JPH056659B2 - - Google Patents
Info
- Publication number
- JPH056659B2 JPH056659B2 JP58236183A JP23618383A JPH056659B2 JP H056659 B2 JPH056659 B2 JP H056659B2 JP 58236183 A JP58236183 A JP 58236183A JP 23618383 A JP23618383 A JP 23618383A JP H056659 B2 JPH056659 B2 JP H056659B2
- Authority
- JP
- Japan
- Prior art keywords
- sensor
- heater
- oxygen sensor
- solid electrolyte
- electrodes
- 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.)
- Expired - Lifetime
Links
- 229910052760 oxygen Inorganic materials 0.000 claims description 69
- 239000001301 oxygen Substances 0.000 claims description 69
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 66
- 238000009792 diffusion process Methods 0.000 claims description 29
- 239000000758 substrate Substances 0.000 claims description 21
- 239000007784 solid electrolyte Substances 0.000 claims description 20
- 239000000919 ceramic Substances 0.000 claims description 19
- 239000002131 composite material Substances 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 9
- 239000000446 fuel Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 4
- 238000001514 detection method Methods 0.000 claims description 3
- 239000011810 insulating material Substances 0.000 claims 1
- 239000012212 insulator Substances 0.000 claims 1
- 239000010410 layer Substances 0.000 description 10
- 238000005086 pumping Methods 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- -1 oxygen ions Chemical class 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- WUOACPNHFRMFPN-SECBINFHSA-N (S)-(-)-alpha-terpineol Chemical compound CC1=CC[C@@H](C(C)(C)O)CC1 WUOACPNHFRMFPN-SECBINFHSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- OVKDFILSBMEKLT-UHFFFAOYSA-N alpha-Terpineol Natural products CC(=C)C1(O)CCC(C)=CC1 OVKDFILSBMEKLT-UHFFFAOYSA-N 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- 229940088601 alpha-terpineol Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/417—Systems using cells, i.e. more than one cell and probes with solid electrolytes
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Measuring Oxygen Concentration In Cells (AREA)
Description
【発明の詳細な説明】
〔発明の利用分野〕
本発明は、自動車のエンジンや、暖房機器のよ
うに燃料を燃焼させる機器の排気ガス中の酸素を
検出する酸素センサに係り、特にストイツクセン
サと希薄酸素センサとを一体に形成した複合酸素
センサとその製造方法に関する。[Detailed Description of the Invention] [Field of Application of the Invention] The present invention relates to an oxygen sensor that detects oxygen in the exhaust gas of an automobile engine or a device that burns fuel such as a heating device, and particularly relates to a stoic sensor. The present invention relates to a composite oxygen sensor in which a dilute oxygen sensor and a dilute oxygen sensor are integrally formed, and a method for manufacturing the same.
燃料の燃焼を利用する暖房器や自動車のエンジ
ン等の燃焼状態を検出する手段として、排気ガス
中の含まれる酸素の濃度を検出する酸素センサが
知られている。
2. Description of the Related Art Oxygen sensors that detect the concentration of oxygen contained in exhaust gas are known as means for detecting the combustion state of heaters, automobile engines, and the like that utilize combustion of fuel.
酸素センサで排気ガス中の酸素の濃度を検出す
る場合、排気ガスもしくは酸素センサを500℃以
上の高温にすることが必要である。また、酸素セ
ンサもしくは排気ガスの温度によつて、酸素セン
サの感度が異なる。さらに、燃焼制御（空燃比の
制御）を行なう場合、排気ガス温度の低い始動時
からの制御が必要である。 When detecting the concentration of oxygen in exhaust gas with an oxygen sensor, it is necessary to heat the exhaust gas or the oxygen sensor to a high temperature of 500°C or higher. Furthermore, the sensitivity of the oxygen sensor differs depending on the temperature of the oxygen sensor or the exhaust gas. Furthermore, when performing combustion control (air-fuel ratio control), it is necessary to perform the control from the time of startup when the exhaust gas temperature is low.
このような要件を満すものとして、たとえば特
開昭55−125448号のFig6に開示されたようにス
トイツクセンサとヒータおよび希薄酸素センサを
一体に形成した複合酸素センサが提案されてい
る。 To meet these requirements, a composite oxygen sensor has been proposed in which a stoic sensor, a heater, and a dilute oxygen sensor are integrated, as disclosed in FIG. 6 of JP-A-55-125448.
