Vol. 9, Supplement A (1993)
Digest of the 16th Chemical Sensor Symposium
April 1-2, 1993
Tokyo Institute of Technology
Abstracts
1
酸化鉄／酸化銅薄膜のガス感度特性
中西博美・平塚信之・原 正史・勝部昭明
埼玉大理工
THE GAS SENSING CHARACTERISTICS OF IRON OXIDE/COPPER OXIDE THIN FILMS
Hiromi NAKANISHI, Nobuyuki HIRATSUKA, Masashi HARA and Teruaki KATSUBE
Graduate School of Sci. and Eng., Saitama Univ.,
Urawa, Saitama 338, Japan
The gas sensor elements composed of iron oxide, copper oxide and iron oxide/copper oxide thin films were fabricated in the oxygen pressure of 4, 20, 40 mTorr by the evaporation method. Both α-Fe2O3 and copper oxide (CuO) films had high sensitivity to i-C4H10 and carbon monoxide (CO) gases because of fine crystallinity of these films. Any disordered film was insensitive. The α-Fe2O3 and the CO films behaved as n-type and p-type semiconductors, respectively. A small sensitivity to CO was observed for the α-Fe2O3 film, however, the sensitivity to CO for the CuO film was as high as the sensitivity to i-C4H10. The sensitivity of mixed phases of α-Fe2O3/CuO was small to both i-C4H10 and CO. CuFe2O4 had the significant sensitivity to these gases with n-type conductivity. Because three films having compositions had various sensitivities, they will provide the possibility of the gas selectivity.
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2
厚膜型SnO2系センサのガス検出特性に及ぼすガスの反応性と拡散性の影響
清水康博・中村優一郎・江頭 誠
長崎大工
EFFECTS OF GAS REACTIVITY AND DIFFUSIVITY ON GAS-SENSING PROPERTIES OF THICK FILM SnO2-BASED SENSORS
Yasuhiro SHIMIZU, Yuichiro NAKAMURA and Makoto EGASHIRA
Department of Materials Science and Engineering, Faculty of Engineering, Nagasaki University
1-14 Bunkyo-machi, Nagasaki 852,Japan
Effects of reactivity and diffusivity on gas-sensing properties of thick film SnO2-based sensors have been investigated by employing several kinds of objective gases. It was confirmed that the interior of a SnO2 sensor exhibits much higher sensitivity than the surface, provided the objective gas permeates into the interior easily than O2, e.g. in the case of H2. In contrast, the reverse tendency was observed under the condition that the permeation of objective gases was further limited than that of O2 owing to their larger molecular diameter and higher viscosity coefficient, e.g. in the cases of CH4 and C2H5OH. Excess enhancement in catalytic activity of sensor materials induced by the noble metal addition resulted in the deterioration of the interior H2 sensitivity, but in the enhancement in the interior CH4 or C2H5OH sensitivity.
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3
希土類金属添加多孔質ニッケルフェライトのガス感度特性
村石賢介・平塚信之・勝部昭明
埼玉大理工
GAS SENSING CHARACTERISTICS OF POROUS NICKEL FERRITE ADDED WITH RARE EARTH METAL OXIDES
Kensuke MURAISHI, Nobuyuki HIRATSUKA and Teruaki KATSUBE
Graduate School of Sci. and Eng., Saitama Univ.,
Urawa, Saitama 338, Japan
The gas sensor using porous nickel ferrite added with rare earth metal oxides was fabricated to investigate its gas sensing characteristics. The fine nickel ferrite powders added with rare earth metal oxides (Y2O3, Sm2O3, and La2O3) by weight and camphor powders were mixed with the same weight and then pressed into disks, they were sintered at the range from 1,100 to 1,250℃ for 2 hrs. in air. The optimum sintering temperature and the optimum amounts of additives were found to be 1100℃ and Y2O3 of 5 wt%, respectively. As a result of the measurements of these gas sensors to saturated hydrocarbon gases, it was confirmed for enhancement of the sensitivities and shortening of the response times by the addition of rare earth metal oxides.
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4
バリスタ型ガスセンサの水素ガス検出特性
林 豊倉・高尾雄二・清水康博・江頭 誠
長崎大工
H2 SENSING PROPERTIES OF VARISTOR GAS SENSORS
Feng-Cang LIN, 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
The I-V characteristics of ZnO varistors have been investigated under different H2 concentration at elevated temperatures. It was revealed that all varistors studied exhibited H2 sensitivity, being accompanied with a shift in the breakdown voltage to a lower electric field in the presence of H2. The highest H2 sensitivity was achieved with the ZnO varistor doped with 1.0 mol% Bi2O3 at 500℃.
