JPS639860A - Oxygen sensor with heater and its production - Google Patents
Oxygen sensor with heater and its productionInfo
- Publication number
- JPS639860A JPS639860A JP61154722A JP15472286A JPS639860A JP S639860 A JPS639860 A JP S639860A JP 61154722 A JP61154722 A JP 61154722A JP 15472286 A JP15472286 A JP 15472286A JP S639860 A JPS639860 A JP S639860A
- Authority
- JP
- Japan
- Prior art keywords
- heater
- tungsten
- sensor
- oxygen sensor
- solid electrolyte
- 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 30
- 239000001301 oxygen Substances 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 25
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 239000000919 ceramic Substances 0.000 claims abstract description 14
- 239000011521 glass Substances 0.000 claims abstract description 14
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 14
- 239000010937 tungsten Substances 0.000 claims abstract description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000007789 gas Substances 0.000 claims abstract description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 5
- 239000011733 molybdenum Substances 0.000 claims abstract description 5
- 238000005245 sintering Methods 0.000 claims description 7
- MGRWKWACZDFZJT-UHFFFAOYSA-N molybdenum tungsten Chemical compound [Mo].[W] MGRWKWACZDFZJT-UHFFFAOYSA-N 0.000 claims description 2
- 238000007639 printing Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 229910000510 noble metal Inorganic materials 0.000 abstract 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 10
- 239000000843 powder Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000005219 brazing Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 210000003097 mucus Anatomy 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
Landscapes
- Measuring Oxygen Concentration In Cells (AREA)
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は内燃機関などの排ガス中の酸素濃度を検知する
ヒータ付酸素センサとその製造方法に関するものである
。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an oxygen sensor with a heater that detects the oxygen concentration in exhaust gas from an internal combustion engine, etc., and a method for manufacturing the sensor.
従来から、ジルコニア焼結体などのイオン伝導固体質（
固体電解質板）に一対の電極を設け、一方の電極側には
被測定ガス中の酸素分圧を、他方の電極側には大気の酸
素分圧を印加し、これら被測定ガスの酸素分圧と基準と
なる大気の酸素分圧との差によって生ずる起電力（又は
電気抵抗）によって酸素濃度を測定する酸素センサは一
般に広く利用されている。Traditionally, ion-conducting solid materials such as zirconia sintered bodies (
A pair of electrodes is provided on a solid electrolyte plate, and the partial pressure of oxygen in the gas to be measured is applied to one electrode, and the partial pressure of atmospheric oxygen is applied to the other electrode. Oxygen sensors that measure oxygen concentration based on the electromotive force (or electrical resistance) generated by the difference between the atmospheric oxygen partial pressure and the reference atmospheric oxygen partial pressure are generally widely used.
また、上記の如き酸素センサにおいて固体電解質表面や
電極近傍には排ガス中に存在するカーボン粉末や未燃焼
粒子等が付着し易く、測定誤差を生じたり、特性の劣化
を招く原因をなしていた。Furthermore, in the above oxygen sensor, carbon powder, unburned particles, etc. present in the exhaust gas tend to adhere to the solid electrolyte surface or near the electrodes, causing measurement errors and deterioration of characteristics.
そのため、酸素センサには、表面に付着した汚染物質の
除去や、低温におけるガス惑応性の向上など双方の目的
を果たすため、酸素センサ自体を８００℃程度に加熱す
るためのヒータを併設したものが使用されている。For this reason, some oxygen sensors are equipped with a heater to heat the oxygen sensor itself to about 800°C in order to accomplish both purposes, such as removing contaminants attached to the surface and improving gas response at low temperatures. It is used.
すなわち、第５図にて要部横断面図（本発明実施例とし
ての第２図Ｙ−Ｙ線断面に相当）を示すように、固体電
解質としてのジルコニアセラミックの板状体Ｊの両面に
白金電極Ｐ＋、Ｐ２をメタライズ手法などにより設けて
構成したセンサ部Ｓに対し、アルミナセラミック体中に
白金ペーストを印刷手法により所定のパターンが埋設さ
れてなるセラミックヒータＨを積層一体化し焼結して製
作した酸素センサが使用されていた。That is, as shown in the main part cross-sectional view in FIG. 5 (corresponding to the Y--Y line cross section in FIG. 2 as an example of the present invention), platinum is applied to both sides of the zirconia ceramic plate J as a solid electrolyte. A ceramic heater H, which has a predetermined pattern embedded in an alumina ceramic body using a printing method using platinum paste, is laminated and manufactured by laminating and sintering the sensor part S, which is constructed by providing electrodes P+ and P2 using a metallization method or the like. An oxygen sensor was used.
