ZnO THICK FILM TYPE GAS SENSOR
Kengo SUZUKI, Sai SAKAI, Tadashi TAKADA and Masanori NAKANE
New Cosmos Electric Co., Ltd.
Mitsuya-Naka Yodogawa-ku, Osaka-shi 532, Japan
High sensitive and high selective sensor for offensive odor gases was studied. It was found that a thick film AnO semiconductor sensor coated with WO3-Al2O3 layer had high sensitivity and high selectivity for offensive odor gases, e.g., H2S, CH3SH, (CH3)3N, etc.(sensitivity to H2S (0.1 PPM) ≧sensitivities to C2H5OH (80 PPM), C2H4 (1000 PPM) or H2 (400 PPM) )
The selectivity was improved by the formation of WO3-Al2O3 layer, and the sensitivity was also increased. Prompt response was obtained by addition of Pd.
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特別講演２
固体電解質を用いた化学センサ
足立吟也
阪大工
GAS SENSORS USING SOLID ELECTROLYTES
Gin-ya ADACHI
Department of Applied Chemistry, Osaka University
Yamadaoka Suita, Osaka 565, Japan
An overview for gas sensors which are for SOx, CO2 and NOx detection has been presented.
Solid electrolytes using alkali metal ions have an advantage of their excellent selectivity for a given gas. The potentiometric measurement with the sensors is the main method for the gas sensing. Development of solid reference electrodes are also reviewed.
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30
SnO2薄膜型ガスセンサ
安川佳和・関 隆和・村松淳一・稲垣訓宏*
クラベ・静大工*
SnO2 FILM-TYPE GAS SENSOR DEVICE
Yoshikazu YASUKAWA, Takakazu SEKI, Jun-ichi MURAMATSU and Norihiro INAGAKI*
Kurabe Industrial Co., Ltd.
4830 Takatsuka Kamimura Hamana-gun 432, Japan
*Faculty of Engineering, Shizuoka University
3-5-1 Johoku Hamamatsu-shi, Shizuoka 432, Japan
Gas sensitivities of the SnO2 film-type devices were investigated. The sensitivity, which means the ratio of the electrical resistance between in air and in CO atmosphere, is enhanced by catalitic action adding Pt to a mixture of Au and SnO2. The gas sensitivity of CO compared to other gases, such as ethanol and propane, is good. When insulating substance is partly uncovered by a mixture of Au and SnO2 the gas sensitivity is stable for a long period.
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31
煙道用NOxセンサの開発（2）―実排気中における特性―
井上智弘・佐竹和子・小林 愛・大越秀樹・中原 毅・武内 隆
徳山曹達
NOx SENSOR FOR EXHAUST MONITORING (2)
Tomohiro INOUE, Kazuko SATAKE, Ai KOBAYASHI, Hideki OHKOSHI, Takeshi NAKAHARA and Takashi TAKEUCHI
TOKUYAMA SODA CO., LTD
2051 Endo Fujisawa-city, Kanagawa 252, Japan
A NOx sensor composed of a gas sensitive oxide semiconductor based on titania, heater and thermistor, has been examined for the use of exhaust monitoring. The thermistor was used to controll the operating temperature strictly.
The high sensitivity and selectivity of the sensor to NO were confirmed in the real exhaust gas of an oil stove, without being influenced by coexisting CO, CO2 and HC. The characteristic have kept for more than 2000 hours. The results show the sensor is appropriate for the use of exhaust monitoring.
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32
金超微粒子担持α-Fe2O3を用いた一酸化炭素検知器の開発
船崎菜穂美・浅野泰一・小林哲彦*・春田正毅*
電気化学計器・阪工試*
DEVELOPMENT OF α-Fe2O3 SENSOR SUPPORTED Au FINE PARTICLES TO CARBON MONOXIDE
Naomi FUNAZAKI, Yasukazu ASANO, Tetsuhiko KOBAYASHI* and Masataka HARUTA*
DKK CORPORATION
Musashino-shi, Tokyo 180, Japan
*Government Industrial Research Institute of Osaka
Ikeda-shi, Osaka 563, Japan
The gas sensor system to detect carbon monoxide using Au-dopedα-Fe2O3 was developed and its longterm stability was tested. The sensor was made by baking the sensing materials on the Au electrode. The system was consisted of the sensor for the carbon monoxide and the alarm unit. The sensor was heated at 200℃. This system could monitor the concentration of carbon monoxide from 5 ppm to 0.2% continuously. It was applied to detect the leak of carbon monoxide in a chemical laboratory. The sensor system was stable for 100 days with ±30% errors.
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33
各種貴金属を担持したTiO2系センサのトリメチルアミンガス検知機構
福田和志・高尾雄二・清水康博・江頭 誠
長崎大工
TRIMETHYLAMINE SENSING MECHANISM OF TiO2-BASED SPECIMENS
Kazushi FUKUDA, 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
Trimethylamine (TMA) sensing mechanism of TiO2-based specimens has been studied from their catalytic activity for TMA oxidation. It was revealed that T80% of each specimen, which was defined as the temperature at which conversion of TMA to CO2 and CO reached 80%, was closely related to the sensor temperature (TM) at the maximum sensitivity (SM). But, the highest value of SM was observed for the specimen, such as TiO2 loaded with 2.0 wt% In (2.0In/TiO2), with moderate catalytic activity. This behavior was anticipated to arise from the sensor configuration used in this study.
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34
リソグラフィによる半導体開接合の作成とセンサ応用
潮 嘉次郎・宮山 勝*・柳田博明*
ニコン・東大先端研*
FABRICATION OF SEMICONDUCTOR OPEN-JUNCTION USING LITHOGRAPHY PROCESS AND APPLICATION TO CHEMICAL SENSOR
Yoshijiro USHIO, 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
Newly designed chemical sensors utilizing interface properties of different semiconductors were fabricated. These sensors consist of thin solid films of semiconductors (CuO〜7000A, ZnO〜5000A) and electrodes (Al〜1000A, Au〜1000A) prepared by RF magnetron sputtering or electron-beam evaporation. Many ditches (width 10μm, pitch 10μm) were formed by photolithography process in order that the interface of CuO/ZuO could be exposed partly to the atmosphere. These open-junctions showed diode rectification and forward currents increased with the increase in humidity at room temperature. Sensitivity varied depending on applied voltage. Effect of the exposure of junctions was clearly confirmed.
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35
ファジィ推論を応用したセンサシステムの信頼性
大藪多可志
金沢女短大
RELIABILITY OF SENSOR SYSTEM APPLYING FUZZY REASONING
Takashi OYABU
Department of Information Engineering, Kanazawa Women's College
Kanazawa-shi, Ishikawa 920-13, Japan
Many sensors and systems have been developed for detecting disasters in domestic circumstances, such as gas leaks and fires. In general, only one sensor is used for detecting one kind of disaster. If there should be a hitch of sensor in this system, it will be immediately ineffective. A new type of system which can detect three kinds of disasters, gas leaks, generation of carbon monoxide gas and fires, isconstructed by the use of four kinds of sensors. The reliability of this system has been improved byusing four sensors. The system adopts still more a fuzzy reasoning which has simple membership functions,and it can estimate the grades of each desaster.
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