JPH10160700A - Manufacture of hydrocarbon detecting sensor - Google Patents
Manufacture of hydrocarbon detecting sensorInfo
- Publication number
- JPH10160700A JPH10160700A JP8315936A JP31593696A JPH10160700A JP H10160700 A JPH10160700 A JP H10160700A JP 8315936 A JP8315936 A JP 8315936A JP 31593696 A JP31593696 A JP 31593696A JP H10160700 A JPH10160700 A JP H10160700A
- Authority
- JP
- Japan
- Prior art keywords
- oxide
- film
- oxidation catalyst
- platinum
- platinum electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、雰囲気中の炭化水
素濃度を測定するための炭化水素検出センサの製造方法
に関し、その構成を簡素化して生産性を高め、さらに小
型化、加熱電力の低減をはかったものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a hydrocarbon detection sensor for measuring the concentration of hydrocarbons in an atmosphere. It was measured.
【０００２】[0002]
【従来の技術】従来この種の炭化水素検出センサは、特
開昭５９−１０９８５６号公報に記載されているものが
一般的である。このセンサは、図６に示すように筒体１
２の内部空間部に、白金電極膜１０ａ、１０ｂを両面に
形成した酸素イオン導電性固体電解質９を配置し、白金
電極膜１０ｂの左側空間部分に酸化触媒１１の粒子群を
充填したものである。そして、通気性の有る蓋１３ａ、
１３ｂで筒体１２を両側から挟みこみ、酸化触媒１１の
粒子群および酸素イオン導電性固体電解質９がこぼれな
いようにしている。また、筒体１２の周囲には加熱体１
４を配置し、酸素イオン導電性固体電解質９および酸化
触媒１１の加熱に用いている。2. Description of the Related Art Conventionally, this kind of hydrocarbon detection sensor is generally described in Japanese Patent Application Laid-Open No. 59-109856. This sensor is, as shown in FIG.
2, an oxygen ion conductive solid electrolyte 9 having platinum electrode films 10a and 10b formed on both sides thereof is disposed in the inner space portion, and particles of the oxidation catalyst 11 are filled in the left space portion of the platinum electrode film 10b. . And a lid 13a having air permeability,
The cylindrical body 12 is sandwiched from both sides by 13b to prevent the particle groups of the oxidation catalyst 11 and the oxygen ion conductive solid electrolyte 9 from spilling. The heating element 1 is provided around the cylinder 12.
4 is used for heating the oxygen ion conductive solid electrolyte 9 and the oxidation catalyst 11.
【０００３】一方、酸素イオン導電性固体電解質９に白
金電極膜１０ａ、１０ｂを形成する同種ガスセンサに着
目すると、特開平５−９９８９４号公報に記載されてい
るものがある。このガスセンサは、図７に示すように、
３価以下の金属またはその酸化物を０．０５〜１０．０
重量％含有する酸素イオン導電性の固体電解質体１５
に、３価以下の金属またはその酸化物を０．０５〜１
０．０重量％含有する電極層１６ａ、１６ｂを積層し、
得られた積層体を酸化性雰囲気中において焼成し、固体
電解質体１５と電極層１６ａ、１６ｂとを接合した構成
である。そして３価以下の金属として、銅、ビスマス、
亜鉛、カドミニウムから選択された少なくとも一種を使
用することが記載されている。On the other hand, focusing on the same type of gas sensor in which platinum electrode films 10a and 10b are formed on the oxygen ion conductive solid electrolyte 9, there is one described in Japanese Patent Application Laid-Open No. 5-99894. This gas sensor, as shown in FIG.
0.05 to 10.0 of trivalent or less metal or its oxide
Oxygen ion conductive solid electrolyte body 15 containing by weight
A trivalent or lower metal or its oxide in an amount of 0.05 to 1
The electrode layers 16a and 16b containing 0.0% by weight are laminated,
The obtained laminate is fired in an oxidizing atmosphere, and the solid electrolyte body 15 and the electrode layers 16a and 16b are joined. And copper, bismuth,
It is described that at least one selected from zinc and cadmium is used.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら従来の炭
化水素検出センサは、図６に示すように筒体１２の内部
空間部に酸化触媒１１の粒子群を充填した構成であるた
め、酸化触媒１１の粒子群の取り扱いが煩雑でその充填
に多くの工数を要し、生産性が向上しない課題があっ
た。また筒体１２の内部空間部に酸素イオン導電性固体
電解質９および酸化触媒１１の粒子群を配置し、加熱体
１４を筒体１２の周囲に配置した構成であるため、セン
サの大型化する課題があった。しかも加熱体１４の熱
が、効果的に酸素イオン導電性固体電解質９や酸化触媒
１１に伝達されにくく、加熱電力が大きい課題もあっ
た。However, the conventional hydrocarbon detection sensor has a structure in which the internal space of the cylindrical body 12 is filled with particles of the oxidation catalyst 11 as shown in FIG. There is a problem that the handling of the particle group is complicated and the filling thereof requires a lot of man-hours, and the productivity is not improved. In addition, since the particle group of the oxygen ion conductive solid electrolyte 9 and the oxidation catalyst 11 is arranged in the internal space of the cylinder 12 and the heating element 14 is arranged around the cylinder 12, the sensor becomes large. was there. In addition, the heat of the heating element 14 is difficult to be effectively transmitted to the oxygen ion conductive solid electrolyte 9 and the oxidation catalyst 11, and there is a problem that the heating power is large.
【０００５】一方、図７に示すような酸素イオン導電性
の固体電解質体１５に電極層１６ａ、１６ｂを形成する
同種ガスセンサは、この技術を安定化ジルコニアの固体
電解質体に応用すると、安定化ジルコニアとの熱膨張係
数の一致や酸素イオン導電性が考慮された材料組成・製
法の電極膜になっていないため、安定化ジルコニアが割
れる、密着性がない、特性が得られないなどの課題があ
る。以下、詳細にその内容を説明する。酸化ビスマス
は、酸素イオン導電性に優れるが熱膨張係数が１４×１
０ー6（ｄｅｇー1）もあり、白金の９×１０ー6（ｄｅ
ｇー1）、安定化ジルコニアの１０×１０ー6（ｄｅｇー1）
と比べてその値が約１．４倍大きい。また、酸化ビスマ
スは８２０℃で溶融し酸素イオン導電性に優れた結合材
となるが、焼成温度が低いと溶融せず結合材の役割をな
さないし、焼成温度が高いと変質して酸素イオン導電性
の低下と結合力の低下が起こる性質がある。一方、酸化
銅や酸化カドミニウムは、熱膨張係数が約１１〜１２×
１０ー6（ｄｅｇー1）であり白金や安定化ジルコニアより
１．１〜１．２倍大きいが、酸素イオン導電性がほとん
どない欠点がある。このように、銅、ビスマス、亜鉛、
カドミニウムの金属酸化物さらに金属を電極層に含有さ
せた白金電極膜を安定化ジルコニアに形成するために
は、安定化ジルコニアとの熱膨張係数の一致や酸素イオ
ン導電性を考慮した最適な結合材組成と製造方法が必要
であり、これらが最適でないとジルコニアが割れる、密
着性がない、特性が得られないの課題が発生する。On the other hand, the same type of gas sensor in which the electrode layers 16a and 16b are formed on an oxygen ion-conductive solid electrolyte body 15 as shown in FIG. 7 can be obtained by applying this technology to a stabilized zirconia solid electrolyte body. Since the electrode film is not made of a material composition and manufacturing method that takes into consideration the thermal expansion coefficient of the zirconia and the oxygen ion conductivity, there are problems such as cracking of stabilized zirconia, lack of adhesion, and inability to obtain characteristics. . Hereinafter, the contents will be described in detail. Bismuth oxide has excellent oxygen ion conductivity, but has a thermal expansion coefficient of 14 × 1.