ところが、上記の如き、セラミックヒータを一体的に備
えた酸素センサでは、センサＳとヒータＨとを一体的に
焼結して構成されたものであることから、固体電解質と
してのジルコニアセラミックがともに焼結する温度雰囲
気中で焼結する必要がある。しかも固体電解質であるジ
ルコニアセラミック板の両面には白金電極を設けるが、
これには一般に白金ペーストを印刷手法により所定のパ
ターンにプリントしたものをセラミックの焼結と併せて
高温度で焼付けている。However, in the oxygen sensor integrally equipped with a ceramic heater as described above, since the sensor S and the heater H are integrally sintered, the zirconia ceramic as the solid electrolyte is not sintered. It is necessary to sinter in an atmosphere at a temperature that is suitable for sintering. Moreover, platinum electrodes are provided on both sides of the zirconia ceramic plate, which is a solid electrolyte.
Generally, this involves printing platinum paste into a predetermined pattern using a printing method, and baking it at a high temperature in conjunction with ceramic sintering.
このように、セラミックヒータもセンサと同時焼結し、
一体化するものであるため白金電極の焼付と同一条件で
焼成できる白金ペーストでもってヒータの発熱抵抗パタ
ーンも構成する必要がある。In this way, the ceramic heater is also co-sintered with the sensor,
Since the heater is integrated, it is also necessary to construct the heating resistance pattern of the heater using a platinum paste that can be fired under the same conditions as the platinum electrode.
したがってセンサを為す白金電極だけでなく、ヒータの
発熱抵抗体をも白金を用いることからコスト的に非常に
高価なものとなる。また発熱抵抗体が白金より成る場合
、抵抗温度係数が小さいため発熱温度のコントロールが
難しく、かつ消費電力が大きいという欠点があった。Therefore, since platinum is used not only for the platinum electrode forming the sensor but also for the heating resistor of the heater, the cost becomes very high. Furthermore, when the heating resistor is made of platinum, the temperature coefficient of resistance is small, making it difficult to control the heating temperature and consuming large amounts of power.
さらに、センサとヒータを同時に一体焼結するものであ
るため、一度の焼結で済むため、生産性が良いように考
えられるが、実際の生産において良品が得られる率、す
なわち歩留りが悪いという不都合があった。Furthermore, since the sensor and heater are sintered simultaneously, productivity is thought to be good because only one sintering process is required, but in actual production, the rate of obtaining good products, that is, the yield rate, is low. was there.
上記事情に鑑み、固体電解質に白金電極を付設して成る
センサと、アルミナセラミック体中にタングステンペー
ストで形成した発熱抵抗体を内蔵してヒータとをそれぞ
れ別途製作しておき、所定の特性を備えた、良品のみを
ガラス付によって接着一体化して酸素センサを構成する
。In view of the above circumstances, a sensor consisting of a solid electrolyte with a platinum electrode attached to it and a heater with a built-in heating resistor made of tungsten paste in an alumina ceramic body were separately fabricated, and each had the specified characteristics. In addition, an oxygen sensor is constructed by bonding and integrating only good products with glass.
以下、図によって本発明実施例を具体的に詳述する。 Hereinafter, embodiments of the present invention will be specifically described in detail with reference to the drawings.
第１図乃至第３図にて本発明によるヒータ付酸素センサ
１の構造を示し、このセンサ１の先端には被測定ガスを
導入するための導入孔２と、後端には基準ガスとしての
大気を導入する大気導入孔３が各々形成されている。こ
のうち導入孔２は、固体電解質板４の片面に設けた白金
電極５が形成された空間５ａに、他方の大気導入孔３は
同じく固体電解質４の他の面に設けた白金電極６が形成
された空間６ａにそれぞれ連通ずるように構成されてい
る。この場合、固体電解質板４の片面に形成された白金
電極６が露出した空間６ａを形成する外壁部材７は固体
電解質板４と同じものでもよいが、アルミナセラミック
で作製したものを接合部８においてガラス付けしたもの
であってもよい。1 to 3 show the structure of a heater-equipped oxygen sensor 1 according to the present invention, and the sensor 1 has an introduction hole 2 at the front end for introducing the gas to be measured, and a rear end for introducing the gas to be measured. Atmosphere introduction holes 3 for introducing the atmosphere are formed respectively. Among these, the introduction hole 2 is formed in a space 5a in which a platinum electrode 5 provided on one side of the solid electrolyte plate 4 is formed, and the other air introduction hole 3 is formed in a space 5a in which a platinum electrode 6 provided on the other side of the solid electrolyte 4 is formed. The space 6a is configured to communicate with each other. In this case, the outer wall member 7 forming the space 6a in which the platinum electrode 6 formed on one side of the solid electrolyte plate 4 is exposed may be the same as the solid electrolyte plate 4, but it may be made of alumina ceramic at the joint portion 8. It may also be made of glass.