すなわち、前記複合酸素センサは、Fig6に示
されているように、下から多孔性おおい層、測定
電極、電気絶縁層、固体電解質板、標準電極、多
孔性電気絶縁層、加熱素子、Ｕ字状絶縁部材、測
定電極、電気絶縁層、固体電解質板、標準電極、
多孔性おおい層の順に積層して成る。 That is, as shown in Fig. 6, the composite oxygen sensor includes, from the bottom, a porous covering layer, a measuring electrode, an electrically insulating layer, a solid electrolyte plate, a standard electrode, a porous electrically insulating layer, a heating element, and a U-shaped Insulating members, measurement electrodes, electrical insulation layers, solid electrolyte plates, standard electrodes,
It consists of porous covering layers laminated in this order.
このような複合酸素センサは、加熱素子の両側
に配置され、固体電解質を挾み込んでいる電極間
に定電流を通過させ、この状態における電極間に
生じる出力電圧を検出して、理論空燃比以上の高
い酸素濃度に制御するストイツクセンサと、固体
電解質を挾み込んでいる電極間に励起電圧として
一定電圧ELを印加し、この状態における電極間
に流れるポンピング電流部から酸素濃度を検出す
る希薄酸素センサとが加熱素子を基準としたとき
対称位置に配置されていないため、加熱素子で加
熱したとき、ストイツクセンサと希薄酸素センサ
の温度を均一にすることができない。このため、
希薄酸素センサの温度の変化による出力の変動を
正確に補正することができない。また、部品の種
類が多く、その加工、組立に多くの工数を要し、
作業性が悪いなどの欠点がある。 Such a composite oxygen sensor is arranged on both sides of a heating element, passes a constant current between electrodes sandwiching a solid electrolyte, detects the output voltage generated between the electrodes in this state, and calculates the stoichiometric air-fuel ratio. A constant voltage EL is applied as an excitation voltage between the stoic sensor that controls the oxygen concentration to the above high level and the electrodes sandwiching the solid electrolyte, and the oxygen concentration is detected from the pumping current flowing between the electrodes in this state. Since the dilute oxygen sensor and the dilute oxygen sensor are not arranged at symmetrical positions with respect to the heating element, the temperatures of the stoic sensor and the dilute oxygen sensor cannot be made uniform when heated by the heating element. For this reason,
It is not possible to accurately correct output fluctuations due to changes in the temperature of the dilute oxygen sensor. In addition, there are many types of parts, and it takes a lot of man-hours to process and assemble them.
It has drawbacks such as poor workability.
本発明の目的は、上記した従来技術の欠点をな
くし、高精度の検出が可能な複合酸素センサとそ
の製造方法を提供するにある。
SUMMARY OF THE INVENTION An object of the present invention is to eliminate the drawbacks of the prior art described above and to provide a composite oxygen sensor capable of highly accurate detection and a method for manufacturing the same.
上記目的を達成するため、本発明においてはス
トイツクセンサと希薄酸素センサを、ヒータをは
さんで相対向するように、かつヒータとの間隔が
等しくなるように配置すると共に、各センサのヒ
ータ側の電極を拡散室で覆うようにしたことを特
徴とする。
In order to achieve the above object, in the present invention, a stoic sensor and a dilute oxygen sensor are arranged so as to face each other with a heater in between, and with the same distance from the heater. The electrode is covered with a diffusion chamber.
また、本発明においては、セラミツクグリーン
シートおよびセラミツク基板に対する所要パター
ンの印刷する工程、グリーンシートおよびセラミ
ツク基板の積層し圧着する工程、および焼結工程
のくり返しにより希薄酸素センサとストイツクセ
ンサとを有する複合酸素センサを製造することを
特徴とする。 Furthermore, in the present invention, a dilute oxygen sensor and a stoic sensor are obtained by repeating the steps of printing a required pattern on a ceramic green sheet and a ceramic substrate, stacking and pressing the green sheet and ceramic substrate, and sintering. It is characterized by manufacturing a composite oxygen sensor.
以下、本発明の一実施例を図面にしたがつて説
明する。
An embodiment of the present invention will be described below with reference to the drawings.