0 over 6 (deg-1) are also available, 9 × 10 over 6 (de platinum
g-1), 10 × 10 over stabilized zirconia 6 (deg-1)
The value is about 1.4 times larger than. Further, bismuth oxide melts at 820 ° C. and becomes a binder having excellent oxygen ion conductivity. However, if the firing temperature is low, it does not melt and does not serve as a binder. There is a property that the property and the binding force decrease. On the other hand, copper oxide and cadmium oxide have a thermal expansion coefficient of about 11 to 12 ×.
10-2 6 (deg-1), and 1.1 to 1.2 times greater than platinum and stabilized zirconia, but there is a drawback with little oxygen ion conductivity. Thus, copper, bismuth, zinc,
In order to form a platinum electrode film containing a metal oxide of cadmium and a metal in the electrode layer on stabilized zirconia, it is necessary to match the thermal expansion coefficient of the stabilized zirconia and the optimal binder considering oxygen ion conductivity. A composition and a production method are required, and if these are not optimal, problems such as cracking of zirconia, lack of adhesion, and inability to obtain characteristics occur.
【０００６】[0006]
【課題を解決するための手段】本発明は上記課題を解決
するために、安定化ジルコニア焼結板の表面に、白金に
酸化ビスマスを１．５〜５wt％混合した白金電極膜を２
個厚膜印刷した後に、酸化触媒粉末を含有とした酸化触
媒膜を前記白金電極膜の片側上部に厚膜印刷して積層
し、前記白金電極膜と前記酸化触媒膜を７００〜１００
０℃で同時に焼成した。また酸化触媒は、融点１１００
℃以上の高活性材料である白金、酸化銅、酸化鉄、酸化
ニッケル、酸化コバルト、酸化マンガン、酸化ガリウ
ム、酸化クロム、酸化チタンの群から選択した少なくと
も１種であるとしたものである。In order to solve the above-mentioned problems, the present invention provides a stabilized zirconia sintered plate having a platinum electrode film comprising platinum and bismuth oxide mixed at 1.5 to 5 wt% on the surface thereof.
After the individual thick film printing, an oxidation catalyst film containing an oxidation catalyst powder is thickly printed and laminated on one upper side of the platinum electrode film, and the platinum electrode film and the oxidation catalyst film are 700 to 100.
Co-fired at 0 ° C. The oxidation catalyst has a melting point of 1100.
The material is at least one selected from the group consisting of platinum, copper oxide, iron oxide, nickel oxide, cobalt oxide, manganese oxide, gallium oxide, chromium oxide, and titanium oxide, which are highly active materials having a temperature of not less than ° C.
【０００７】上記発明によれば、酸化触媒膜は厚膜印刷
という簡単な製法で白金電極膜に固定化されるため、取
り扱いが簡単になり生産性が向上する。しかも白金電極
膜は、安定化ジルコニアとの熱膨張係数の一致や酸素イ
オン導電性を考慮した結合材組成と製造方法であるた
め、高活性なセンサがジルコニア割れなどの不良品を製
造することなく高い部留まりで得られる。According to the above invention, the oxidation catalyst film is fixed to the platinum electrode film by a simple manufacturing method called thick film printing, so that the handling is simplified and the productivity is improved. Moreover, since the platinum electrode film is a binder composition and manufacturing method that takes into account the matching of thermal expansion coefficient with stabilized zirconia and oxygen ion conductivity, highly active sensors do not produce defective products such as zirconia cracks. Obtained with a high yield.
【０００８】また本発明は上記課題を解決するために、
酸化触媒膜および白金電極膜付き安定化ジルコニア焼結
板と、ヒータ膜付きフォルステライト基板とを、熱膨張
係数が安定化ジルコニアおよびフォルステライト基板と
概略同じである硝子膜を介して接合固定したものであ
る。そのため、ヒータ膜が効果的に安定化ジルコニア焼
結板や酸化触媒膜に伝達され、センサの小型化および加
熱電力の低減ができる。[0008] In order to solve the above problems, the present invention provides:
A stabilized zirconia sintered plate with an oxidation catalyst film and a platinum electrode film and a forsterite substrate with a heater film bonded and fixed via a glass film whose thermal expansion coefficient is approximately the same as that of the stabilized zirconia and forsterite substrates It is. Therefore, the heater film is effectively transmitted to the stabilized zirconia sintered plate or the oxidation catalyst film, and the sensor can be downsized and the heating power can be reduced.
【０００９】[0009]
【発明の実施の形態】本発明は、酸化イットリウム８モ
ル％とジルコニア９２モル％からなる安定化ジルコニア
焼結板の表面に、白金に酸化ビスマスを１．５〜５wt％
混合した白金電極膜を２個厚膜印刷した後に、酸化触媒
粉末を含有とした酸化触媒膜を前記白金電極膜の片側上
部に厚膜印刷して積層し、前記白金電極膜と前記酸化触
媒膜を７００〜１０００℃で同時に焼成した構成と製法
であり、前記酸化触媒が白金、酸化銅、酸化鉄、酸化ニ
ッケル、酸化コバルト、酸化マンガン、酸化ガリウム、
酸化クロム、酸化チタンの群から選択した少なくとも１
種であるとしたものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a stabilized zirconia sintered plate comprising 8 mol% of yttrium oxide and 92 mol% of zirconia.
After printing two mixed platinum electrode films in a thick film, an oxidation catalyst film containing an oxidation catalyst powder is thickly printed on one side of the platinum electrode film and laminated, and the platinum electrode film and the oxidation catalyst film are stacked. Are simultaneously calcined at 700 to 1000 ° C. and the production method, wherein the oxidation catalyst is platinum, copper oxide, iron oxide, nickel oxide, cobalt oxide, manganese oxide, gallium oxide,
At least one selected from the group consisting of chromium oxide and titanium oxide
It is assumed to be a seed.
【００１０】そして酸化触媒は膜化して白金電極膜に積
層化し同時焼成するため、簡単な製法で酸化触媒が固定
でき、取り扱いが簡素化されて生産性が向上する。ま
た、白金電極膜は安定化ジルコニアとの熱膨張係数の一
致や酸素イオン導電性を考慮した結合材組成と製造方法
であるため、ジルコニア割れなどの不良品を製造するこ
となく高い部留まりで高活性なセンサが得られる。また
酸化触媒は、融点１１００℃以上の高活性な酸化触媒で
あるため、検出感度の高いセンサが得られる。Since the oxidation catalyst is formed into a film, laminated on a platinum electrode film, and fired simultaneously, the oxidation catalyst can be fixed by a simple manufacturing method, handling is simplified, and productivity is improved. In addition, since the platinum electrode film is a binder material composition and a production method that takes into account the matching of thermal expansion coefficient with stabilized zirconia and oxygen ion conductivity, high yield and high yield can be achieved without producing defective products such as zirconia cracks. An active sensor is obtained. Further, since the oxidation catalyst is a highly active oxidation catalyst having a melting point of 1100 ° C. or higher, a sensor having high detection sensitivity can be obtained.