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5
In2O3系センサ素子のTMAガス感度の膜厚依存性
高尾雄二・韓 美化・清水康博・江頭 誠
長崎大工
CORRELATION BETWEEN TMA SENSITIVITY AND THICKNESS OF In2O3-BASED SENSORS
Yuji TAKAO, Mi How Han, Yasuhiro SHIMIZU and Makoto EGASHIRA
Department of Materials Science and Engineering, Fadulty of Engineering, Nagasaki University
1-14 Bunkyo-machi, Nagasaki 852, Japan
Attempts were made to clarify the relationship between trimethylamine (TMA) sensitivity and thickness of In2O3-MgO(5 mol%)-based sensors with interior electrodes. For every sensor, the TMA sensitivity increased with an increase in sensor thickness up to about 0.4 mm thick. This suggests that permeation of O2 into the interior (near electrodes) is restricted more and more with an increase in sensor thickness, leading to lower surface coverage of chemisorbed oxygen at the steady-state and then higher sensitivity. The less activity of Au for promoting readsorption of O2 is responsible for the much more pronounced sensitivity enhancement observed in this thickness range. Further thickening the sensor resulted in a significant decrease in sensitivity, especially for the sensors loaded with 0.5 wt% Ru or Pd, whereas the sensitivity remained almost constant at 0.4-1.0 mm in the case of the sensor with lower catalytic activity (the sensor loaded with 0.5 wt% Au). Thus, it was confirmed that the reactivity and the diffuseness of TMA determined the sensitivity of thick film sensors with interior electrodes.
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6
魚介類の鮮度センサとしての酸化亜鉛薄膜へのAl添加効果
河合孝明・椿野史朗・南戸秀仁
金沢工大デバイス研
DOPING EFFECT OF ALUMINUM IMPURITY FOR ZINC OXIDE THIN FILM AS THE FRESHNESS SENSOR FOR SEA FOODS
Takaaki KAWAI, Shiro TSUBAKINO and Hidehito NANTO
Electron Device System Research Laboratory, Kanazawa Institute of Technology
7-1 Oogigaoka Nonoichimachi, P. O. Kanazawa-South, Ishikawa 921, Japan
The dependence of the content of aluminum (Al) impurities doped into zinc oxide (ZnO) thin film gas sensor on sensing characteristics for exposure to odor from sea foods. The sensitivity of the ZnO thin film gas sensor for odor from sea foods is improved by doping the Al impurity. The high sensitivity of the Al-doped ZnO thin film gas sensor for exposure to odor from sea foods such as sea bream, oyster, salmon, squed and sardine is attributed to the high sensitivity and excellent selectivity for amine gases such as trimethylamine and dimethylamine.
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7
酸化スズ系ガスセンサによる室内環境モニタリング
大藪多可志・石坂昭三・木村春彦*・松浦吉展**・天本太郎**・梶山裕久**
富山国際大・金沢大工*・フィガロ技研**
MONITORING OF AIR POLLUTION USING TIN OXIDE GAS SENSOR
Takashi OYABU, Shozo ISHIZAKA, Haruhiko KIMURA*, Yoshinobu MATSUURA**, Taro YAMAMOTO**, Yoshihisa KAJIYAMA**
Toyama University of International Studies
Oyama-Cho, Toyama 930-12, Japan
*Kanazawa University, Faculty of Technology
Kanazawa-shi, Ishikawa 920, Japan
**Figaro Engineering Inc.,
Senbanishi, Minoo City, Osaka 562, Japan
Measuring indoor air pollution is tried using a tin oxide gas sensor. Air pollution of daily living is neglected and only an additional pollution above the usual level is roughly measured. Sensor outputs for the past three weeks are measured every twenty minutes and the data are averaged in each measuring time. The data which are inputed every moment from the sensor, are compared with the mean values. If there is a deviation among the data, the grade of the deviation is outputed. This method can also cancel fluctuations of the sensor output in seasons. When the data exceeds a setting level (2.5 V in this system), an alarm is outputed.
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8
酸化鉄薄膜のNO2検知特性
松嶋茂憲・國次真輔・小林健吉郎・岡田元次
愛媛大工
NO2 SENSING PROPERTIES OF Fe2O3 THIN FILM
Shigenori MATSUSHIMA, Shinsuke KUNITSUGU, Kenkichiro KOBAYASHI and Genji OKADA
Department of Applied Chemistry, Faculty of Engineering, Ehime University
3 Bunkyo-cho Matsuyama-shi Ehime 790, Japan
W-doped Fe2O3 films have been fabricated on polycrystalline alumina substrates by RF magnetron sputtering method, and effects of annealing temperature on NO2 sensing properties of the films have been examined. The crystal structure of the sputtered film is changed from Fe3O4 to α-Fe2O3 after annealing at temperatures of 500〜700℃ in air. By elevating an annealing temperature, the particle size fairly increases, whereas the NO2-gas sensitivity of the film decreases. These results suggest that the NO2 sensitivity of W-doped Fe2O3 film depends on the microstructure, e.g., particle size.
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9
煙道用NOxセンサの開発 (3)―NO応答特性に与える共存ガスの影響―
片山 愛・佐竹和子・大越秀樹・中原 毅・武内 隆
徳山曹達
NOX SENSOR FOR EXHAUST MONITORING (3)
〜INFLUENCE OF COEXISTING GASES ON RESPONSE TO NO〜
Ai KATAYAMA, Kazuko SATAKE, Hideki OHKOSHI, Takeshi NAKAHARA and Takashi TAKEUCHI
TOKUYAMA SODA CO., LTD.,
2051 Endo Fujisawa-city, Kanagawa 252, Japan
A NOx sensor made of titania doped with 3-valent element has been developed. The response to NO under interference gases such as C3H6, CO, SO2, O2 and H2O was examined in this sensor. In the laboratory tests, it is found that the influence of interference gases is negligible except the cases of H2O 0 ppm or of rich burned condition. The characteristics of the sensor in various combustion equipments agrees with the results obtained in laboratory tests.