第１図および第２図は、本発明による複合酸素
センサの一実施例を示すものである。同図におい
て、複合酸素センサ１は、電極２ａ，２ｂ，２
ｃ，２ｄを支持する固体電解質セラミツク基板
（以下単に基板という）３ａ，３ｄ、絶縁層４ａ，
４ｂを介してヒータ５を支持する固体電解質セラ
ミツク基板（以下単に基板という）３ｂ，３ｃ
と、基板３ｂ，３ｃの間を接合する接合層３ｅ、
および基板３ａ，３ｄの外側面を覆う被覆層６
ａ，６ｂから成る。そして、基板３ａと基板３ｂ
の間、および基板３ｃと基板３ｄの間には、電極
２ｂ，２ｃを囲む拡散室７ａ，７ｂが形成されて
いる。また、これら拡散室７ａ，７ｂは、拡散穴
８ａ，８ｂによつて外部と連通している。 1 and 2 show an embodiment of a composite oxygen sensor according to the present invention. In the figure, a composite oxygen sensor 1 includes electrodes 2a, 2b, 2
solid electrolyte ceramic substrates (hereinafter simply referred to as substrates) 3a, 3d supporting the electrodes c, 2d, insulating layers 4a,
solid electrolyte ceramic substrates (hereinafter simply referred to as substrates) 3b, 3c that support the heater 5 via 4b;
and a bonding layer 3e bonding between the substrates 3b and 3c,
and a coating layer 6 that covers the outer surfaces of the substrates 3a and 3d.
It consists of a and 6b. Then, the substrate 3a and the substrate 3b
Diffusion chambers 7a, 7b surrounding the electrodes 2b, 2c are formed between the substrates 3c and 3d. Further, these diffusion chambers 7a, 7b communicate with the outside through diffusion holes 8a, 8b.
このような構成において、たとえば、電極２
ａ，２ｂをストイツクセンサとし、電極２ｃ，２
ｄを希薄酸素センサとする。ここで、ストイツク
センサとは第２図において電極２ｂ−２ａ間に電
極２ｂを陽極として定電流Ip′を通電する定電流
励起法を採用し、ストイツクセンサの拡散室７ａ
内に拡散穴８ａより流入する一酸化炭素より多い
酸素を酸素イオンで固体電解質セラミツク基板３
ａを通過させることで供給し、空燃比によらず拡
散室７ａ内を高い酸素濃度に制御する。また、希
薄酸素センサとは第２図において、電極２ｄ−２
ｃ間に電極２ｄを陽極にして、励起電圧ELを印
加すると、拡散室７ｂ内の酸素分子は固体電解質
セラミツク基板３ｄを酸素イオンで通過して排気
ガス中に放出される。これに伴い、拡散室７ｂ内
には拡散孔８ｂより拡散律速に基づき酸素分子が
流入する。この酸素量に応じて希薄酸素センサの
電極２ｄ−２ｃ間にポンピング電流Ipが流れる。
このポンピング電流Ipと排気ガス中の酸素分圧
Po2の間には次式が成り立つことが一般に知られ
ている。 In such a configuration, for example, the electrode 2
a, 2b are stoic sensors, electrodes 2c, 2
Let d be a dilute oxygen sensor. Here, the stoic sensor employs a constant current excitation method in which a constant current Ip' is passed between electrodes 2b and 2a with electrode 2b as an anode in FIG.
The solid electrolyte ceramic substrate 3 uses oxygen ions to absorb more oxygen than carbon monoxide flowing into the solid electrolyte ceramic substrate 3 through the diffusion hole 8a.
The oxygen is supplied by passing through the oxygen a, and the inside of the diffusion chamber 7a is controlled to have a high oxygen concentration regardless of the air-fuel ratio. In addition, the dilute oxygen sensor is the electrode 2d-2 in FIG.
When the excitation voltage EL is applied with the electrode 2d used as an anode between the electrodes 2d and 3c, the oxygen molecules in the diffusion chamber 7b pass through the solid electrolyte ceramic substrate 3d as oxygen ions and are released into the exhaust gas. Accordingly, oxygen molecules flow into the diffusion chamber 7b from the diffusion hole 8b based on the diffusion rate. A pumping current Ip flows between the electrodes 2d and 2c of the dilute oxygen sensor depending on the amount of oxygen.