【００１１】さらに、白金電極膜は、酸化ビスマス量を
Ｂ、酸化カドミニウム量をＣ、その混合比をＣ／Ｂとす
ると、０．１≦Ｃ／Ｂ≦１なる条件で両材料を混合した
ものである。Further, when the amount of bismuth oxide is B, the amount of cadmium oxide is C, and the mixing ratio is C / B, the platinum electrode film is a mixture of both materials under the condition of 0.1 ≦ C / B ≦ 1. It is.
【００１２】そして、白金電極膜に融点８２０℃の酸化
ビスマスとともに融点７００℃の酸化カドミニウムをさ
らに小量混合することでこれら結合材の融解性が向上
し、白金電極膜と安定化ジルコニア焼結板との密着性が
良くなって白金電極膜から安定化ジルコニア焼結板への
酸素伝達特性が向上する。そのため、検出感度の高いセ
ンサが得られる。Further, by further mixing a small amount of cadmium oxide having a melting point of 700 ° C. together with bismuth oxide having a melting point of 820 ° C. in the platinum electrode film, the melting properties of these binders are improved, and the platinum electrode film and the stabilized zirconia sintered plate are mixed. And the oxygen transfer characteristic from the platinum electrode film to the stabilized zirconia sintered plate is improved. Therefore, a sensor having high detection sensitivity can be obtained.
【００１３】また酸化触媒が、白金または酸化銅である
としたものである。白金および酸化銅は、炭化水素の酸
化能力が高い。しかも熱膨張係数が、白金は９×１０ー6
（ｄｅｇー1）、酸化銅は１１×１０ー6（ｄｅｇー1）であ
り、安定化ジルコニア焼結板の１０×１０ー6（ｄｅ
ｇー1）と概略同じある。従って、酸化触媒が白金電極膜
に良好に固定化され、検出感度の高いセンサが得られ
る。[0013] Further, the oxidation catalyst is platinum or copper oxide. Platinum and copper oxide have a high ability to oxidize hydrocarbons. Moreover, the coefficient of thermal expansion is 9 × 10-6 for platinum.
(Deg-1), copper oxide is 11 × 10 over 6 (deg-1), 10 × 10 over 6 (de stabilized zirconia sintered plate
g -1 ). Therefore, the oxidation catalyst can be satisfactorily immobilized on the platinum electrode membrane, and a sensor with high detection sensitivity can be obtained.
【００１４】さらに、ジルコニア焼結板と、前記ジルコ
ニア焼結板の片側表面に形成した２個の白金電極膜と、
前記白金電極膜の片側上部に積層固定されており酸化触
媒を主成分とした酸化触媒膜と、前記ジルコニア焼結板
の他面側に形成されており熱膨張係数が９〜１１×１０
ー6（ｄｅｇー1）の硝子膜と、前記硝子膜に積層固定した
フォルステライト基板と、前記フォルステライト基板の
他面側に形成したヒータ膜から構成としたものである。Further, a zirconia sintered plate, and two platinum electrode films formed on one surface of the zirconia sintered plate,
An oxidation catalyst film which is laminated and fixed on one upper side of the platinum electrode film and has an oxidation catalyst as a main component, and which is formed on the other surface side of the zirconia sintered plate and has a thermal expansion coefficient of 9 to 11 × 10
-6 (deg -1 ), a forsterite substrate laminated and fixed to the glass film, and a heater film formed on the other surface of the forsterite substrate.
【００１５】そして、硝子膜は熱膨張係数がジルコニア
焼結板およびフォルステライト基板と概略同じであるた
め、白金電極膜付きジルコニア焼結板とヒータ膜付きフ
ォルステライト基板とが簡単に固定できる。また酸化触
媒は膜であるため簡単に白金電極膜に固定できる。従っ
て、ヒータ膜が効果的にジルコニア焼結板や酸化触媒膜
に伝達され、センサの小型化および加熱電力の低減がで
きる。Since the glass film has substantially the same thermal expansion coefficient as the zirconia sintered plate and the forsterite substrate, the zirconia sintered plate with the platinum electrode film and the forsterite substrate with the heater film can be easily fixed. Further, since the oxidation catalyst is a film, it can be easily fixed to the platinum electrode film. Therefore, the heater film is effectively transmitted to the zirconia sintered plate or the oxidation catalyst film, and the size of the sensor can be reduced and the heating power can be reduced.
【００１６】また、硝子膜が酸化アルミナが３〜７％、
酸化ホウソが３〜７％、酸化カルシウムが１〜２％、酸
化ストロンチウムが４〜６％、酸化バリウムが０．２〜
１．５％、酸化ナトリウムが１０〜１３％、酸化カリウ
ムが４〜８％、酸化チタンが６〜９％、残部が酸化珪素
であるとしたものである。Further, the glass film is made of 3 to 7% alumina oxide,
Boro oxide 3-7%, calcium oxide 1-2%, strontium oxide 4-6%, barium oxide 0.2-
1.5%, sodium oxide is 10 to 13%, potassium oxide is 4 to 8%, titanium oxide is 6 to 9%, and the remainder is silicon oxide.
【００１７】そして、これら材料組成の硝子は、熱膨張
係数が９〜１１×１０ー6（ｄｅｇー1）でありジルコニア
焼結板とフォルステライト基板とを良好に接合固定でき
る。しかも、７００〜１０００℃の焼成で接合固定でき
るため、白金電極膜や酸化触媒膜への影響が少なく検出
感度の高いセンサが得られる。[0017] Then, the glass of the material composition has a thermal expansion coefficient of 9 to 11 × 10 over 6 (deg-1), and a forsterite board zirconia sintered plate can be satisfactorily bonded and fixed. In addition, the sensor can be bonded and fixed by firing at 700 to 1000 ° C., so that a sensor having little influence on the platinum electrode film and the oxidation catalyst film and having high detection sensitivity can be obtained.
【００１８】また、酸化触媒膜が、酸化触媒の粒子群を
耐熱繊維束に内部に充填した構成のマットであるとした
ものである。Further, the oxidation catalyst film is a mat having a structure in which particles of the oxidation catalyst are filled in heat-resistant fiber bundles.
【００１９】そして、マットとすることで、酸化触媒膜
は簡単に白金電極膜に固定でき、取り扱いが簡素化され
て生産性が向上する。By using a mat, the oxidation catalyst film can be easily fixed to the platinum electrode film, the handling is simplified, and the productivity is improved.
【００２０】（実施例）以下、本発明の実施例を添付図
面に基づいて説明する。Embodiments of the present invention will be described below with reference to the accompanying drawings.
