JPS6318262A - Oxygen sensor - Google Patents
Oxygen sensorInfo
- Publication number
- JPS6318262A JPS6318262A JP61160816A JP16081686A JPS6318262A JP S6318262 A JPS6318262 A JP S6318262A JP 61160816 A JP61160816 A JP 61160816A JP 16081686 A JP16081686 A JP 16081686A JP S6318262 A JPS6318262 A JP S6318262A
- Authority
- JP
- Japan
- Prior art keywords
- green sheet
- oxygen
- heater
- cap
- printed
- 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
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 61
- 239000001301 oxygen Substances 0.000 title claims abstract description 61
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 58
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000758 substrate Substances 0.000 claims abstract description 6
- 239000012528 membrane Substances 0.000 claims description 18
- 239000000919 ceramic Substances 0.000 claims description 14
- 229910002076 stabilized zirconia Inorganic materials 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 29
- 229910052697 platinum Inorganic materials 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 abstract description 6
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 239000005394 sealing glass Substances 0.000 abstract description 3
- 230000005855 radiation Effects 0.000 abstract description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract 4
- 230000000087 stabilizing effect Effects 0.000 abstract 2
- 230000006698 induction Effects 0.000 abstract 1
- 239000002002 slurry Substances 0.000 description 21
- 238000002156 mixing Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000005498 polishing Methods 0.000 description 6
- 238000007639 printing Methods 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 230000017525 heat dissipation Effects 0.000 description 3
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 238000007606 doctor blade method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- -1 fatty acid esters Chemical class 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 101100245253 Caenorhabditis elegans pas-5 gene Proteins 0.000 description 1
- 235000009852 Cucurbita pepo Nutrition 0.000 description 1
- 241000219104 Cucurbitaceae Species 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910009498 Y2O1 Inorganic materials 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 238000000861 blow drying Methods 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000002241 glass-ceramic Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 150000003459 sulfonic acid esters Chemical class 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Abstract
Description
【発明の詳細な説明】 〔発明の目的〕 （産業上の利用分野） 本発明は酸素センサおよびその製造方法に関する。[Detailed description of the invention] [Purpose of the invention] (Industrial application field) The present invention relates to an oxygen sensor and a method for manufacturing the same.
（従来の技術）
ホームエレクトロニスの第１歩として家庭用電気機器の
独立したまたは機器相互および全体の最適運転制御があ
る。これらは従来より大きいエネルギー効率、遠隔より
の無人運転、ネットワークコンピュータによる制御が可
能といった特徴を持っている。(Prior Art) The first step in home electronics is to control the optimal operation of household electric appliances independently, mutually, and as a whole. These have features such as greater energy efficiency than conventional systems, remote unmanned operation, and the ability to be controlled by network computers.
従来、人が電気機器の始動や運転中の動作条件を判断し
ていた。上述した電気機器は細かい制御や無人の始動お
よび運転継続が要求されており、人定式りに情報を電気
機器に送るものとしてセンサがある。Traditionally, people have been responsible for determining the operating conditions of electrical equipment during startup and operation. The above-mentioned electrical equipment requires detailed control and unattended start-up and continuous operation, and sensors are used to send information to the electrical equipment in a manual manner.
そのうち酸素センサは人間にとって重要な空気中の酸素
濃度から主に室内空気調整装置の制御を行なうことがで
き、室内空気の汚れによる不快感や酸欠による事故を防
ぐ目的に使われている。酸素センサの構造は第２図に示
すヒータ線を有する（５０）キャップ、酸素ポンプ機能
を有する安定化ジルコニア（５１）酸素ポンプ膜とから
なっていた。安定化ジルコニアとはＺｎＯ２にＹ２Ｏ１
，ＣａＯ，、ＭｇＯのうち１種を添加した焼結体を指す
。この５１酸素ポンプ膜の両側に酸素を透ス＆するよう
な５２．５３電極（たとえばＰｔ：白金）が形成してお
り５１の両側の酸素濃度により一種の濃淡電池を形成す
る。Among these, oxygen sensors can mainly control indoor air conditioning systems based on the oxygen concentration in the air, which is important for humans, and are used to prevent discomfort caused by dirty indoor air and accidents caused by lack of oxygen. The structure of the oxygen sensor consisted of a cap (50) having a heater wire as shown in FIG. 2, and a stabilized zirconia (51) oxygen pump membrane having an oxygen pumping function. Stabilized zirconia is ZnO2 and Y2O1
, CaO, and MgO. 52 and 53 electrodes (for example, Pt: platinum) that allow oxygen to pass through are formed on both sides of this 51 oxygen pump membrane, and a kind of concentration cell is formed depending on the oxygen concentration on both sides of 51.