This pumping current Ip and the oxygen partial pressure in the exhaust gas
It is generally known that the following equation holds between Po 2 .
Ip＝（4F・Ｄ・Ｓ／Ｒ・Ｔ・１）・Po2 ここで、 Ｆ：フアラデー定数 Ｄ：酸素ガスの拡散定数 Ｓ：拡散孔の断面積 Ｒ：気体定数 Ｔ：絶対温度 １：拡散孔の長さ を表すものとする。Ip=(4F・D・S/R・T・1)・Po 2 Here, F: Faraday constant D: Diffusion constant of oxygen gas S: Cross-sectional area of diffusion hole R: Gas constant T: Absolute temperature 1: Diffusion shall represent the length of the hole.
上記定電流Ip′にて励起されたストイツクセン
サの空気過剰率λと出力電圧e0との関係、励起電
圧ELにて励起された希薄酸素センサの空気過剰
率λと出力電流Ipとの関係を第７図に示す。スト
イツクセンサの電極間に生じる出力電圧e0は排気
ガス中の酸素濃度が拡散室７ａ内の酸素濃度と比
較して大きい場合は（空気過剰率λ＜１の場合）、
電流Ip′により拡散室７ａ内の酸素濃度を理論空
燃比以上にしようとして、排気ガス中の酸素を酸
素イオンの形で拡散室７ａに送りこむため出力電
圧e0が大きく、λ≧1.0では出力電圧e0は小さく
なる。また、希薄酸素センサが発生するポンピン
グ電流Ipは排気ガス中の酸素分圧によつて定まる
値で、空気過剰率λ＜1.0の時は０に近い値を取
りつづけ、λが1.0以上のときは排気ガス中の酸
素分圧PO2の増加分に比例して大きくなる。 The relationship between the excess air ratio λ of the stoic sensor excited with the above constant current Ip′ and the output voltage e 0 , and the relationship between the excess air ratio λ of the lean oxygen sensor excited with the excitation voltage EL and the output current Ip is shown in Figure 7. The output voltage e 0 generated between the electrodes of the stoic sensor is, when the oxygen concentration in the exhaust gas is larger than the oxygen concentration in the diffusion chamber 7a (when the excess air ratio λ<1),
In order to make the oxygen concentration in the diffusion chamber 7a higher than the stoichiometric air-fuel ratio by the current Ip', oxygen in the exhaust gas is sent into the diffusion chamber 7a in the form of oxygen ions, so the output voltage e 0 is large, and when λ≧1.0, the output voltage e 0 becomes smaller. In addition, the pumping current Ip generated by the dilute oxygen sensor is a value determined by the oxygen partial pressure in the exhaust gas, and it continues to take a value close to 0 when the excess air ratio λ < 1.0, and when λ is 1.0 or more, the pumping current Ip is determined by the oxygen partial pressure in the exhaust gas. It increases in proportion to the increase in the oxygen partial pressure PO 2 in the exhaust gas.
このように、ヒータ５と各センサの間隔を等距
離とし、ヒータ５による各センサの加熱が均一に
行なわれるので、ストイツクセンサにより理論空
燃比を正確に検出し、この時の希薄酸素センサの
出力電流が０となるように補正するだけで、燃焼
効率が最も良いとされる空気過剰率λ＝1.0〜1.5
の範囲を正確に検出できる。 In this way, the distance between the heater 5 and each sensor is made equal, and each sensor is heated uniformly by the heater 5. Therefore, the stoichiometric sensor can accurately detect the stoichiometric air-fuel ratio, and the lean oxygen sensor at this time can Excess air ratio λ = 1.0 to 1.5, which is considered to have the best combustion efficiency, by simply correcting the output current to 0
The range of can be detected accurately.
第３図ないし第６図は、前記複合酸素センサ１
の製造工程を示すものである。 3 to 6 show the composite oxygen sensor 1
This shows the manufacturing process.