【００２１】図１は、本発明の実施例である炭化水素検
出センサの断面図である。炭化水素検出センサは、酸化
イットリウム８モル％とジルコニア９２モル％からなる
安定化ジルコニア焼結板１と、安定化ジルコニア焼結板
１の表面に形成した２個の白金電極膜２ａ、２ｂと、片
側の白金電極膜２ｂの上部に積層した酸化触媒膜３とか
ら構成される。白金電極膜２ａ、２ｂは、高粘性有機溶
剤に小量の酸化ビスマス粉末３と多量の白金粉末２を混
合したペーストの厚膜印刷膜である。酸化触媒膜３は、
高粘性有機溶剤に多量の白金、酸化銅、酸化鉄、酸化ニ
ッケル、酸化コバルト、酸化マンガン、酸化ガリウム、
酸化クロム、酸化チタンの群から選択した少なくとも１
種の酸化触媒粉末５を混合したペーストの厚膜印刷膜で
ある。白金電極膜２ａ、２ｂと酸化触媒膜３は７００〜
１０００℃で同時に焼成する。FIG. 1 is a sectional view of a hydrocarbon detection sensor according to an embodiment of the present invention. The hydrocarbon detection sensor includes a stabilized zirconia sintered plate 1 composed of 8 mol% of yttrium oxide and 92 mol% of zirconia, and two platinum electrode films 2 a and 2 b formed on the surface of the stabilized zirconia sintered plate 1. And an oxidation catalyst film 3 laminated on one side of the platinum electrode film 2b. The platinum electrode films 2a and 2b are thick print films of a paste in which a small amount of bismuth oxide powder 3 and a large amount of platinum powder 2 are mixed in a high-viscosity organic solvent. The oxidation catalyst film 3
A large amount of platinum, copper oxide, iron oxide, nickel oxide, cobalt oxide, manganese oxide, gallium oxide,
At least one selected from the group consisting of chromium oxide and titanium oxide
It is a thick print film of a paste in which various kinds of oxidation catalyst powders 5 are mixed. The platinum electrode films 2a and 2b and the oxidation catalyst film 3 are 700 to
Simultaneous firing at 1000 ° C.
【００２２】安定化ジルコニア焼結板１は、その片側表
面に２個の白金電極膜２ａ、２ｂを形成しており、その
他面側には熱膨張係数が９〜１１×１０ー6（ｄｅｇー1）
の硝子膜６を介してヒータ膜８付きフォルステライト基
板７を固定している。The stabilized zirconia sintered plate 1, two platinum electrodes film 2a on its one surface, 2b forms a thermal expansion coefficient of the other surface side 9 to 11 × 10 over 6 (deg chromatography 1 )
The forsterite substrate 7 with the heater film 8 is fixed via the glass film 6.
【００２３】白金電極膜２ａ、２ｂおよびヒータ膜８に
は、白金と硝子１〜５wt％との混合物であるリ−ド線固
定材（記載せず）を介して白金リード線（記載せず）が
固定されている。Platinum lead wires (not shown) are applied to the platinum electrode films 2a and 2b and the heater film 8 via a lead wire fixing material (not shown) which is a mixture of platinum and glass at 1 to 5% by weight. Has been fixed.
【００２４】材料について記す。白金電極膜２ａ、２ｂ
は、白金に混合された酸化ビスマス量をＢとすると１．
５wt％≦Ｂ≦５wt％であり、必要に応じて酸化カドミニ
ウムの量をＣとしその混合比をＣ／Ｂとすると０．１≦
Ｃ／Ｂ≦１なる条件でさらに混合したものである。な
お、これら値は焼成後の値である。硝子膜６は、酸化ア
ルミナが３〜７％、酸化ホウソが３〜７％、酸化カルシ
ウムが１〜２％、酸化ストロンチウムが４〜６％、酸化
バリウムが０．２〜１．５％、酸化ナトリウムが１０〜
１３％、酸化カリウムが４〜８％、酸化チタンが６〜９
％、残部が酸化珪素である。この材料組成の硝子は、熱
膨張係数が９〜１１×１０ー6（ｄｅｇー1）であるため、
安定化ジルコニア焼結板とフォルステライト基板とを良
好に接合固定できる。しかも、７００〜１０００℃の焼
成で良好に接合固定できるため、白金電極膜や酸化触媒
膜への熱影響が少ない。ヒータ膜８は、白金である。The materials will be described. Platinum electrode films 2a, 2b
Means that the amount of bismuth oxide mixed with platinum is B.
5 wt% ≦ B ≦ 5 wt%, and if necessary, the amount of cadmium oxide is C and the mixing ratio is C / B, and 0.1 ≦
The mixture was further mixed under the condition of C / B ≦ 1. These values are values after firing. The glass film 6 is composed of 3 to 7% alumina oxide, 3 to 7% boron oxide, 1 to 2% calcium oxide, 4 to 6% strontium oxide, 0.2 to 1.5% barium oxide, Sodium is 10
13%, potassium oxide 4-8%, titanium oxide 6-9
%, The balance being silicon oxide. For glass the material composition, thermal expansion coefficient of 9 to 11 × 10 over 6 (deg-1),
The stabilized zirconia sintered plate and the forsterite substrate can be bonded and fixed well. In addition, since it can be bonded and fixed well by firing at 700 to 1000 ° C., there is little thermal influence on the platinum electrode film and the oxidation catalyst film. The heater film 8 is made of platinum.
【００２５】動作について説明する。図１において、ヒ
ータ膜８が直流電圧（記載せず）の印加により発熱し４
５０℃に加熱されると、ジルコニア焼結板１および酸化
触媒膜３はフォルステライト基板７および硝子膜６を介
して４５０℃に加熱される。次に、炭化水素（例えば一
酸化炭素）と酸素を含むガスがセンサに接触すると、酸
化触媒膜３が配置された白金電極膜２ｂ側では、炭化水
素と酸素が酸化触媒膜３によって反応して炭化水素が消
滅するとともに酸素濃度が減少する。一方、他方の白金
電極膜２ａ側は、酸素がそのまま存在する。従って、白
金電極膜２ｂ側と白金電極膜２ａ側とで酸素濃度の差が
生じて酸素が移動し、炭化水素濃度に対応したセンサ出
力が生じる。The operation will be described. In FIG. 1, the heater film 8 generates heat by applying a DC voltage (not shown).
When heated to 50 ° C., the zirconia sintered plate 1 and the oxidation catalyst film 3 are heated to 450 ° C. via the forsterite substrate 7 and the glass film 6. Next, when a gas containing hydrocarbons (for example, carbon monoxide) and oxygen comes into contact with the sensor, hydrocarbons and oxygen react on the platinum electrode film 2b on which the oxidation catalyst film 3 is disposed by the oxidation catalyst film 3. As the hydrocarbons disappear, the oxygen concentration decreases. On the other hand, oxygen exists as it is on the other platinum electrode film 2a side. Therefore, a difference in oxygen concentration occurs between the platinum electrode film 2b side and the platinum electrode film 2a side, oxygen moves, and a sensor output corresponding to the hydrocarbon concentration is generated.
【００２６】本発明の効果を、酸化触媒として白金を用
いた炭化水素検出センサで確認した。The effect of the present invention was confirmed with a hydrocarbon detection sensor using platinum as an oxidation catalyst.
【００２７】ジルコニア焼結板として、安定化ジルコニ
ア（ＺｒＯ2の９２モル％とＹ2Ｏ3の８モル％の固溶
体）の粉末に有機溶剤を混合してシート状に成型した乾
燥品を１４００℃で４時間焼成し１０mm角に切断した板
を準備した。As a zirconia sintered plate, a dried product obtained by mixing an organic solvent with powder of stabilized zirconia (a solid solution of 92 mol% of ZrO 2 and 8 mol% of Y 2 O 3 ) and forming a sheet was used at 1400 ° C. For 4 hours and cut into a 10 mm square plate.
【００２８】白金電極膜用ペーストとして、白金の粉末
９７wt％と酸化ビスマス粉末３wt％と高粘性有機溶剤１
９wt％の混合物を準備した。そしてジルコニア焼結板の
片面にこの白金電極膜用ペーストを厚膜印刷し、乾燥さ
せた。As a paste for a platinum electrode film, 97 wt% of platinum powder, 3 wt% of bismuth oxide powder, and a high-viscosity organic solvent 1
A 9 wt% mixture was prepared. Then, this platinum electrode film paste was thickly printed on one side of the zirconia sintered plate and dried.