このように構成されたセンサＳに対し、タングステン又
はタングステン−モリブデンなどのペーストを用い印刷
手法によりアルミナセラミック体９中に発熱抵抗体１０
を埋設したヒータＨの片面を上記センサＳの一面にガラ
ス付によって全面的にガラス接着させる。For the sensor S configured in this manner, a heating resistor 10 is attached to the alumina ceramic body 9 by a printing method using a paste such as tungsten or tungsten-molybdenum.
One side of the heater H, which is embedded therein, is completely bonded to one side of the sensor S by glass bonding.
なお、白金電極５．６は後端からり−ド５ｂ、６ｂによ
って各々導出され、また発熱抵抗体１０には同じく後端
に備えたリード１０ａから通電されるようになっている
。The platinum electrodes 5.6 are led out through leads 5b and 6b from the rear end, respectively, and the heating resistor 10 is energized from a lead 10a also provided at the rear end.
次に、上記の如く構成されたヒータ付酸素センサ１の製
法について述べる。Next, a method for manufacturing the heater-equipped oxygen sensor 1 constructed as described above will be described.
第４図には焼結一体化及びガラス接着を行う前の各部材
の立体構成図を示す。これにおいて、まず、固体電解質
板４を製作すべく、ジルコニア粉末から形成したジルコ
ニア生シート４０の両面に、白金微粉末やガラス粉末、
有機粘液等で形成した白金ペーストでもって白金電極パ
ターン５０．６０と、これに連続したリードパターン５
１．６１をスクリーン印刷によって付着せしめた後、他
のジルコニア生シート４１．４２を積層して一体焼結す
る。また、外壁部材７を製作すべくアルミナ生シー）７
０と、第３図で示した空間６ａとする切抜きを施したア
ルミナ生シート７１を重ね合′わせ一体焼結することに
よってセンサＳが製作される。FIG. 4 shows a three-dimensional configuration diagram of each member before sintering and integrating and glass bonding. In this process, first, in order to manufacture the solid electrolyte plate 4, fine platinum powder, glass powder, etc.
A platinum electrode pattern 50.60 made of platinum paste made of organic mucus or the like, and a lead pattern 5 continuous thereto.
After 1.61 is attached by screen printing, other green zirconia sheets 41.42 are laminated and integrally sintered. In addition, in order to manufacture the outer wall member 7, alumina raw material) 7
The sensor S is fabricated by overlapping and integrally sintering a raw alumina sheet 71 with a cutout to form the space 6a shown in FIG. 3.
上記のように製作した白金電極５ （５０）、６ （６
０）を備えたジルコニア焼結体に対し、外壁部材７ （
７０，７１）をガラス接着することによってセンサＳが
完成する。Platinum electrodes 5 (50), 6 (6
0), the outer wall member 7 (
70, 71) are bonded to glass to complete the sensor S.
一方、セラミックヒータＨはアルミナ生シート９０に、
タングステン又はタングステンとモリブデンなどの微粉
末とガラス粉末や有機性粘液などを練り合わせてなるタ
ングステンペーストでもって発熱抵抗体ｌＯとする導電
パターン１００をスクリーン印刷した後、他のアルミナ
生シート９１を重ね合わせ焼結一体化することによりヒ
ータＨが製作される。On the other hand, ceramic heater H is made of raw alumina sheet 90,
After screen-printing a conductive pattern 100 to serve as a heating resistor 10 using a tungsten paste made by kneading fine powder such as tungsten or tungsten and molybdenum with glass powder or organic slime, another raw alumina sheet 91 is superimposed and fired. The heater H is manufactured by integrating them.
上述のようにして、それぞれ製作されたセンサＳ、ヒー
タＨは所定の機能、特性を備えたものであるかどうかの
製品検査をした後の良品のみを用い、センサＳとヒータ
Ｈとを接着面１１においてガラス付けを行うとともに各
リード５ｂ、６ｂ。The sensor S and heater H manufactured as described above are inspected to ensure that they have the prescribed functions and characteristics, and only good products are used, and the sensor S and heater H are bonded together. 11, each lead 5b, 6b is attached with glass.
１０ａをロウ付は等の手段により接合することによって
ヒータ付酸素センサｌとして完成される。By joining 10a by brazing or other means, the oxygen sensor 1 with a heater is completed.
なお、上記におけるガラス接着を行うために用いるガラ
ス材は接着する両部材のほぼ中間の熱膨張率をもったも
のが望ましい。Note that it is desirable that the glass material used for the glass bonding described above has a coefficient of thermal expansion approximately intermediate between the two members to be bonded.
