JPH02203267A - Production of limiting current type oxygen sensor - Google Patents
Production of limiting current type oxygen sensorInfo
- Publication number
- JPH02203267A JPH02203267A JP1024601A JP2460189A JPH02203267A JP H02203267 A JPH02203267 A JP H02203267A JP 1024601 A JP1024601 A JP 1024601A JP 2460189 A JP2460189 A JP 2460189A JP H02203267 A JPH02203267 A JP H02203267A
- Authority
- JP
- Japan
- Prior art keywords
- glass
- cap
- pellet
- coated
- glass powder
- 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.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims description 12
- 229910052760 oxygen Inorganic materials 0.000 title claims description 12
- 239000001301 oxygen Substances 0.000 title claims description 12
- 239000011521 glass Substances 0.000 claims abstract description 48
- 239000000843 powder Substances 0.000 claims abstract description 26
- 239000008188 pellet Substances 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 10
- 239000000758 substrate Substances 0.000 claims description 22
- 238000010304 firing Methods 0.000 claims description 16
- 239000011247 coating layer Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 239000010410 layer Substances 0.000 claims description 6
- 239000010416 ion conductor Substances 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000001354 calcination Methods 0.000 abstract 4
- 239000004020 conductor Substances 0.000 abstract 1
- 239000000853 adhesive Substances 0.000 description 9
- 230000001070 adhesive effect Effects 0.000 description 9
- 239000011800 void material Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 3
- 230000002950 deficient Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 206010021143 Hypoxia Diseases 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052839 forsterite Inorganic materials 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
Landscapes
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Abstract
Description
この発明は、安定化ジルコニアなどを酸素イオン導電体
として利用する限界電流式酸素センサの製造方法の改良
に関する。この限界電流式酸素センサはボイラ、自動車
エンジン等の燃焼制御、あるいはマンホール等での酸欠
モニター等に利用されている。The present invention relates to an improvement in a method for manufacturing a limiting current type oxygen sensor that uses stabilized zirconia or the like as an oxygen ion conductor. This limiting current type oxygen sensor is used for combustion control in boilers, automobile engines, etc., and oxygen deficiency monitoring in manholes, etc.
従来の限界電流式酸素センサのうち、ヒーターを有する
保持基板にセンサ本体を結合させるタイプのものでは、
予め限界電流式酸素センサ本体を作っておき、これに、
予めヒーターが形成された保持基板を接着剤で接着させ
て製造するようにしている。Among the conventional limiting current type oxygen sensors, the type in which the sensor body is connected to a holding board with a heater,
Make the limiting current type oxygen sensor body in advance, and attach it to it.
The device is manufactured by bonding a holding substrate on which a heater is formed in advance with an adhesive.
しかしながら、従来のように接着工程を別個に行なうの
では製造工程数が増え、生産性が悪いという問題がある
。また、接着剤あるいは接着剤の隙間により生じた空洞
部によりヒーターの熱伝導が妨げられる分だけヒーター
の熱効率が低下するという問題もある。
この発明は、製造工程数が少なく生産性が良好で、且つ
ヒーターの熱効率も改善可能な、限界電流式酸素センサ
の製造方法を提供することを目的とする。However, if the bonding process is performed separately as in the past, the number of manufacturing steps increases, resulting in poor productivity. Another problem is that the thermal efficiency of the heater is reduced to the extent that heat conduction of the heater is hindered by the adhesive or the cavity created by the gap between the adhesives. SUMMARY OF THE INVENTION An object of the present invention is to provide a method for manufacturing a limiting current type oxygen sensor, which has a small number of manufacturing steps, has good productivity, and can also improve the thermal efficiency of a heater.
上記目的を達成するため、この発明による限界電流式酸
素センサの製造方法においては、表裏両面に電極を有す
るイオン導電体ベレットに対し、まずその一方の面に高
温で散逸する材料を塗布し、さらにその材料の塗布層の
全体を覆い尽くすように上記のベレットの一方面にガラ
ス微粉末を塗布した後直ちにこのガラス微粉末塗布層表
面に保持基板を密着させ、その状態で焼成工程を行うこ
とが特徴となっている。In order to achieve the above object, in the method for manufacturing a limiting current type oxygen sensor according to the present invention, an ionic conductor pellet having electrodes on both the front and back surfaces is first coated with a material that dissipates at high temperature, and then Immediately after applying fine glass powder to one side of the pellet so as to cover the entire coating layer of the material, a holding substrate is brought into close contact with the surface of the fine glass powder coating layer, and the firing process is performed in this state. It has become a feature.