【００２９】酸化触媒膜用ペーストとして、酸化触媒粉
末である白金１００wt％と高粘性有機溶剤１９wt％の混
合物を準備した。そして前述の乾燥済みの白金電極膜の
片側に積層して、この酸化触媒膜用ペーストを厚膜印刷
し乾燥させた。As a paste for an oxidation catalyst film, a mixture of 100% by weight of platinum as an oxidation catalyst powder and 19% by weight of a highly viscous organic solvent was prepared. Then, the above-mentioned dried platinum electrode film was laminated on one side, and this oxidation catalyst film paste was thickly printed and dried.
【００３０】また、フォルステライト製基板を準備し白
金製ヒータ膜を片側に形成した。さらに硝子膜用ペース
トとして、酸化アルミナが３〜７％、酸化ホウソが３〜
７％、酸化カルシウムが１〜２％、酸化ストロンチウム
が４〜６％、酸化バリウムが０．２〜１．５％、酸化ナ
トリウムが１０〜１３％、酸化カリウムが４〜８％、酸
化チタンが６〜９％、残部が酸化珪素である硝子粉末６
０wt％と高粘性の有機溶剤４０wt％の混合物を準備し
た。そして、この硝子膜用ペーストをフォルステライト
製基板の他面側に厚膜印刷し、乾燥させた。その後、乾
燥硝子膜を介してフォルステライト製基板とジルコニア
焼結板とを積層した。A forsterite substrate was prepared, and a platinum heater film was formed on one side. Furthermore, as a paste for a glass film, alumina oxide is 3 to 7%, and boron oxide is 3 to 7%.
7%, calcium oxide 1-2%, strontium oxide 4-6%, barium oxide 0.2-1.5%, sodium oxide 10-13%, potassium oxide 4-8%, titanium oxide 6-9% glass powder 6 with the balance being silicon oxide
A mixture of 0 wt% and 40 wt% of a highly viscous organic solvent was prepared. Then, this glass film paste was thick-film-printed on the other surface side of the forsterite substrate and dried. Thereafter, the forsterite substrate and the zirconia sintered plate were laminated via the dried glass film.
【００３１】最後にこれら白金電極膜と酸化触媒膜から
なる積層膜を、９２０℃で１０分同時焼成した。白金電
極膜は、この焼成により有機溶剤が除去されて白金９７
wt％と酸化ビスマス３wt％の混合膜となるとともに、酸
化ビスマスの溶融により白金粉末がジルコニア焼結板に
密着固定され、溶融時の酸化ビスマスの体積膨張により
多孔質な膜となる。一方、酸化触媒膜は、この焼成によ
り有機溶剤が除去されて酸化銅の酸化触媒１００wt％と
なるのだが、白金電極膜に混合されている酸化ビスマス
が微量混入し、白金電極膜に強固に固定される。また硝
子膜は、この焼成により有機溶剤が除去されて硝子とな
り、フォルステライト製基板とジルコニア焼結板とを接
合固定した。最後にリード線を付け完成である。Finally, the laminated film comprising the platinum electrode film and the oxidation catalyst film was simultaneously fired at 920 ° C. for 10 minutes. The organic solvent is removed from the platinum electrode film by this baking to remove the platinum 97
In addition to forming a mixed film of wt% and bismuth oxide 3 wt%, the platinum powder is adhered and fixed to the zirconia sintered plate by melting the bismuth oxide, and becomes a porous film due to the volume expansion of the bismuth oxide at the time of melting. On the other hand, in the oxidation catalyst film, the organic solvent is removed by this baking and the oxidation catalyst of copper oxide becomes 100% by weight. However, a trace amount of bismuth oxide mixed in the platinum electrode film is mixed and firmly fixed to the platinum electrode film. Is done. In addition, the organic solvent was removed from the glass film by this firing to form glass, and the forsterite substrate and the zirconia sintered plate were bonded and fixed. Finally, lead wires are attached and the process is completed.
【００３２】４５０℃において一酸化炭素濃度とセンサ
出力の関係を測定した結果を図２に示す。酸化触媒とし
て白金を用いた本発明品は、一酸化炭素濃度に対応した
センサ出力が生じていることがわかる。FIG. 2 shows the result of measuring the relationship between the concentration of carbon monoxide and the sensor output at 450 ° C. It can be seen that the product of the present invention using platinum as an oxidation catalyst generates a sensor output corresponding to the concentration of carbon monoxide.
【００３３】本発明の効果を、白金電極膜に混合される
酸化ビスマスの量を変化させた炭化水素検出センサで確
認した。なお酸化触媒は白金を用いている。The effect of the present invention was confirmed with a hydrocarbon detection sensor in which the amount of bismuth oxide mixed with the platinum electrode film was changed. Note that platinum is used as the oxidation catalyst.
【００３４】実験は、白金電極膜用ペーストとして、白
金粉末と酸化ビスマス粉末からなる固定分１００wt％に
高粘性有機溶剤１９wt％を混合するに際し酸化ビスマス
の量を変化させた混合物を使用した以外は、前述と同じ
構成、材料、製造方法である。The experiment was conducted in the same manner as the paste for the platinum electrode film except that a mixture obtained by changing the amount of bismuth oxide at the time of mixing 19 wt% of a highly viscous organic solvent with a fixed amount of 100 wt% of platinum powder and bismuth oxide powder was used. , The same configuration, material, and manufacturing method as described above.
【００３５】一酸化炭素濃度１０００ppmの４５０℃に
おいて、酸化ビスマス量とセンサ出力の関係を測定した
結果を図３に示す。FIG. 3 shows the result of measuring the relationship between the amount of bismuth oxide and the sensor output at 450 ° C. at a carbon monoxide concentration of 1000 ppm.
【００３６】白金電極膜に混合される酸化ビスマスが
１．５〜５wt％のセンサは、大きな値のセンサ出力が得
られた。一方、１．５wt％未満にすると、結合材である
酸化ビスマスが不足しているため、白金粉末とジルコニ
ア焼結板との密着不良が発生してセンサ出力が極端に低
下した。また、５wt％を越えると熱膨張係数の大きい酸
化ビスマスの影響でセンサ割れが起こり不良品が多発し
た。以上のことより、酸化ビスマスは結合材としての役
割をはたすための混合量とそれにともなう熱膨張係数の
増大を考慮すると、１．５〜５wt％が密着性が良好なセ
ンサが得られる点で適切であり、特に２〜５wt％は密着
性が優れる点で最適である。The sensor containing 1.5 to 5% by weight of bismuth oxide mixed with the platinum electrode film provided a large sensor output. On the other hand, when the content is less than 1.5% by weight, bismuth oxide as a binder is insufficient, and poor adhesion between the platinum powder and the zirconia sintered plate occurs, resulting in an extremely low sensor output. On the other hand, when the content exceeds 5 wt%, sensor cracks occur due to the influence of bismuth oxide having a large thermal expansion coefficient, and defective products frequently occur. From the above, considering the amount of bismuth oxide to serve as a binder and the accompanying increase in the coefficient of thermal expansion, 1.5 to 5 wt% is appropriate in that a sensor with good adhesion can be obtained. In particular, 2 to 5% by weight is optimal in that the adhesiveness is excellent.