まず、第３図に示すように、４枚の固体電解質
セラミツクグリーンシート（以下単にグリーンシ
ートという）３a′，３b′，３c′，３d′を準備する。
グリーンシート３a′，３d′に拡散穴８ａ，８ｂを
形成したのち、グリーンシート３a′，３d′の両面
に、酸素検出用の電極パターン２a′，２b′と２c′，
２d′をそれぞれ印刷形成する。この電極パターン
２a′，２b′，２c′，２d′は、白金ペースト、たと
えば、白金粉末とエチルセルロースとカルビトー
ルの混合物を、スクリーン印刷等によつてグリン
シート３a′，３b′上に印刷して成る。ついで、電
極２b′，２c′を覆うように有機ペーストのパター
ン７a′，７b′を印刷形成する。このパターン７
a′，７b′の有機ペーストは、たとえば、エチセル
とα−テルピネオールとの混合物を用いる。 First, as shown in FIG. 3, four solid electrolyte ceramic green sheets (hereinafter simply referred to as green sheets) 3a', 3b', 3c', and 3d' are prepared.
After forming diffusion holes 8a and 8b in the green sheets 3a' and 3d', electrode patterns 2a', 2b' and 2c' for oxygen detection are formed on both sides of the green sheets 3a' and 3d'.
2d' are printed and formed, respectively. These electrode patterns 2a', 2b', 2c', and 2d' are made by printing platinum paste, for example, a mixture of platinum powder, ethyl cellulose, and carbitol, on the green sheets 3a', 3b' by screen printing or the like. Become. Next, organic paste patterns 7a' and 7b' are printed to cover the electrodes 2b' and 2c'. This pattern 7
As the organic paste a' and 7b', for example, a mixture of ethycel and α-terpineol is used.
一方、グリーンシート３c′には、アルミナペー
スト、たとえば、アルミナとエチセルおよびテル
ピネオールの混合物により、絶縁パターン４b′を
印刷形成したのち、この絶縁パターン４b′上に、
白金ペーストでヒータパターン５′を印刷形成す
る。 On the other hand, an insulating pattern 4b' is printed on the green sheet 3c' using alumina paste, for example, a mixture of alumina, ethycel, and terpineol, and then, on this insulating pattern 4b',
A heater pattern 5' is formed by printing using platinum paste.
前記各パターン２a′，２b′と２c′，２d′，７a′
，
７b′，４b′，５′を乾燥硬化させたのち、第４図
に示すように、グリーンシート３a′と３b′，３
c′と３d′をそれぞれ圧着する。この圧着は、たと
えば、120℃、80気圧のホツトプレスで行なう。
ついで、各積層体１a′と１b′を140℃で30分間加
熱し、パターン７a′，７b′を形成する有機ペース
トを蒸発させて除去し、拡散室７ａ，７ｂを形成
したのち、1500℃で２時間焼成する。この状態
で、グリーンシート３a′，３b′，３c′，３d′はそ
れぞれ、基板３ａ，３ｂ，３ｃ，３ｄとなり、電
極パターン２a′，２b′，２c′，２d′はそれぞれ電
極２ａ，２ｂ，２ｃ，２ｄとなる。また、絶縁パ
ターン４b′は絶縁層４ｂに、ヒータパターン５′
はヒータ５になる。ついで、第５図に示すよう
に、ヒータ５の上に絶縁パターン４a′を印刷形成
すると共に、基板３ｂ上に、２％のSiO2粉末と
固体電解質粉末を含むペースト１e′を印刷する。
そして、積層体１ａを1500℃で１時間焼結したの
ち、積層体１ａ，１ｂを積層し、さらに、1450℃
で１時間焼結する。そして第６図に示すように、
一体化したのち、その表裏面にスピネルをスパツ
タリングして、被覆層６ａ，６ｂを形成し、複合
酸素センサ１が完成する。 Each of the patterns 2a', 2b' and 2c', 2d', 7a'
，
After drying and curing the green sheets 7b', 4b', and 5', as shown in FIG.
Crimp c' and 3d' respectively. This crimping is performed, for example, using a hot press at 120° C. and 80 atm.
Next, each laminate 1a' and 1b' was heated at 140°C for 30 minutes to evaporate and remove the organic paste forming patterns 7a' and 7b' to form diffusion chambers 7a and 7b, and then heated at 1500°C. Bake for 2 hours. In this state, the green sheets 3a', 3b', 3c', 3d' become the substrates 3a, 3b, 3c, 3d, respectively, and the electrode patterns 2a', 2b', 2c', 2d' become the electrodes 2a, 2b, 3d, respectively. 2c and 2d. Further, the insulating pattern 4b' is attached to the insulating layer 4b, and the heater pattern 5'
becomes heater 5. Next, as shown in FIG. 5, an insulating pattern 4a' is printed on the heater 5, and a paste 1e' containing 2% SiO 2 powder and solid electrolyte powder is printed on the substrate 3b.