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10
Ptイオン交換ゼオライト触媒を添加したWO3素子のNO検知特性
張 華民・玉置 純・三浦則雄・山添 f
九大総合理工
NITROGEN MONOOXIDE SENSING PROPERTIES OF WO3 ELEMENT ADDED WITH Pt ION EXCHANGED ZEOLITE CATALYST
Hua-Min ZHANG, 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
In order to improve the NO sensitivity of WO3 element, Pt ion exchanged zeolite catalyst, having high NO oxidation activity, was added to the element. The zeolite catalyst (ferrierite) loaded with a small amount of Pt, such as 1.6 wt% Pt, was found to enhance the NO sensitivity especially in the lower concentration range below 10 ppm. Such improvement is considered to result from an increase in the NO oxidation activity of the sensor element without inducing the strong electronic interaction between Pt particles and WO3 particles.
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特別講演１
セラミック化学センサの最近の動向
一ノ瀬昇
早大理工
R & D TRENDS IN CHEMICAL SENSORS
Noboru ICHINOSE
Department of Materials Science and Engineering, Waseda University
Shinjuku, Tokyo 169, Japan
Many kinds of sensors are used for the electronic applications. Among them, ceramic sensors are particularly notoworthy, because ceramic materials excel over single crystals and thin films in physical and chemical stability as well as mass productibility. Typical recently developed ceramic sensors include temperature sensors, such as negative-temperature-coefficient, positive-temperature-coefficient and critical-temperature resistors; pressure sensors, which utilize the piezoelectric effects; gas and humidity sensors, which detect adsorption and desorption of gases by changes in electrical conductivity; and infrared sensors, which utilize the pyroelectric effect.
Here, we have reported on research and development trends on chemical sensors such as gas and humidity sensors forcused for mew technologies using ultrafine particles and p-n contacts.
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11
表面プラズモン現象を利用した光センサによる化学種の検出
並平英治・出田和彦・荒川 剛
近畿大九州工
SURFACE PLASMON RESONANCE STUDY FOR THE DETECTION OF SOME CHEMICAL SPECIES
Eiji NAMIRA, Kazuhiko IDETA and Tsuyoshi ARAKAWA
Department of industrial Chemistry, Faculty of Engineering, Kinki University in Kyushu
Iizuka, Fukuoka 820, Japan
An optical chemical sensor based on laser excited surface plasma resonance has been developed for detecting some chemical species. When the medium outside a silver thin film was changed from air to a squalane thin film, the resonance angle changed from 42.3° to 22.9°. Moreover, as a squalene thin film was exposed some gas-adsorbing organic materials (ethane, propane etc), the angle of incidence was varied. Also, in the case of Nafion film, it was found that some chemical species, e.g., methylene blue, Ru(byp)32+ could be detected.
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12
クレシルバイオレット―高分子複合膜を用いた光化学センサ
定岡芳彦・松口正信・酒井義郎・村田雄貴
愛媛大工
OPTICAL PROPERTIES OF CRESYL VIOLET-POLYMER COMPOSITES FOR QUANTIFICATION OF HUMIDITY AND AMMONIA GAS IN AMBIENT AIR
Yoshihiko SADAOKA, Yoshiro SAKAI and Yu-uki MURATA
Department of Applied Chemistry, Faculty of Engineering, Ehime University
Matsuyama 790, Japan
For the dye-poly (ethylene oxide) composite, the spectrum was sensitive to the concentration of ammonia in air i.e., the absorbance at 600 nm decreased but at 460 nm increased with the increase in ammonia content in the air. The ammonia molecule interacts chemically with the monocationic form of the dye and forms a weak charge-transfer complex. For the dye-Nafion composite, the absorbance at 610 nm increased as the humidity increased. Increasing the water content of the film induced the formation of lower protonated forms of the dye trapped within the Nafion matrix.
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13
メチルカルサイン―高分子複合膜を用いた光学的湿度センサ
定岡芳彦・酒井義郎・王 暁梅
愛媛大工
OPTICAL PROPERTIES OF METHYL CALCEIN-DOPED POLYMER THIN FILMS AND IT'S APPLICATION TO OPTICAL SENSOR FOR QUANTIFICATION OF ATMOSPHERIC HUMIDITY
Yoshihiko SADAOKA, Yoshiro SAKAI and Xiaomei WANG
Department of Applied Chemistry, Faculty of Engineering, Ehime University
Matauyama 790, Japan
The humidity sensor utilizes a fluorescent dye (methyl calcein) entrapped within poly (ethylene oxide) or poly (acrylic acid) matrix. The fluorescence intensity increases strongly and linearly with increasing humidity. The wavelength of fluorescence maximum is 525 nm for the composite with poly (acrylic acid) in a whole range of the humidity. For the poly (ethylene oxide) composite, the fluorescence maximum in a lower humidity region is about 550 nm and shifts to lower wavelenghs. In both cases, the intensity of the fluorescence increased linearly with humidity. The 90% response and recovery time for humidity changes is less than 20 s for the poly (ethylene oxide) composite, while a longer time is observed for the poly (acrylic acid) composite.