【００３７】本発明の効果を、白金電極膜と酸化触媒膜
からなる積層膜の焼成温度を変化させた炭化水素検出セ
ンサで確認した。なお酸化触媒は白金を用いている。The effect of the present invention was confirmed by a hydrocarbon detection sensor in which the firing temperature of a laminated film comprising a platinum electrode film and an oxidation catalyst film was changed. Note that platinum is used as the oxidation catalyst.
【００３８】実験は、白金電極膜と酸化触媒膜の積層膜
を同時焼成する温度を変化させた以外は、前述と同じ構
成、材料、製造方法である。In the experiment, the same configuration, material, and manufacturing method as described above were used, except that the temperature for simultaneously firing the stacked film of the platinum electrode film and the oxidation catalyst film was changed.
【００３９】一酸化炭素濃度１０００ppmの４５０℃に
おいて、焼成温度とセンサ出力の関係を測定した結果を
図４に示す。FIG. 4 shows the result of measuring the relationship between the firing temperature and the sensor output at 450 ° C. at a carbon monoxide concentration of 1000 ppm.
【００４０】焼成温度が７００〜１０００℃のセンサ
は、密着性が良好であるため大きな値のセンサ出力が得
られた。一方、７００℃未満では白金電極膜の焼成不充
分のため白金粉末とジルコニア焼結板との接触状態が悪
くなって密着不良が発生しセンサ出力が極端に低下し
た。また１０００℃を越えると白金電極膜に混合される
酸化ビスマスが変質を起こしてその酸素イオン導電性低
下と密着不良が発生しセンサ出力が極端に低下した。The sensor having a firing temperature of 700 to 1000 ° C. had a large sensor output because of good adhesion. On the other hand, when the temperature is lower than 700 ° C., the sintering of the platinum electrode film is insufficient, so that the contact state between the platinum powder and the zirconia sintered plate is deteriorated. When the temperature exceeds 1000 ° C., the bismuth oxide mixed with the platinum electrode film is deteriorated, and the oxygen ion conductivity is lowered and the adhesion is poor, so that the sensor output is extremely lowered.
【００４１】以上のことより、積層膜の焼成温度は、結
合材として使用する酸化ビスマスの焼成温度の変化にと
もなう結合力の変化を考慮すると、７００〜１０００℃
が密着性が良好なセンサが得られる点で適切であり、特
に７５０〜９５０℃が密着性が優れる点で最適である。From the above, the firing temperature of the laminated film is set at 700 to 1000 ° C. in consideration of the change in the bonding force due to the change in the firing temperature of bismuth oxide used as the binder.
Is suitable in that a sensor having good adhesion can be obtained, and 750 to 950 ° C. is particularly suitable in terms of excellent adhesion.
【００４２】またこのことより、ジルコニア焼結板とフ
ォルステライト基板とを接合固定する硝子は、白金電極
膜焼成と同温度である７００〜１０００℃で焼成する
と、白金電極膜や酸化触媒膜への影響が少ないことがわ
かる。Further, from this, the glass for bonding and fixing the zirconia sintered plate and the forsterite substrate is fired at 700 to 1000 ° C., which is the same temperature as the firing of the platinum electrode film, so that the platinum electrode film and the oxidation catalyst film can be formed. It can be seen that the influence is small.
【００４３】本発明の効果を、白金電極膜に酸化カドミ
ニウムをさらに混合しその混合割合を変化させた炭化水
素検出センサで確認した。なお酸化触媒は白金を用いて
いる。The effect of the present invention was confirmed by a hydrocarbon detection sensor in which cadmium oxide was further mixed into a platinum electrode film and the mixing ratio was changed. Note that platinum is used as the oxidation catalyst.
【００４４】実験は、白金電極膜用ペーストとして、白
金粉末と酸化ビスマス粉末と酸化カドミニウム粉末から
なる固定分１００wt％に高粘性有機溶剤１９wt％を混合
するに際し、酸化ビスマスと酸化カドミニウムの混合比
の量を変化させた混合物を使用した以外は、前述と同じ
構成、材料、製造方法である。酸化カドミニウムは、融
点７００℃、熱膨張係数１２×１０ー6（ｄｅｇー1）で、
酸化ビスマスより低融点、低熱膨張係数である。In the experiment, as a paste for a platinum electrode film, a mixing ratio of bismuth oxide and cadmium oxide was determined by mixing a fixed amount of 100% by weight of platinum powder, bismuth oxide powder and cadmium oxide powder with 19% by weight of a highly viscous organic solvent. The same configuration, materials, and production method as described above, except that a mixture of varying amounts was used. Oxidation cadmium, the melting point 700 ° C., a thermal expansion coefficient of 12 × 10 over 6 (deg-1),
It has a lower melting point and lower thermal expansion coefficient than bismuth oxide.
【００４５】一酸化炭素濃度１０００ppmの４５０℃に
おいて、酸化ビスマスと酸化カドミニウムの混合比とセ
ンサ出力の関係を、酸化ビスマスの混合量を変化させて
測定した結果を図５に示す。FIG. 5 shows the relationship between the mixing ratio of bismuth oxide and cadmium oxide and the sensor output at 450 ° C. with a carbon monoxide concentration of 1000 ppm, with the mixing amount of bismuth oxide varied.
【００４６】酸化ビスマス量（Ｂ）と酸化カドミニウム
量（Ｃ）の混合比（Ｃ／Ｂ）が０．１〜１のセンサは、
酸化ビスマス単独の場合と比較して大きな値のセンサ出
力が得られた。これは、低融点、低熱膨張係数の酸化カ
ドミニウムをさらに混合することで両者の相乗効果が発
揮され、白金電極膜とジルコニア焼結板との接触状態が
良くなって密着性が一層向上し、白金粉末からジルコニ
ア焼結板への酸素伝達特性が向上するためである。一
方、混合比（Ｃ／Ｂ）が１．０倍を越えると、酸化ビス
マスのもつ優れた酸素イオン導電性特性が酸素イオン導
電性のない酸化カドミニウムにより低下して、白金粉末
からジルコニア焼結板への酸素伝達が悪くなり必要な電
極特性が得られない。また、混合比（Ｃ／Ｂ）が０．１
未満は両者の相乗効果が生じないため、センサ出力は増
大しないし密着性も向上しない。A sensor in which the mixing ratio (C / B) of the amount of bismuth oxide (B) and the amount of cadmium oxide (C) is 0.1 to 1 is as follows:
A large sensor output was obtained as compared with the case of using bismuth oxide alone. This is because, by further mixing cadmium oxide having a low melting point and a low coefficient of thermal expansion, a synergistic effect of the two is exhibited, the contact state between the platinum electrode film and the zirconia sintered plate is improved, and the adhesion is further improved. This is because the oxygen transfer characteristics from the powder to the zirconia sintered plate are improved. On the other hand, when the mixing ratio (C / B) exceeds 1.0, the excellent oxygen ion conductivity of bismuth oxide is reduced by cadmium oxide having no oxygen ion conductivity, and the zirconia sintered plate is reduced from platinum powder. Oxygen transmission to the electrode becomes poor, and required electrode characteristics cannot be obtained. Further, the mixing ratio (C / B) is 0.1
Since the synergistic effect of the two does not occur, the sensor output does not increase and the adhesion does not improve.