第２図では安定化ジルコニアの一方の面が被測定雰囲気
に直接接し、他方は酸素が通過できる小さな穴を通じて
同じ雰囲気に接している。この状態で図のように直流電
圧を印加すると電気化学ポンプ作用で５３カソード側の
空間の酸素を５２アノード側にくみ出す酸素ポンプ機能
を有する。印加電圧を増すとくみ出される酸素量は増加
する。In FIG. 2, one side of the stabilized zirconia is in direct contact with the atmosphere to be measured, and the other side is in contact with the same atmosphere through a small hole through which oxygen can pass. In this state, when a DC voltage is applied as shown in the figure, it has an oxygen pumping function that pumps out oxygen in the space on the cathode side 53 to the anode side 52 by electrochemical pumping action. Increasing the applied voltage increases the amount of oxygen pumped out.
外部に連通ずる穴を通過する酸素量が律速になると電圧
を増加しても電流はほぼ一定値となる。この電流値を限
界電流と呼ぶ。限界電流は雰囲気の酸素濃度が大きいほ
ど大きな値をとり、限界電流の測定により酸素濃度の測
定ができる。第３図に限界電流型酸素センサの電圧特性
原理を示す。If the amount of oxygen passing through the hole communicating with the outside becomes rate-determining, the current will remain approximately constant even if the voltage is increased. This current value is called the limiting current. The limiting current takes on a larger value as the oxygen concentration in the atmosphere increases, and the oxygen concentration can be measured by measuring the limiting current. Figure 3 shows the principle of voltage characteristics of a limiting current type oxygen sensor.
上述した安定化ジルコニアの酸素ポンプ作用は３５０℃
〜５００℃以上の温度で起こり、そのため従来の酸素セ
ンサは第２図の５０キヤツプ上に５４ヒータが形成され
ている。この場合ヒータで発生した熱は５０キヤツプ中
を通り５１酸素ポンプ膜へ伝達する。このため５１酸素
ポンプ膜の動作温度を維持する場合、５０キヤツプ中で
の熱抵抗や外部への放熱を考慮してヒータを作動させる
必要がある。これは結果としてヒータ消費電力の増大を
招きヒータ寿命の低下、始動後センサ安定までの長時間
化やセンサ全体を断熱するため、センサの実装に対しス
ペース増大の原因となる。The oxygen pumping effect of the stabilized zirconia mentioned above is 350℃
This occurs at temperatures above 500 DEG C., which is why the conventional oxygen sensor has a heater 54 formed on a cap 50 in FIG. In this case, the heat generated by the heater passes through the cap 50 and is transferred to the oxygen pump membrane 51. Therefore, in order to maintain the operating temperature of the 51 oxygen pump membrane, it is necessary to operate the heater while taking into consideration the thermal resistance in the 50 cap and heat radiation to the outside. This results in an increase in the power consumption of the heater, a reduction in the life of the heater, a longer period of time for the sensor to stabilize after startup, and an increase in the space for mounting the sensor because the entire sensor is insulated.
また従来５１酸素ポンプ膜は円柱状の安定化ジルコニア
焼結体をから切り出したのち１００μｍ以下に研磨をす
ることにより得ていた。このため工数が多く、研磨の際
の割れによる不良率も高いという問題点を有していた。Conventionally, the 51 oxygen pump membrane was obtained by cutting out a cylindrical stabilized zirconia sintered body and then polishing it to a thickness of 100 μm or less. This has resulted in problems such as a large number of man-hours and a high defect rate due to cracks during polishing.
（発明が解決しようとする問題点）
本発明は上記の問題点を解消し、外部への放熱、ヒータ
消費電力が少なくまた製造工程において切り出しや研磨
の不要な酸素センサおよびその製造方法の提供を目的と
する。(Problems to be Solved by the Invention) The present invention solves the above-mentioned problems, and provides an oxygen sensor and its manufacturing method that has low heat dissipation to the outside, low heater power consumption, and does not require cutting or polishing in the manufacturing process. purpose.
（問題点を解決するための手段）
本発明は第１図に示す酸素センサの構造図のうち
１キヤツプがヒータ内蔵のアルミナ多層基板と例えば酸
化ジルコニウム９２ｍｏ１％、酸化イッリウム８ｍｏ１
％からなる電極を有する２酸素ポンプ膜とから構成され
る外部への放熱やヒータ電流の少ないことを特徴とする
酸素センサであり、工数が多く、不良率の大きい切り出
しや研磨の工程の不要なセラミックグリーンシートを用
い友ることにより２酸素ポンプを製造することが好まし
い。(Means for Solving the Problems) In the present invention, in the structural diagram of the oxygen sensor shown in FIG.