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14
ポリ（カルボン酸ビニルエステル）を用いた容量型湿度センサ
松口正信・新本征史・定岡芳彦・酒井義郎・黒岩孝朗*
愛媛大工・山武ハネウェル*
CAPACITIVE-TYPE HUMIDITY SENSOR USING POLY (CARBOXYLIC ACID VINYL ESTERS)
Masanobu MATSUGUCHI, Masafumi SHINMOTO, Yoshihiko SADAOKA, Yoshiro SAKAI and Takaaki KUROIWA*
Department of Applied Chemistry, Faculty of Engineering, Ehime University
Matsuyama, Ehime 790, Japan
*Fujisawa Factory, Yamatake-Honeywell Company, Limited,
Fujisawa, Kanagawa 251, Japan
Capacitive-type humidity sensors were prepared using four kinds of the polymerized carboxylic acid vinyl esters. These polymers were hydrophobic and the sensors fabricated with them showed little hysteresis. In the case of unsaturated carboxylic acid vinyl esters monomer, the cross-linking reaction is expected to proceed. The sensitivity of the sensors composed of the cross-linked polymer film are larger than those of linear polymer. This can be explained by the difference of free space around the polar groups. Further, the temperature coefficient of the sensor and resistivity to acetone vapor were improved by cross-linking. Consequently, present polymers which are hydrophobic and cross-linkable are suitable for capacitive-type humidity sensors.
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15
過酸化ポリ酸から導かれるタングステンブロンズによる湿度センサ
露本伊佐男・岸本 昭・工藤徹一
東大生研
HUMIDITY SENSOR USING TUNGSTEN BRONZES DERIVED FROM PEROXO-POLYTUNGSTIC ACID
Isao TSUYUMOTO, Akira KISHIMOTO and Tetsuichi KUDO
Institute of Industrial Science, University of Tokyo
7-22-1 Roppongi Minato-ku, Tokyo 106, Japan
Peroxo-polytungstic acid, formed by the direct reaction of metallic tungsten with hydrogen peroxide, precipitated an amorphous salt with potassium ion. Heating this precursor salt at relatively low temperature yielded hexagonal or tetragonal tungsten bronze. This hexagonal tungsten bronze was pressed into pellets and re-heated in H2 at 500℃. Electrical conductivity of this specimen was measured at room temperature. Under dry atmosphere the conductivity was metallic like conventional tungsten bronze, but the resistivity was significantly increased and became semiconductive with only slight humidity. In addition, the conductivity of this semiconductive sample was recovered under dry conditions. Resistivity changes were measured under different PH2O. It was found that the saturated resistivity was dependent on the pressure of water vapor.
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16
複合酸化物を用いた容量型NOxセンサ
佐藤しのぶ・石原達己・水原由加子・滝田祐作
大分大工
MIXED OXIDE CAPACITOR AS A NEW TYPE NOX SENSOR BASED ON THE CAPACITANCE CHANGE
Shinobu SATO, Tatsumi ISHIHARA, Yukako MIZUHARA and Yusaku TAKITA
Department of Applied Chemistry, Faculty of Engineering, Oita University
700 Dannoharu, Oita 870-11, Japan
Detection of nitrogen oxide in the effluent gas is critically demanded from the environmental problems. Therefore, various types of NOx sensors are proposed, however, the capacitive types NOx sensor have not yet been proposed to date. In this study, we investigated the effects of nitrogen oxide on the capacitance of the binary oxides generally contains WO3. It is found that the capacitance of the mixed oxide contained WO3 depended strongly on the concentration of NO and consequently, these mixed oxides are usable as a NOx sensor based on the capacitance change. In particular, NiO-WO3 element with Pt electrode exhibits the stable response and the high sensitivity to NO. The sensitivity to 100 ppm NO (Cair/CNO) and the 90% response time are 30 and 14 s at 270℃, respectively on this sensor. Furthermore, the capacitance of the NiO-WO3 element linearly decreased with the increases in the NO concentration from 20 to 300 ppm. Therefore, the concentration of NO can be measured from the capacitance of this NiO-WO3 element.
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17
容量型CO2センサにおけるBaTiO3の原子価制御による低温作動化
西雄一郎・石原達己・水原由加子・滝田祐作
大分大工
LOW TEMPERATURE OPERATION OF THE CAPACITIVE TYPE CO2 SENSOR, CuO-BaTiO3, BY THE PARTIAL SUBSTITUTION OF BaTiO3
Yuichiro NISHI, Tatsumi ISHIHARA, Yukako MIZUHARA and Yusaku TAKITA
Department of Applied Chemistry, Faculty of Engineering, Oita University
700 Dannoharu, Oita 870-11, Japan
It is well-known that partial substitution of BaTiO3 is greatly affected the dielectric and the semiconducting property. In this study, effects of the partial substitution of BaTiO3 on the CO2 sensing characteristics of CuO-BaTiO3 were investigated. The sensitivity as well as the operating temperature were strongly depended on the dopant to BaTiO3. The sensitivity to CO2 in the low temperature region was enhanced by the partial substitution of Pb, Ca, Mg, or Pr for Ba in BaTiO3. In particular, partial substitution of Ca in BaTiO3 is effective for enhancing the sensitivity in the temperature range from 350 to 450℃. Although the response time was prolonged and the sensitivity to CO2 in the concentration range below 0.1% was decreased, it was decreased, it is concluded that the doping of Ca is useful for the improvement of the CO2 sensing characteristics of CuO-BaTiO3 capacitor. This is because that the interference of humidity is remarkably reduced and the optimum operation temperature can be lowered to the temperature range from 400 to 450℃.