After sintering the laminate 1a at 1500°C for 1 hour, the laminates 1a and 1b were stacked, and then the laminate 1a was sintered at 1450°C.
Sinter for 1 hour. And as shown in Figure 6,
After integration, spinel is sputtered on the front and back surfaces to form coating layers 6a and 6b, and the composite oxygen sensor 1 is completed.
前記のように、本発明によれば、拡散穴８を明
ける以外は全て印刷と焼結によつて形成すること
ができ、部品点数の削減が可能になり、加工が容
易になる。 As described above, according to the present invention, everything except the formation of the diffusion holes 8 can be formed by printing and sintering, making it possible to reduce the number of parts and making processing easier.
以上述べた如く、本発明によれば、高精度の測
定が可能な複合酸素センサを提供することができ
る。また、複合酸素センサの加工を容易にし、作
業性を大巾に向上させることができるなどの効果
がある。
As described above, according to the present invention, a composite oxygen sensor capable of highly accurate measurement can be provided. Further, there are effects such as making it easier to process the composite oxygen sensor and greatly improving workability.
第１図は本発明による複合酸素センサの平面
図、第２図は第１図の−断面図、第３図ない
し第６図は本発明による複合酸素センサの製造工
程を示す工程図で、それぞれＡは第２図に対応す
る断面図、ＢはＡの底面図、第７図はストイツク
センサの空気過剰率に対する出力電圧の関係及び
希薄酸素センサの空気過剰率に対する出力電圧の
関係を示す図である。
１……複合酸素センサ、２ａ，２ｂ，２ｃ，２
ｄ……電極、３ａ，３ｂ，３ｃ，３ｄ……基板、
３ｅ……接合層、４ａ，４ｂ……絶縁層、５……
ヒータ、７ａ，７ｂ……拡散室、８ａ，８ｂ……
拡散孔。
FIG. 1 is a plan view of a composite oxygen sensor according to the present invention, FIG. 2 is a cross-sectional view taken from FIG. A is a sectional view corresponding to FIG. 2, B is a bottom view of A, and FIG. 7 is a diagram showing the relationship between the output voltage and the excess air ratio of the stoic sensor and the relationship between the output voltage and the excess air ratio of the lean oxygen sensor. It is. 1... Composite oxygen sensor, 2a, 2b, 2c, 2
d...electrode, 3a, 3b, 3c, 3d...substrate,
3e... bonding layer, 4a, 4b... insulating layer, 5...
Heater, 7a, 7b... Diffusion chamber, 8a, 8b...
Diffusion pore.
Claims (1)
質セラミツク基板と、該第１の固体電解質セラミ
ツク基板の両面の前記拡散孔の周囲に電極を形成
しこの電極間に定電流を流すことにより電極間の
起電力が測定され理論空燃比に対応して出力急変
があるストイツクセンサと、 被測定ガスの拡散孔を有する第２の固体電解質
セラミツク基板と、該第２の固体電解質セラミツ
ク基板の両面の前記拡散孔の周囲に電極を形成し
この電極間に定電圧を印加することにより限界電
流が測定される限界電流式希薄酸素センサと、 前記ストイツクセンサと前記希薄酸素センサの
間に、絶縁材でコーテイングされ、さらに固体電
解質セラミツクの間に挾持されたヒータと、 前記ストイツクセンサと希薄酸素センサのヒー
タ側の電極を囲むよう形成された拡散室とを備
え、 前記ヒータに対し前記ストイツクセンサと、前
記希薄酸素センサとが対称的に一体に結合されて
いることを特徴とする複合酸素センサ。 ２ 拡散孔を形成した固体電解質セラミツクグリ
ーンシートの両面に、拡散孔を中央にして白金ペ
ーストで検出用の電極パターンを印刷形成し、そ
の電極パターンの一方を有機物ペーストで覆つた
未焼成のストイツクセンサと希薄酸素センサを形
成し、固体電解質セラミツクグリーンシートの一
面に絶縁ペーストを塗布し、その上に白金ペース
トでヒータパターンを印刷した未焼成のヒータを
形成し、前記ストイツクセンサと希薄酸素センサ
のいずれか一方のセンサの有機ペースト塗布面に
前記ヒータの非パターン面を重ねて加熱圧着し、
他方のセンサの有機ペースト塗布面に固体電解質
セラミツクグリーンシートを加熱圧着し、それぞ
れ有機ペーストを加熱除去して拡散室を形成して
のち、焼結してストイツクセンサと希薄酸素セン
サ及びヒータを形成し、このヒータの上に絶縁ペ
ーストを塗布して焼結したのち、焼結された絶縁
物とヒータのないストイツクセンサもしくは希薄
酸素センサのセラミツク面との間に固体電解質ペ
ーストを塗布して圧着したのち、焼結して前記ス
トイツクセンサと前記希薄酸素センサとが前記ヒ
ータに対して対称的となるよう一体に接合するこ