【００４７】以上のことより、酸化ビスマス量（Ｂ）と
酸化カドミニウム量（Ｃ）の混合比（Ｃ／Ｂ）は０．１
〜１が、両者の相乗効果で密着性が向上する、酸素伝達
特性が向上する点で適切である。From the above, the mixing ratio (C / B) of the amount of bismuth oxide (B) and the amount of cadmium oxide (C) is 0.1
Nos. 1 to 1 are appropriate in that adhesion is improved by a synergistic effect of the two, and oxygen transfer characteristics are improved.
【００４８】本発明の効果を、酸化触媒として各種金属
酸化物を用いた炭化水素検出センサで確認した。検討し
た金属酸化物は、酸化鉄、酸化ニッケル、酸化コバル
ト、酸化マンガン、酸化ガリウム、酸化クロム、酸化チ
タンである。実験は、酸化触媒膜用ペーストとして、金
属酸化物粉末１００wt％と高粘性の有機溶剤１９wt％の
混合物を使用した以外は、前述と同じ構成・材料・製造
方法である。白金電極膜と酸化触媒膜からなる積層膜
は、これら金属酸化物がいずれも融点１０００℃以上で
あることを考慮して、９２０℃で１０分同時焼成してい
る。The effect of the present invention was confirmed by a hydrocarbon detection sensor using various metal oxides as an oxidation catalyst. The metal oxides examined were iron oxide, nickel oxide, cobalt oxide, manganese oxide, gallium oxide, chromium oxide, and titanium oxide. The experiment was conducted in the same manner as described above except that a mixture of 100 wt% of metal oxide powder and 19 wt% of a highly viscous organic solvent was used as the paste for the oxidation catalyst film. The laminated film composed of the platinum electrode film and the oxidation catalyst film is simultaneously fired at 920 ° C. for 10 minutes in consideration of the fact that these metal oxides all have a melting point of 1000 ° C. or more.
【００４９】一酸化炭素濃度１０００ppmの４５０℃に
おいて、得られるセンサ出力を表１に示す。Table 1 shows the sensor outputs obtained at 450 ° C. with a carbon monoxide concentration of 1000 ppm.
【００５０】[0050]
【表１】 [Table 1]
【００５１】また発明の効果を、白金を酸化触媒として
用い白金粒子群を耐熱繊維束に内wt％に充填した構成の
マット状酸化触媒膜で確認した。このマット状酸化触媒
膜の本発明品は、一酸化炭素濃度１０００ppmの４５０
℃において、３０mｖの高センサ出力を得ることができ
た。Further, the effect of the present invention was confirmed with a mat-like oxidation catalyst film having a structure in which platinum particles were filled in a heat-resistant fiber bundle in an amount of wt% using platinum as an oxidation catalyst. The mat-shaped oxidation catalyst film of the present invention has a carbon monoxide concentration of 1000 ppm of 450 ppm.
At 30 ° C., a high sensor output of 30 mv could be obtained.
【００５２】[0052]
【発明の効果】以上の説明から明らかなように本発明の
炭化水素検出センサによれば、次の効果が得られる。As is apparent from the above description, the following effects can be obtained according to the hydrocarbon detection sensor of the present invention.
【００５３】（１）酸化触媒は膜化して白金電極膜に積
層化し同時焼成するため、簡単な製法で酸化触媒が固定
でき、取り扱いが簡素化されて生産性が向上する。また
白金電極膜は、安定化ジルコニアとの熱膨張係数の一致
や酸素イオン導電性を考慮した結合材組成、製造方法で
あるため、ジルコニア割れなどの不良品を製造すること
なく高い部留まりで、高活性なセンサが得られる。さら
に酸化触媒は、融点１１００℃以上の高活性な酸化触媒
であるため、検出感度の高いセンサが得られる。(1) Since the oxidation catalyst is formed into a film, laminated on a platinum electrode film, and fired at the same time, the oxidation catalyst can be fixed by a simple production method, handling is simplified, and productivity is improved. In addition, the platinum electrode film is a binder composition and production method that takes into account the thermal expansion coefficient of the stabilized zirconia and the oxygen ion conductivity, so that high yields can be obtained without producing defective products such as zirconia cracks. A highly active sensor is obtained. Further, since the oxidation catalyst is a highly active oxidation catalyst having a melting point of 1100 ° C. or higher, a sensor having high detection sensitivity can be obtained.
【００５４】（２）白金電極膜に酸化カドミニウムをさ
らに小量混合することで酸化ビスマスの融解性が向上
し、白金電極膜と安定化ジルコニア焼結板との密着性が
良くなる。そのため、白金電極膜から安定化ジルコニア
焼結板への酸素伝達特性が向上し、検出感度の高いセン
サが得られる。(2) By further mixing cadmium oxide in the platinum electrode film in a smaller amount, the melting property of bismuth oxide is improved, and the adhesion between the platinum electrode film and the stabilized zirconia sintered plate is improved. Therefore, the oxygen transfer characteristic from the platinum electrode film to the stabilized zirconia sintered plate is improved, and a sensor with high detection sensitivity can be obtained.
【００５５】（３）炭化水素の酸化能力が高く熱膨張係
数が概略同じの白金または酸化銅を、酸化触媒として使
用したため、酸化触媒が白金電極膜に良好に固定化さ
れ、検出感度の高いセンサを得ることができる。(3) Since platinum or copper oxide having a high oxidizing ability for hydrocarbons and having substantially the same coefficient of thermal expansion was used as an oxidation catalyst, the oxidation catalyst was well fixed to the platinum electrode film, and a sensor with high detection sensitivity was used. Can be obtained.
【００５６】（４）安定化ジルコニアおよびフォルステ
ライトと熱膨張係数が概略同じの硝子膜を使用したた
め、白金電極膜付き安定化ジルコニア焼結板とヒータ膜
付きフォルステライト基板とが簡単に固定できる。また
酸化触媒は膜であるため簡単に白金電極膜に固定でき
る。従って、ヒータ膜が効果的に安定化ジルコニア焼結
板や酸化触媒膜に伝達され、センサの小型化および加熱
電力の低減ができる。(4) Since a glass film having substantially the same thermal expansion coefficient as that of stabilized zirconia and forsterite is used, the stabilized zirconia sintered plate with a platinum electrode film and the forsterite substrate with a heater film can be easily fixed. Further, since the oxidation catalyst is a film, it can be easily fixed to the platinum electrode film. Therefore, the heater film is effectively transmitted to the stabilized zirconia sintered plate or the oxidation catalyst film, and the size of the sensor can be reduced and the heating power can be reduced.
【００５７】（５）熱膨張係数が９〜１１×１０ー6（ｄ
ｅｇー1） であり７００〜１０００℃の焼成で接合固定
できる硝子膜を使用したため、白金電極膜や酸化触媒膜
への影響が少なく検出感度の高いセンサが得ることがで
きる。[0057] (5) Thermal expansion coefficient of 9 to 11 × 10 over 6 (d
Since a glass film which is eg -1 ) and can be bonded and fixed by firing at 700 to 1000 ° C. is used, it is possible to obtain a sensor which has little influence on the platinum electrode film and the oxidation catalyst film and has high detection sensitivity.
【００５８】（６）マット状の酸化触媒膜にしたため、
白金電極膜に簡単に固定でき、取り扱いが簡素化されて
生産性を向上することができる。また、酸化触媒膜の活
性が高まり、センサ出力の高い高感度センサを得ること
ができる。(6) Since the oxidation catalyst film has a mat shape,
It can be easily fixed to the platinum electrode membrane, handling is simplified, and productivity can be improved. Further, the activity of the oxidation catalyst film is increased, and a high-sensitivity sensor having a high sensor output can be obtained.