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18
リチウムイオン伝導体を用いたヒーター組込式炭酸ガスセンサ
今中信人・村田年秀・足立吟也
阪大工
A HEATER COMBINED CARBON DIOXIDE GAS SENSOR BASED ON LITHIUM IONIC CONDUCTOR
Nobuhito IMANAKA, Toshihide MURATA and Gin-ya ADACHI
Department of Applied Chemistry, Faculty of Engineering, Osaka University
2-1 Yamadaoka Suita, Osaka 565, Japan
A heater combined CO2 sensor was set up with the combination of both the lithium ionic conducting solid electrolyte (LiTi2(PO4)3+0.2Li3PO4) and an oxide ionic conductor{(Bi2O3)0.75 (Y2O3)0.25}. The oxide ionic conductor was employed for the purpose of getting rid of a reference CO2 source. The application of the oxide conductor also contributed to obtain the CO2 sensor which detected the CO2 concentration accurately even under continuously changing oxygen contents. A linear relation was obtained between the sensor output and the logalithm of the CO2 concentration. The slope of the line was almost equal to the value calculated from the Nernst equation . The remarkable advantage of the heater combined CO2 sensor is that the whole sensor probe can be directly inserted into the detecting atmosphere.
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19
Li2CO3 - Li3PO4 - Al2O3系固体電解質を用いたCO2ガスセンサ
成田英和*・張 益燦*・水崎純一郎・田川博章
横浜国大環境研・曙ブレーキ中研*
CO2 GAS SENSOR USING SOLID ELECTROLYTE OF THE Li2CO3 - Li3PO4 - Al2O3 SYSTEM
Hidekazu NARITA*, Zhang Yi CAN*, Junichiro MIZUSAKI and Hiroaki TAGAWA
Institute of Environmental Science and Technology, Yokohama National University
156 Tokiwadai Hodagaya-ku, Yokohama 240, Japan
*Akebono Brake Research and Development Center, Ltd.
4-71 Higashi 5-chome Hnyu-shi, Saitama 348, Japan
Li2CO3-Li3PO4 is known as a lithium ion conductor. We investigated the application of Li2CO3-based solid solution as an electrolyte of CO2 gas sensor. We used the mixture of Li2CO3-Li3PO4 solid solution and Al2O3 as electrolyte and made a CO2 concentration cell, with N2-21%O2 containing 1000 ppmCO2 as the reference gas and N2-21%O2 containing 20-1000 ppmCO2 as sample gases. The sensor worked at 350-600℃. The EMF of the CO2 sensor essentially obeyed the Nernst equation. We found that the response rate of the sensor in humid gas were slower than in dry gas. However, the humid gas didn't influence the EMF of the sensor.
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20
亜硝酸ナトリウム系補助相を用いた固体電解質NOxセンサ
姚 勝・清水陽一・三浦則雄・山添 f
九大総合理工
SOLID ELECTROLYTE NOX SENSOR USING SODIUM NITRITE-BASED AUXILIARY PHASE
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
An Na+-conductor (NASICON)-based solid electrolyte sensor fitted with an NaNO2-Li2CO3 (9:1 in molar ratio) auxiliary phase showed excellent sensing characteristics to very dilute NO2 in air. The electromotive force, EMF, followed the Nernst's equation for 0.005-200 ppm NO2 at 150℃, the Nernst's slop indicating one-electron reduction of NO2. The 90% response time to 10 ppm and 5 ppb NO2 were 8 s and 4 min, respectively. Furthermore, the present sensor was found to be hardly affected by CO2 up to 40 vol%.
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21
ガルバニ電池式オゾンセンサの開発 (1)
人見周二・工藤寿士
日本電池
DEVELOPMENT OF GALVANIC OZONE SENSOR (1)
Shuji HITOMI and Hisashi KUDO
Japan Storage Battery Co., Ltd.
Nishinosho Kisshoin Minami-ku, Kyoto 601, Japan
A new galvanic ozone sensor which is able to be calibrated with air and can be used continuously in a high ozone concentration atmosphere ahs been developed.
The sensor is a composite cell of O3-Ag/AgCl cell and O2-Pb cell using a common cathode (Au plate covered with FEP membrane). The sensor is based on a principle that an ozone concentration can be known by the ratio of O3-Ag/AgCl cell voltage to O2-Pb cell voltage, in the air, which realizes the calibrating function.
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22
酸化白金薄膜電極を用いた定電位電解式酸性ガスセンサ
石地 徹・芝崎克一・高橋勝緒*
理研計器・理化学研究所*
AMPEROMETRIC ACIDIC GAS SENSOR BASED ON REDUCTION OF PLATIUM OXIDE THIN-FILM ELECTRODE
Toru ISHIJI, Yoshikazu SHIBASAKI and Katsuo TAKAHASHI*
Riken Keiki Co. Ltd.,
2-7-6 Azusawa Itabashi-ku, Tokyo 174, Japan
*The Institute fo Physical and Chemical Research (RIKEN)
2-1 Hirosawa Wako-shi, Saitama 351-01, Japan
Electrochemical reduction properties of platinum oxide was studied to develop an amperometric acidic gas sensor. The reduction current of PtO obtained by voltummetry was related to the hydrogen ion concentration in an supporting electrolyte solution. The gas permeable PtO electrode (GPE) was prepared on a PTFE membrane by a reactive sputter coating. The sensor constructed with GPE showed a good current response for HCl gas and CO2 at the optimum electrode potential determined by the solution system. The linear relationship between the reduction current and the HCl gas concentration was obtained. As for CO2, the current is found to be proportional to the suqare root of the gas concentration.