畝上のように本発明によれば、ヒータ付酸素センサにお
いて、タングステン又はタングステンとモリブデン材料
から成る発熱抵抗体をアルミナセラミック体中に埋設、
内蔵したセラミックヒータと、別途製作した酸素センサ
とをガラス接着して構成、製作したことから、低消費電
力で、かつ発熱抵抗体として貴金属である白金を使用し
ないことから大幅なコストダウンを図ることが可能とな
り、しかも別途に製作したセンサ、ヒータのうち選別し
た良品のみを用いてガラス接着して構成することから歩
留率が非常に良いなどすぐれた特長をもっている。According to the present invention, in the oxygen sensor with a heater, a heating resistor made of tungsten or tungsten and molybdenum material is embedded in an alumina ceramic body.
The built-in ceramic heater and the separately manufactured oxygen sensor are constructed and manufactured by bonding them to glass, resulting in low power consumption and significant cost reductions as platinum, a precious metal, is not used as the heating resistor. Moreover, it has excellent features such as a very high yield rate because it is constructed by bonding glass using only selected good quality sensors and heaters that were manufactured separately.
第１図は本発明実施例によるヒータ付酸素センサの平面
図、第２図は第１図におけるヒータ付酸素センサのＸ−
Ｘ線断面図、第３図は第２図におけるＹ−Ｙ線断面図で
あり、第４図は本発明実施例によるヒータ付酸素センサ
の製造方法を説明するための立体構成図である。第５図
は従来のヒータ付酸素センサの要部横断面図である。
１：ヒータ付酸素センサ
２；導入孔
３：大気導入孔
４：固体電解質
５．６：白金電極
Ｈ：ヒータ
Ｓ：センサFIG. 1 is a plan view of an oxygen sensor with a heater according to an embodiment of the present invention, and FIG. 2 is a plan view of the oxygen sensor with a heater in FIG.
3 is a sectional view taken along the line Y--Y in FIG. 2, and FIG. 4 is a three-dimensional configuration diagram for explaining a method of manufacturing an oxygen sensor with a heater according to an embodiment of the present invention. FIG. 5 is a cross-sectional view of a main part of a conventional oxygen sensor with a heater. 1: Oxygen sensor with heater 2; Introduction hole 3: Air introduction hole 4: Solid electrolyte 5.6: Platinum electrode H: Heater S: Sensor
Claims (2)
電極を設けて成るセンサ部に、タングステン又はタング
ステン−モリブデン系の発熱体が埋設されたセラミック
ヒータをガラス接着したことを特徴とするヒータ付酸素
センサ。(1) A heater characterized in that a ceramic heater in which a tungsten or tungsten-molybdenum heating element is embedded is bonded to a sensor portion comprising platinum electrodes facing each other on both sides of a solid electrolyte plate. With oxygen sensor.
る固体電解質板に対し、上記各白金電極に気体を導くた
めの切欠溝、孔などを形成したセラミック生シートを積
層し焼結一体化して酸素センサを得る工程と、 アルミナ生シート間にタングステン又はタングステン−
モリブデン系の発熱体を介在させ焼結一体化してセラミ
ックヒータを得る工程と、 上記各工程により得た酸素センサとセラミックヒータと
をガラス接着する工程よりなるヒータ付酸素センサの製
造方法。(2) On a solid electrolyte plate with platinum electrodes facing each other on both sides, green ceramic sheets with grooves, holes, etc. formed for guiding gas to each of the platinum electrodes are laminated and sintered into one piece. tungsten or tungsten between the raw alumina sheets.
A method for manufacturing an oxygen sensor with a heater, which comprises a step of obtaining a ceramic heater by sintering and integrating a molybdenum-based heating element, and a step of bonding the oxygen sensor obtained through each of the above steps to the ceramic heater with glass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61154722A JPH0814564B2 (en) | 1986-06-30 | 1986-06-30 | Oxygen sensor with heater and method of manufacturing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61154722A JPH0814564B2 (en) | 1986-06-30 | 1986-06-30 | Oxygen sensor with heater and method of manufacturing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS639860A true JPS639860A (en) | 1988-01-16 |
| JPH0814564B2 JPH0814564B2 (en) | 1996-02-14 |
Family
ID=15590529
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61154722A Expired - Fee Related JPH0814564B2 (en) | 1986-06-30 | 1986-06-30 | Oxygen sensor with heater and method of manufacturing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0814564B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003107035A (en) * | 2001-09-27 | 2003-04-09 | Kyocera Corp | Oxygen sensor |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5589742A (en) * | 1978-12-28 | 1980-07-07 | Toray Ind Inc | Oxygen concentration cell of solid electrolyte |
-
1986
- 1986-06-30 JP JP61154722A patent/JPH0814564B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5589742A (en) * | 1978-12-28 | 1980-07-07 | Toray Ind Inc | Oxygen concentration cell of solid electrolyte |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003107035A (en) * | 2001-09-27 | 2003-04-09 | Kyocera Corp | Oxygen sensor |
| JP4721593B2 (en) * | 2001-09-27 | 2011-07-13 | 京セラ株式会社 | Oxygen sensor |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0814564B2 (en) | 1996-02-14 |
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