イオン導電体ベレットの一方の面にまず高温で散逸する
材料を塗布し、さらにその材料の塗布層の全体を覆い尽
くすように上記のベレットの一方面にガラス微粉末を塗
布した後直ちにこのガラス微粉末塗布層表面に保持基板
を密着させ、その状態で焼成工程を行うと、ガラス一体
層によるガラスキャップが形成され、このガラスキャッ
プは上記ベレッ１−に封着された状態になるとともに、
上記の保持基板がこのガラスキャップに接着されること
になる。また、この焼成工程で上記の材料は酸化あるい
は蒸発して散逸してしまうため、その部分に空隙が形成
されるが、上記のようにガラスキャップがベレットに封
着されるため、この空隙は気密に保たれることになる。
そして、−度の焼成工程で、気密な空隙を形成するガラ
スキャップを形成することができるとともに、保持基板
を接着できるため、製造工程数が少なくなり、生産性に
優れることになる。
また、接着剤を用いないため、その分だけ熱伝導に優れ
、保持基板に設けられたヒーターの熱効率が向上する。
そして接着剤の隙間により形成される空洞部も形成され
ないため、この点でも熱伝導が優れる。
さらに、焼成前のガラスに対する保持基板の密着はある
程度ラフなものでよいので、不良品発生のリスクが少な
く、量産性に優れる。First, a material that dissipates at high temperature is applied to one side of the ionic conductor pellet, and then a fine glass powder is applied to one side of the above-mentioned pellet so as to cover the entire coated layer of the material. When the holding substrate is brought into close contact with the surface of the powder coating layer and the firing process is performed in this state, a glass cap is formed by the glass integral layer, and this glass cap is sealed to the bellet 1-, and
The holding substrate described above will be adhered to this glass cap. Also, during this firing process, the above materials oxidize or evaporate and dissipate, so a void is formed in that area, but since the glass cap is sealed to the pellet as described above, this void is airtight. will be maintained. In addition, a glass cap that forms an airtight gap can be formed in a second firing process, and a holding substrate can be bonded to the glass cap, which reduces the number of manufacturing steps and improves productivity. Furthermore, since no adhesive is used, thermal conductivity is excellent, and the thermal efficiency of the heater provided on the holding substrate is improved. Also, since no cavities are formed due to gaps between adhesives, heat conduction is excellent in this respect as well. Furthermore, the adhesion of the holding substrate to the glass before firing may be rough to some extent, so there is less risk of producing defective products and it is excellent in mass production.
つぎにこの発明の一実施例について図面を参照ｊ、なが
ら説明する。図面は製造過程に沿ったもので、この順に
述べて行く。まず、第１図に示すように、たとえば安定
化ジルコニア（ＺｒＯ２−８ｎｏ１％Ｙ２Ｏ３）のベレ
ット１に小孔２を設けたものを用意し、この両面に小孔
２を塞がないようにして電極３．４をそれぞれ形成する
。具体的にはたとえば白金などの材料をペースト状にし
たものをスクリーン印刷により塗工して必要に応じて乾
燥させた後、たとえば１０００°Ｃで３０分焼成して形
成する。
つぎに第２図のようにアルミナ粉（あるいは高温で酸化
または蒸発して散逸する他の有機材料）をペースト状に
したものをスクリーン印刷によりベレット１の電ｆ！４
側に塗布してアルミナ粉塗布Ｍ５を形成する。このとき
、図示のように小孔２にもアルミナ粉が詰まるが、この
小孔２は直径が２０μｍ〜３０μｍ程度のきわめて細い
ものであるから詰まらないこともあり、それでもよい。
さらに、第３図に示すように、このアルミナ粉塗布層５
の上にペースト状にしたガラス微粉末をスクリーン印刷
により塗工し、アルミナ粉塗布層５を覆い尽くすガラス
微粉末塗布層６１を形成する。このガラスとしてはたと
えば岩城ガラス株式会社製に一４００６ＡとＺｒＯ２−
３ｉｏ１％Ｙ２Ｏ３とを混合比１：１で混合したものな
どを使用できる。
その直後に、第４図に示すようにヒーター８が形成され
た保持基板（たとえばアルミナ板でなる〉９を、このガ
ラス微粉末塗布層６１に密着させる。
この状態で、これを乾燥のための仮焼成を経、あるいは
この仮焼成を経ずに、たとえば９５０°Ｃの炉に３０分
入れて焼成を行う。すると、第５図に示すようにガラス
微粉末塗布ｌｌ６１はガラス−体層となり、このガラス
一体層により形成されたガラスキャップ６ができあがる
。アルミナ粉塗布、！５はこの焼成工程で酸化して気化
しあるいは蒸発して散逸し、その結果その部分が空隙７
となって残り、気密性の高い空隙７が得られる。すなわ
ち、気密な空隙７を形成するためのガラスキ・ヤップ６
がジルコニアベレット１に封着されたことになる。また
、小孔２の部分も貫通する。そして、この焼成により、