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23
マイクロマシン技術による小型ガラス複合電極の開発
鈴木博章・菅間明夫
富士通研
DEVELOPMENT OF A MINIATURE DOUBLE-BARRELED GLASS ELECTRODE USING MICROMACHINING TECHNIQUES
Hiroaki SUZUKI and Akio SUGAMA
FUJITSU LABORATORIES LTD.
Atsugi-shi, Kanagawa 243-01, Japan
A miniature double-barreled glass electrode was batch-fabricated using micromachining techniques. Two Ag/AgCl reference electrodes, one for the glass electrode and the other for the outer reference electrode, were formed on both surfaces of a glass substrate. The containers for the electrolyte solution were made by anisotropically etching silicon substrates. A 20-μm-thick glass membrene was bonded to the container for the glass electrode. To make it more sensitive to pH variation, 5-μm-thick Na-Ca glass was sputtered on the membrane. The glass and silicon substrates were bonded either by field-assisted bonding or using a photoresist layer as an adhesive. Its response time was less than 5 s. The glass membrane potential varied against pH with a gradient of about -50 mV/pH at 25℃.
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24
チアミンピロリン酸の添加を必要としないリン酸イオンセンサの開発
鈴木正康・倉田浩伸・山本弘之*・軽部征夫**
九工大情報工・鶴見精機*・東大先端研**
DEVELOPMENT OF PHOSPHATE ION SENSOR USING RECOMBINANT PYRUVATE OXIDASE
Masayasu SUZUKI, Hironobu KURATA, Hiroyuki YAMAMOTO* and Isao KARUBE**
Faculty of Computer Science and Systems Engineering, Kyushu Institute of Technology
Iizuka, Fukuoka 820, Japan
*The Turumi-Seiki Co., Ltd,
Yokohama, Kanagawa 230, Japan
**Research Center for Advanced Science and Technology, University of Tokyo
Meguro, Tokyo 153, Japan
Phosphate ion sensor was developed by the use of recombinant pyruvate oxidase from Lactobacillus plantarum and electrochemical detector.
Response time for phosphate ion was 80 s and total measurement time for one sample was 3 min. Citrate buffer solution(pH 6.3) was most suitable for the measurement and optimum flow rate was 0.6 ml/min. Measurement range of phosphate ion by 3-electrodes system was 0.1-10μM. But this sensitivity was not enough for practical use in dam-lake. By using 2-electrodes system, the sensitivity was remarkably improved and 15 nM phosphate ion could be detected. This detection limit is almost enough for dam-lakd monitoring.
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25
酵素／脂質コンプレックスを用いたグルコースセンサのFIA系への応用
水谷文雄・矢吹聡一・曽良達生
工技院生命研
ENZYME/LIPID-COMPLEX-BASED GLUCOSE ELECTRODE FOR FLOW INJECTION
Fumio MIZUTANI, Soichi YABUKI and Tatsuo KATSURA
National Institute of Bioscience and Human-Technology
1-1 Higashi Tsukuba, Ibaraki 305, Japan
The amperometric determination of glucose was performed using a flow injection system with a thin-layer cell and a glassy carbon electrode coated with a Nafion layer containing lipid-modified glucose oxidase. The electrode exhibited a linear response for glucose concentration up to 10 mM with a sampling rate of 250 samples per hour. The liftime of the electrode was 3 months without significant decrease in sensitivity.
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26
酵素電着法により作製したEEEセンサの応答特性
矢尾板仁・宇佐美将太*・内山俊一*・碇山義人**・山内 繁
国立リハ研・埼玉工大工*・東工大生命理工**
FABRICATION OF ENZYME EMBODIED ELECTRODE (EEE) SENSOR BY ELECTROADSORPTION
Masashi YAOITA, Shouta USAMI*, Shunichi UCHIYAMA*, Yoshihito IKARIYAMA** and Shigeru YAMAUCHI
Research Institute of National Rehabilitation Center for the Disabled
Tokorozawa, Saitama 359, Japan
*Dept. of Environmental Engineering, Saitama Institute of Technology
Okabe, Saitama 369-02, Japan
**Dept. of Bioengineering, Tokyo Institute of Technology
O-okayama, Tokyo 152, Japan
In order to fabricate an enzyme embodied electrode (EEE) with high response current, glucose oxidase (GOD) was immobilized by electroadsorption on a platinized platinum electrode. Sensor response was defined as a transient current at 40 ms to a potentiostatic pulse of 0.5 V (vs.Ag/AgCl). Optimum condition of the potentiostatic electroadsorption was 0.5 V and 5 min. With this condition an EEE with doubled response current was fabricated. The response of this electrode to ascorbate solution was the same as that of the previous electrodes.