とを特徴とする複合酸素センサの製造方法。[Scope of Claims] 1. A first solid electrolyte ceramic substrate having diffusion holes for a gas to be measured, electrodes being formed around the diffusion holes on both sides of the first solid electrolyte ceramic substrate, and a distance between the electrodes being defined. A stoic sensor that measures an electromotive force between electrodes by passing a current and has a sudden change in output in response to a stoichiometric air-fuel ratio; a second solid electrolyte ceramic substrate having a diffusion hole for a gas to be measured; A limiting current type dilute oxygen sensor in which a limiting current is measured by forming electrodes around the diffusion holes on both sides of a solid electrolyte ceramic substrate and applying a constant voltage between the electrodes; A heater coated with an insulating material and further sandwiched between solid electrolyte ceramics is provided between the sensors, and a diffusion chamber is formed to surround the electrodes on the heater side of the stoic sensor and the dilute oxygen sensor, A composite oxygen sensor characterized in that the stoic sensor and the dilute oxygen sensor are integrally coupled symmetrically to a heater. 2. An unfired stoichiometric ceramic green sheet with a detection electrode pattern printed on both sides of a solid electrolyte ceramic green sheet with diffusion holes formed therein using platinum paste with the diffusion hole in the center, and one side of the electrode pattern covered with an organic paste. A sensor and a dilute oxygen sensor are formed, an insulating paste is applied to one side of a solid electrolyte ceramic green sheet, and an unfired heater is formed on which a heater pattern is printed with platinum paste. The non-patterned surface of the heater is placed on the organic paste coated surface of one of the sensors and bonded by heat and pressure,
A solid electrolyte ceramic green sheet is heat-pressed onto the organic paste-coated surface of the other sensor, and the organic paste is removed by heating to form a diffusion chamber, and then sintered to form a stoic sensor, a dilute oxygen sensor, and a heater. After applying an insulating paste on this heater and sintering it, a solid electrolyte paste is applied and crimped between the sintered insulator and the ceramic surface of the stoic sensor or dilute oxygen sensor without a heater. A method for manufacturing a composite oxygen sensor, characterized in that the stoic sensor and the dilute oxygen sensor are then sintered and joined together so as to be symmetrical with respect to the heater.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58236183A JPS60128344A (en) | 1983-12-16 | 1983-12-16 | Composite oxygen sensor and its manufature |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58236183A JPS60128344A (en) | 1983-12-16 | 1983-12-16 | Composite oxygen sensor and its manufature |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60128344A JPS60128344A (en) | 1985-07-09 |
| JPH056659B2 true JPH056659B2 (en) | 1993-01-27 |
Family
ID=16996999
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58236183A Granted JPS60128344A (en) | 1983-12-16 | 1983-12-16 | Composite oxygen sensor and its manufature |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60128344A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0778487B2 (en) * | 1986-11-04 | 1995-08-23 | 株式会社ユニシアジェックス | Method of manufacturing oxygen sensor for internal combustion engine |
| DE19746516C2 (en) * | 1997-10-22 | 2001-09-27 | Bosch Gmbh Robert | Planar sensor element |
-
1983
- 1983-12-16 JP JP58236183A patent/JPS60128344A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60128344A (en) | 1985-07-09 |
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