ガラスキャップ６の表面に保持基板９が接着されること
になる。
ここで、−度の焼成によりガラスキャップ６の形成と、
このガラスキャップ６への保持基板９の接着とが同時に
達成される。したがって、工程数が減り、生産性が向上
する。しかも、焼成前にはガラス微粉末塗布層６１と保
持基板９とは単に密着させておくだけで、焼成によって
ガラスキャップ６と保持基板９とが接着することになる
ため、密着させる作業は比較的ラフでも許されることに
なる。さらにこのようにガラスの焼成によって接着され
るため、その接着力は大きく、且つ接着剤を介在させな
いためヒーター８の熱効率も上がる。
実際に上記の材料で製造したところ、ガラスキャップ６
と保持基板９との接着性は良好で、且つヒーター８の熱
効率も上がって酸素センサとしての良好な特性が得られ
ることが確認できた。また、ガラスキャップ６となるガ
ラスとして旭ガラス株式会社製ＡＳＦ−２００を使用し
、保持基板９としてフォルステライト板を使用して作っ
た実例においてもガラスキャップ６と保持基板９との接
着力に問題はなく、しかもヒーター８の効率が従来より
３０％程度向上し、特性の良好な限界電流式酸素センサ
が得られたことが確認できた。
なお、ガラスキャップ６となるガラスとしては上記のガ
ラス以外に軟化点９００℃〜１０００°Ｃ程度以上の高
融点ガラス、結晶化ガラスなどを使用することができる
。また、上記では省略しているが、ジルコニアペレット
１の面から保持基板９の面にまで伸びる電極３．４のリ
ード部分を、上記のガラスキャップ６の形成のための焼
成時に同時に形成することもできる。この場合、第４図
のようにガラス微粉末塗布層６１を保持基板９に密着さ
せた状態で、ペースト状のリード材料をジルコニアペレ
ット１の面から保持基板９の表面に至るパターンにスク
リーン印刷により形成しておけば、ガラスキャップ６の
形成のための焼成時に、このリード部分が同時に焼成さ
れてできあがることになる。Next, an embodiment of the present invention will be described with reference to the drawings. The drawings follow the manufacturing process and will be described in this order. First, as shown in Fig. 1, a pellet 1 made of, for example, stabilized zirconia (ZrO2-8no1%Y2O3) with small holes 2 is prepared, and the electrodes are placed on both sides of the pellet without blocking the small holes 2. 3.4 respectively. Specifically, it is formed by applying a paste of material such as platinum by screen printing, drying if necessary, and then baking at, for example, 1000° C. for 30 minutes. Next, as shown in Figure 2, alumina powder (or other organic material that oxidizes or evaporates at high temperatures and dissipates) is made into a paste and screen printed to make the pellet 1 electric f! 4
Coat on the side to form alumina powder coating M5. At this time, as shown in the figure, the small hole 2 is also clogged with alumina powder, but since the small hole 2 is extremely thin with a diameter of about 20 μm to 30 μm, it may not be clogged, so this is fine. Furthermore, as shown in FIG. 3, this alumina powder coating layer 5
Fine glass powder in the form of a paste is applied thereon by screen printing to form a fine glass powder coating layer 61 that completely covers the alumina powder coating layer 5. Examples of this glass include ZrO2-4006A and ZrO2- manufactured by Iwaki Glass Co., Ltd.
A mixture of 3io1% Y2O3 at a mixing ratio of 1:1 can be used. Immediately after that, as shown in FIG. 4, a holding substrate (for example, made of an alumina plate) 9 on which a heater 8 is formed is brought into close contact with this fine glass powder coating layer 61. In this state, it is placed for drying. After pre-firing or without this pre-firing, it is fired by placing it in a furnace at 950°C for 30 minutes.Then, as shown in FIG. 5, the glass fine powder coating 1161 becomes a glass body layer. The glass cap 6 formed by this glass integral layer is completed.The alumina powder coating, !5, oxidizes and vaporizes or evaporates and dissipates in this firing process, and as a result, the area becomes the void 7.