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27
酸性ウレアーゼカラムを用いた尿素のフローカロリメトリックバイオセンシング
佐藤生男・新井誠一
神奈川工科大工
FLOW-CALORIMETRIC BIOSENSING OF UREA USING AN ACID UREASE COLUMN
Ikuo SATOH and Seiichi ARAI
Department of Chemical Technology, Faculty of Engineering, Kanagawa Institute of Technology
1030 Shimo-Ogino Atsuhi-shi, Kanagawa 243-02, Japan
Flow-injection calorimetric technique was applied to microdetermination of urea in acidic media. Acid urease was immobilized onto porous glass beads and then packed into a small polymer column. The proposed system was equipped with the enzyme-column and a flow-calorimetric device (enzyme thermistor). The heat evolution due to the enzymatic hydrolysis of urea was continuously detected with the device. The calibration graph was linear from 0.05 to 50 mM urea for 1.0-mL injections. The relative standard deviation for 1.0 mM urea was 1.3% (n=10). The assay took 6 min.
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28
シリコーン制限透過膜を用いたISFET型無希釈グルコースセンサの試作
齋藤 敦・伊藤成史・木村 純・栗山敏秀*
NEC 資源・環境研、マイクロエレ研*
DEVELOPMENT OF AN ISFET GLUCOSE SENSOR WITH A SILICONE RUBBER MEMBRANE WHICH HAS GLUCOSE RESTRICTED PERMEABILITY
Atsushi SAITO, Narushi ITO, Jun KIMURA and Toshihide KURIYAMA*
Resources & Environment Protection Research Laboratories
*Microelectronics Research Laboratories
NEC Corporation
4-1-1 Miyazaki, Miyamae-ku, Kawasaki, Kanagawa 216, Japan
An ion-sensitive field-effect transistor (ISFET) glucose sensor with a silicone rubber membrane which has glucose restricted permeability was fabricated. Its operation was demonstrated in monitoring glucose concentration in serum and suction effusion fluid without sample dilution.
This sensor characteristics were evaluated by measuring glucose in HEPES-NaOH buffer (20 mM, 100 mM, pH 7.5) and NaCl solution (150 mM). The silicone membrane, which restricts glucose diffusion, expands the linear calibration range up to 500 mg/dl glucose. This membrane also restricts buffer species diffusion so that the sensor outputs are not affected by solution buffer capacity. Moreover, investigating the relationship between the sensor response and dissolved oxygen concentration, this sensor showed constant outputs in solutions containing from 1.5 to 7.5 ppm oxygen. This sensor was mounted onto a flow cell, into which serum samples and HEPES buffer solution (20 mM, pH 7.5) were alternately fed by a peristaltic pump. It takes 15 minutes to measure one sample. In 20 measurements on the same serum sample, the sensor output precision was found to be 4.7%, this sensor is able to measure glucose concentration in the from 100 mg/dl to 500 mg/dl range.
This sensor was applied to monitor glucose concentration in glucose loaded rabbit suction effusion fluid. The glucose level profile, obtained by this sensor, showed a good correlation with that measured by a conventional glucose analyzer.
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29
光重合性ハイドロゲルを用いた表面光検出型マルチ酵素センサの試作
清水正章・金井康通・内田秀和・周 春光・勝部昭明
埼玉大工
INTEGRATED SPV BIOSENSOR EMPLOYING A PHOTO-POLYMERIZED HYDROGEL
Masaki SHIMIZU, Yasuyuki KANAI, Hidekazu UCHIDA, Chun Guang ZHOU and Teruaki KATSUBE
Faculty of Engineering, Saitama University
255 Shimo-Okubo Urawa-shi, Saitama 338, Japan
A monolithically integrated biosensor is constructed using surface photovoltage technology combined with new patterning methods for multiple enzyme integration. The advantage of this method is the simple structure of the system which allows better flexibility to integrate multiple sensing membranes on a single chip semiconductor surface. Two kinds of patterning methods are successfully applied: one is a photo-patterning technique using a water soluble photo-polymer and another is a pen printing method which provides a simple method suitable for mass production.
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30
導電率検出器を用いる免疫測定法の開発
柳生田薫・辺見彰秀・浅野泰一・陳 健源*・軽部征夫*
電気化学計器・東大先端研*
DEVELOPMENT OF IMMUNO-SENSING SYSTEM USING CONDUCTIVITY DETECTOR
Kaoru YAGIUDA, Akihide HEMMI, Yasukazu ASANO, Chien-Yuan CHEN *and Isao KARUBE*
DKK Corporation
Musashino-shi, Tokyo 180, Japan
*Research Center for Advanced Science and Technology, The University of Tokyo
Meguro-ku, Tokyo 153, Japan
For the purpose of establishing a practically applicable measuring system for portable immuno-sensor, we have developed a novel immunoassay method based on the measurement of conductivity. Anti-mouse immunoglobline G (IgG) antibody was immobilized onto the surface of platinum electrode. Mouse IgG were reacted with antibody for 15 min. The conductivity of the electrode increased with the increment of IgG concentration. A linear relationship was obtained between the conductivity and mouse IgG concentration. However, this relationship was found only in water solution. Selectivity of this detection system was satisfactory, and reproducibility was good.