【図１】本発明の実施例の炭化水素検出センサの断面図FIG. 1 is a cross-sectional view of a hydrocarbon detection sensor according to an embodiment of the present invention.
【図２】同炭化水素検出センサの効果特性図FIG. 2 is an effect characteristic diagram of the hydrocarbon detection sensor.
【図３】同炭化水素検出センサの効果特性図FIG. 3 is an effect characteristic diagram of the hydrocarbon detection sensor.
【図４】同炭化水素検出センサの効果特性図FIG. 4 is an effect characteristic diagram of the hydrocarbon detection sensor.
【図５】同炭化水素検出センサの効果特性図FIG. 5 is an effect characteristic diagram of the hydrocarbon detection sensor.
【図６】従来の炭化水素検出センサの断面図FIG. 6 is a cross-sectional view of a conventional hydrocarbon detection sensor.
【図７】従来の炭化水素検出センサの断面図FIG. 7 is a cross-sectional view of a conventional hydrocarbon detection sensor.
１ 安定化ジルコニア焼結板 ２ 白金 ２ａ、２ｂ 白金電極膜 ３ 酸化ビスマス ４ 酸化触媒膜 ５ 酸化触媒 ６ 硝子膜 ７ フォルステライト基板 ８ 白金ヒータ膜 DESCRIPTION OF SYMBOLS 1 Stabilized zirconia sintered board 2 Platinum 2a, 2b Platinum electrode film 3 Bismuth oxide 4 Oxidation catalyst film 5 Oxidation catalyst 6 Glass film 7 Forsterite substrate 8 Platinum heater film
Claims (6)
２モル％からなる安定化ジルコニア焼結板の表面に、白
金に酸化ビスマスを１．５〜５wt％混合した白金電極膜
を２個厚膜印刷した後に、酸化触媒粉末を含有した酸化
触媒膜を前記白金電極膜の片側上部に厚膜印刷して積層
し、前記白金電極膜と前記酸化触媒膜を７００〜１００
０℃で同時に焼成し、前記酸化触媒が白金、酸化銅、酸
化鉄、酸化ニッケル、酸化コバルト、酸化マンガン、酸
化ガリウム、酸化クロム、酸化チタンの群から選択した
１種である炭化水素検出センサの製造方法。(1) 8 mol% of yttrium oxide and 9 of zirconia
On a surface of a stabilized zirconia sintered plate composed of 2 mol%, two platinum electrode films in which bismuth oxide is mixed with 1.5 to 5 wt% of platinum are printed in a thick film, and then an oxidation catalyst film containing an oxidation catalyst powder is formed. A thick film is printed and laminated on one upper side of the platinum electrode film, and the platinum electrode film and the oxidation catalyst film are 700 to 100
Simultaneous firing at 0 ° C., wherein the oxidation catalyst is a hydrocarbon detection sensor selected from the group consisting of platinum, copper oxide, iron oxide, nickel oxide, cobalt oxide, manganese oxide, gallium oxide, chromium oxide, and titanium oxide. Production method.
ム量をＣとし、その混合比をＣ／Ｂとすると、０．１≦
Ｃ／Ｂ≦１なる条件で混合した白金電極膜を有する請求
項１記載の炭化水素検出センサの製造方法。2. The amount of bismuth oxide is B, the amount of cadmium oxide is C, and the mixing ratio is C / B.
The method for producing a hydrocarbon detection sensor according to claim 1, further comprising a platinum electrode film mixed under a condition of C / B ≦ 1.
項１記載の炭化水素検出センサの製造方法。3. The method according to claim 1, wherein the oxidation catalyst is platinum or copper oxide.
ルコニア焼結板の片側表面に形成した２個の白金電極膜
と、前記白金電極膜の片側上部に積層固定されており酸
化触媒を主成分とした酸化触媒膜と、前記安定化ジルコ
ニア焼結板の他面側に形成されており熱膨張係数が９〜
１１×１０ー6（ｄｅｇー1）の硝子膜と、前記硝子膜に積
層固定したフォルステライト基板と、前記フォルステラ
イト基板の他面側に形成したヒータ膜を備えた請求項１
ないし３のいずれか１項記載の炭化水素検出センサの製
造方法。4. A stabilized zirconia sintered plate, two platinum electrode films formed on one surface of the stabilized zirconia sintered plate, and an oxidation catalyst laminated and fixed on one upper portion of the platinum electrode film. An oxidation catalyst film as a main component and a stabilized zirconia sintered plate formed on the other surface side and having a thermal expansion coefficient of 9 to
2. A method according to claim 1 , further comprising a glass film of 11.times.10.sup. -6 (deg.sup. -1 ), a forsterite substrate laminated and fixed to said glass film, and a heater film formed on the other surface of said forsterite substrate.
4. The method for producing a hydrocarbon detection sensor according to any one of claims 1 to 3.
ホウソが３〜７％、酸化カルシウムが１〜２％、酸化ス
トロンチウムが４〜６％、酸化バリウムが０．２〜１．
５％、酸化ナトリウムが１０〜１３％、酸化カリウムが
４〜８％、酸化チタンが６〜９％、残部が酸化珪素であ
る請求項４記載の炭化水素検出センサの製造方法。5. A glass film comprising 3 to 7% of alumina oxide, 3 to 7% of boron oxide, 1 to 2% of calcium oxide, 4 to 6% of strontium oxide, and 0.2 to 1% of barium oxide.
The method for producing a hydrocarbon detection sensor according to claim 4, wherein 5%, 10% to 13% of sodium oxide, 4% to 8% of potassium oxide, 6% to 9% of titanium oxide, and the remainder are silicon oxide.
維束の内部に充填した構成のマットである請求項４記載
の炭化水素検出センサの製造方法。6. The method for manufacturing a hydrocarbon detection sensor according to claim 4, wherein the oxidation catalyst film is a mat having a configuration in which particles of the oxidation catalyst are filled in a heat-resistant fiber bundle.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8315936A JP3036443B2 (en) | 1996-11-27 | 1996-11-27 | Manufacturing method of hydrocarbon detection sensor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8315936A JP3036443B2 (en) | 1996-11-27 | 1996-11-27 | Manufacturing method of hydrocarbon detection sensor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10160700A true JPH10160700A (en) | 1998-06-19 |
| JP3036443B2 JP3036443B2 (en) | 2000-04-24 |
Family
ID=18071392
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8315936A Expired - Fee Related JP3036443B2 (en) | 1996-11-27 | 1996-11-27 | Manufacturing method of hydrocarbon detection sensor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3036443B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10282054A (en) * | 1997-04-03 | 1998-10-23 | Nippon Soken Inc | Hydrocarbon sensor |
| WO2002047806A1 (en) * | 2000-12-14 | 2002-06-20 | The University Of Hong Kong | Methods and apparatus for the oxidation of glucose molecules |
-
1996
- 1996-11-27 JP JP8315936A patent/JP3036443B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10282054A (en) * | 1997-04-03 | 1998-10-23 | Nippon Soken Inc | Hydrocarbon sensor |
| WO2002047806A1 (en) * | 2000-12-14 | 2002-06-20 | The University Of Hong Kong | Methods and apparatus for the oxidation of glucose molecules |
| US7419580B2 (en) | 2000-12-14 | 2008-09-02 | The University Of Hong Kong | Methods and apparatus for the oxidation of glucose molecules |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3036443B2 (en) | 2000-04-24 |
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