, and a highly airtight void 7 is obtained. That is, a glass cover 6 for forming an airtight void 7 is used.
is sealed to the zirconia pellet 1. It also penetrates through the small hole 2. And by this firing,
A holding substrate 9 is bonded to the surface of the glass cap 6. Here, the formation of the glass cap 6 by - degree firing,
This adhesion of the holding substrate 9 to the glass cap 6 is achieved at the same time. Therefore, the number of steps is reduced and productivity is improved. Moreover, the fine glass powder coating layer 61 and the holding substrate 9 are simply brought into close contact with each other before firing, and the glass cap 6 and the holding substrate 9 are bonded together by firing, so the work of bringing them into close contact is relatively easy. Even if it's rough, it will be forgiven. Furthermore, since the glass is bonded by firing the glass, its adhesive strength is large, and since no adhesive is used, the thermal efficiency of the heater 8 is also increased. When actually manufactured using the above material, the glass cap 6
It was confirmed that the adhesion between the substrate and the holding substrate 9 was good, and the thermal efficiency of the heater 8 was also increased, resulting in good characteristics as an oxygen sensor. In addition, even in an example in which ASF-200 manufactured by Asahi Glass Co., Ltd. was used as the glass for the glass cap 6 and a forsterite plate was used as the holding substrate 9, there was a problem with the adhesive strength between the glass cap 6 and the holding substrate 9. Moreover, it was confirmed that the efficiency of the heater 8 was improved by about 30% compared to the conventional one, and that a limiting current type oxygen sensor with good characteristics was obtained. In addition to the above-mentioned glasses, high melting point glass having a softening point of about 900° C. to 1000° C. or more, crystallized glass, etc. can be used as the glass forming the glass cap 6. Further, although omitted above, the lead portion of the electrode 3.4 extending from the surface of the zirconia pellet 1 to the surface of the holding substrate 9 may be formed at the same time as the firing for forming the glass cap 6 described above. can. In this case, with the glass fine powder coating layer 61 in close contact with the holding substrate 9 as shown in FIG. If formed, this lead portion will be fired at the same time when the glass cap 6 is fired to form it.
この発明の限界電流式酸素センサの製造方法によれば、
−度の焼成工程で気密な空隙を形成するガラス一体層の
形成と保持基板の接着とを達成できるため、製造工程数
が少なくなり、生産性を向上させることができる。また
、接着剤を用いないため、その分だけ熱伝導に優れ、保
持基板に設けられたヒーターの熱効率が向上する。さら
に不良品の発生率が小さく量産性にも優れる。According to the method for manufacturing a limiting current type oxygen sensor of the present invention,
Since the formation of an integral glass layer that forms an airtight void and the adhesion of the holding substrate can be achieved in a second firing step, the number of manufacturing steps can be reduced and productivity can be improved. Furthermore, since no adhesive is used, thermal conductivity is excellent, and the thermal efficiency of the heater provided on the holding substrate is improved. Furthermore, the incidence of defective products is low and mass productivity is excellent.
第１図、第２図、第３図、第４図及び第５図はこの発明
の一実施例にかかる製造過程の各段階での断面図である
。
１・・・安定化ジルコニアペレット、２・・・小孔、３
．４・・・電極、５・・・アルミナ粉塗布層、６・・・
ガラスキャップ、６１・・・ガラス微粉末塗布層、７・
・・空隙、８・・・ヒーター、９・・・保持基板。1, 2, 3, 4, and 5 are cross-sectional views at each stage of the manufacturing process according to an embodiment of the present invention. 1... Stabilized zirconia pellet, 2... Small hole, 3
．． 4... Electrode, 5... Alumina powder coating layer, 6...
Glass cap, 61...Glass fine powder coating layer, 7.
...Gap, 8...Heater, 9...Holding substrate.
Claims (1)
対し、まずその一方の面に高温で散逸する材料を塗布し
、さらにその材料の塗布層の全体を覆い尽くすように上
記のペレットの一方面にガラス微粉末を塗布した後直ち
にこのガラス微粉末塗布層表面に保持基板を密着させ、
その状態で焼成工程を行うことを特徴とする限界電流式
酸素センサの製造方法。(1) First, a material that dissipates at high temperature is applied to one side of an ionic conductor pellet that has electrodes on both the front and back sides, and then one side of the pellet is coated so as to cover the entire coated layer of the material. Immediately after applying fine glass powder to the surface of the fine glass powder coating layer, a holding substrate is brought into close contact with the surface of the fine glass powder coating layer.
A method for manufacturing a limiting current type oxygen sensor, characterized in that a firing process is performed in this state.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1024601A JPH02203267A (en) | 1989-02-02 | 1989-02-02 | Production of limiting current type oxygen sensor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1024601A JPH02203267A (en) | 1989-02-02 | 1989-02-02 | Production of limiting current type oxygen sensor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02203267A true JPH02203267A (en) | 1990-08-13 |
Family
ID=12142672
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1024601A Pending JPH02203267A (en) | 1989-02-02 | 1989-02-02 | Production of limiting current type oxygen sensor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02203267A (en) |
-
1989
- 1989-02-02 JP JP1024601A patent/JPH02203267A/en active Pending
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