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31
リサイクル品を用いた使い捨て型小型酸素電極の開発
鈴木博章
富士通研
DEVELOPMENT OF A DISPOSABLE MINIATURE OXYGEN ELECTRODE USING RECYCLED MATERIALS
Hiroaki SUZUKI
FUJITSU LABORATORIES LTD.
Atsugi-shi, Kanagawa 243-01, Japan
This paper describes a remarkably inexpensive disposable Clark oxygen electrode fabricable with recycled materials and without expensive processes. The sensor consists of recycled polyester overhead transparencies on which the cathode and anode patterns are deposited by vacuum vaporation, recycled copier paper to hold the electrolyte, and a gas-permeable membrane.
Although deceptively simple in terms of structure and fabrication, the electrode performed well as an oxygen sensor and proved surprisingly durable-----its 90% response time was between 60 and 70 s, with a good linear relationship between generated current and dissolved oxygen concentration.
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32
フォトリソグラフィー法によりパターン化した肝細胞を用いた毒物センシング
大橋昭王・宮本重幸・木村 純・赤池敏宏*
NEC 資源研・環境研、東工大生命理工*
TOXICITY SENSING USING PATTERN-CULTURED HEPATOCYTES BY PHOTOLITHOGRAPHIC METHOD
Akio OHASHI, Shigeyuki MIYAMOTO, Jun KIMURA and Toshihiro AKAIKE*
NEC Corporation, Resources & Environment Protection Research Laboratories
Kawasaki, Kanagawa 216, Japan
*Faculty of Bioscience and Biotechnology, Tokyo Institute of Technology
Yokohama, Kanagawa 227, Japan
Recently, toxicity tests and safety evaluations using cultured cells have been studied for chemicals as an alternative to animal experiments. Hepatocytes (liver cells) are suitable for this purpose since liver is the main metaboloic organ of the body and the main site of detoxication. We have already established a method of hepatocyte patterning on the collagen patterned plates made by a photholitographic method. In this paper, hepatocytes are cultured with various chemicals, such as tetrachloromethane, and hepatocyte pattern formation is observed.
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33
遺伝子組み換え菌を用いた環境中難分解性化合物の発光モニタリング
小山隆史・小畠英理・碇山義人・相澤益男
東工大生命理工
BIOLUMINESCENT MONITORING OF HARDLY DECOMPOSABLE CHEMICAL COMPOUNDS IN THE INVIRONMENT BY RECOMBINANT E. coli
Takashi KOYAMA, Eiry KOBATAKE, Yoshihito IKARIYAMA and Masuo AIZAWA
Department of Bioengineering, Tokyo Institute of Technology
4259 Nagatsuta Midori-ku Yokohama, Kanagawa 227, Japan
Recently, new approaches to monitor hardly decomposable chemical compounds by taking advantages of excellent metabolisms of bacteria, are being gaining strong impetus. Benzene, toluene, xylene (BTX), which are massively produced on a large scale in industrial circles, are dischrged and accumulated in the environment. Monitoring these organic compounds has significant meaning for the prevention of environmental destruction.
A new strategy toward the detection of aromatic hydrocarbons with a recombinant E.coli has been taken. We have constructed a light-generating plasmid (pTSN 316). A fragment from TOL plasmid bearing the promoter (Ps) of the xylS gene for a transcriptional activator, was fused to the luciferase gene of firefly (Photinus pyralis). The E.coli strain containing this plasmid (HB101(pTSN316)) can emit photons in the presence of a benzene derivative. The xylR regulatory gone of TOL plasmid plays an important role to induce luciferase. This system can be used to measure the BTX concentration.
The bioluminescence of the luminous E.coli increased according to BTX concentration. When compared at 0.8 or 0.9 mM concentration, the bioluminescence became smaller in order of m-xylene, p-xylene, toluene, and benzene. This indicates that specific binding between the regulatory protein, XylR, and BTX is very important. Moreover, we made a device by immobilizing the recombinat E.coli to the tip of a fiber optic, and tried the measurement of BTX concentration in a batch system. In this result, several ppm of BTX was measured.
These findings suggest that realtime monitoring of BTX is possible. And the aromatic hydrocarbon concentration can be easily measured by using the proposed fiber optic device. We believe that substances of environmental deterioration can be sensitively monitored in this method.
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特別講演２
化学センサを用いる流れ分析用検出器の開発とその応用
浅野泰一
電気化学計器
DEVELOPMENT OF DETECTOR USING CHEMICAL SENSOR FOR FLOW ANALYSIS ITS APPLICATIONS
Yasukazu ASANO
Research Center, DKK CORPORATION
4-13-14 Kitamachi Kichijoji Musashino, Tokyo 180, Japan
Taste of food has been usually evaluated by an organoleptic test in food munufacturing processes at present. However, it takes times and cost for this evaluation test. Therefore, it is expected to developed a sensing system for evaluation of taste of foods. We have found that L-lactate played a significant role in the taste of consomme soup by a a preliminaly experiment with HPLC. In this paper, I would like to talk about a Flow Injection System (FIA) with oxygen detector and enzyme-column for L-lactate analysis we developed. The multiple regression analysis was performed with the organoleptic values and 5 parameter (L-lactate Brix, Flavor, IMP, L-gultamate). The correlation coefficient between the organoleptic test and this flow analysis was 0.806. As a result, FIA system using the chemical oxygen detector was useful for the quality control of L-lactate in consomme soup.
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