This oxygen sensor is characterized by low heat dissipation to the outside and low heater current, and is composed of a two-oxygen pump membrane with an electrode of Preferably, the two-oxygen pump is manufactured by using ceramic green sheets.
（作用）
まず酸素センサのうち１キヤツプは酸化アルミニウムを
９２〜９６重ｉ％含有する通常のアルミナグリーンシー
ト上に第１図の３小孔をあけたのち白金（ｐｔ）ペース
トを用いてヒータを形成する。(Function) First, for one cap of the oxygen sensor, three small holes as shown in Fig. 1 are made on a normal alumina green sheet containing 92 to 96% aluminum oxide by weight, and then a heater is attached using platinum (PT) paste. Form.
白金（Ｐｔ）ペースト乾燥後、アルミナグリーンシート
上および４ヒータ上にアルミナグリーンシートと同組成
の誘電体ペーストで絶縁層を印刷する。After drying the platinum (Pt) paste, an insulating layer is printed on the alumina green sheet and the four heaters using a dielectric paste having the same composition as the alumina green sheet.
印刷は通常の厚膜印刷法を使用した。その後誘電体ペー
スト乾燥し、１５５０℃〜１６５０℃で焼成を行ない、
ヒータ内蔵キャップを得ることができる。For printing, a normal thick film printing method was used. After that, the dielectric paste is dried and fired at 1550°C to 1650°C.
You can get a cap with a built-in heater.
このためヒータ部の熱は酸素ポンプ膜により近い位置で
発生するため■キャップ外側での温度も下げることがで
きヒータ消費電力を低減可能になった。このキャップ上
に以下に述べる酸素ポンプ獲を形成し酸素センサとする
。Therefore, the heat in the heater part is generated closer to the oxygen pump membrane, which allows the temperature outside the cap to be lowered, making it possible to reduce heater power consumption. An oxygen pump cap as described below is formed on this cap to form an oxygen sensor.
次に酸素センサの製造方法についてのべる。酸素ポンプ
膜は酸化物換算で９２ｍｏ１％の酸化ジルコニウム（Ｚ
ｒ Ｏ，）と８ｍｏ１％の酸化イツトリウムを含ム安
定化ジルコニアセラミックを使用する。酸化イツトリウ
ムの代りに酸化カルシウムまたは酸化マグネシウムを１
．６ ｍｏ １％ 使用してもよい。Next, the method for manufacturing the oxygen sensor will be described. The oxygen pump membrane is made of 92 mo1% zirconium oxide (Z
A stabilized zirconia ceramic containing 8 mo1% of yttrium oxide is used. 1 calcium oxide or magnesium oxide instead of yttrium oxide
．． 6 mo 1% may be used.
上記のセラミック粉末を用いてグリーンシートを形成す
るが通常その平均粒径は０．３〜０．５μｍでこの範囲
を超えると好適な焼結体を得ることが困難で好ましくな
い。グリーンシート中の有機バインダとしては例えばポ
リビニルアルコール、ポリアクリル酸エステル、ポリメ
タクリル酸エステル等の一般に用いられるものを使用す
ることができる。この有機バインダの上記セラミックの
スラリ中における配合割合は上記セラミックス粉末のス
ラリ全重量に対して３〜２０％（以下チは重量％の略で
ある）、好ましくは５〜１８％である。The above ceramic powder is used to form a green sheet, but its average particle size is usually 0.3 to 0.5 μm, and if it exceeds this range, it is difficult to obtain a suitable sintered body, which is not preferred. As the organic binder in the green sheet, commonly used organic binders such as polyvinyl alcohol, polyacrylic ester, polymethacrylic ester, etc. can be used. The blending ratio of this organic binder in the ceramic slurry is 3 to 20% (hereinafter "ch" is an abbreviation for weight %), preferably 5 to 18%, based on the total weight of the ceramic powder slurry.
配合割合が３％未満の場合は、製造上の他工程（印刷、
加工）に耐えつる強度に不足を生じ、２０％を超える場
合には脱脂、ち密な焼結が困難となって焼結体に反りを
生じ良好な酸素ポンプ膜を得ることがむづかしい。上記
セラミック粉末、有機バインダに有機溶媒、界面活性剤
、可塑剤を添加しこれらを均一に分散させてスラリを調
整する。ここで使用する有機溶媒としては一般に用いら
れているものであり、メチルエチルケトン、１．１．１
−１−リクロルエタン、トルエン、キシレン、ｎ−ブタ
ノール、酢酸メチル等を挙げることができる。スラリ中
の配合割合は１０〜５１．０％である。５１．０％以上
では脱泡が困難となり、１０％以下ではスラリ化しない
もしくはスラリ粘度が高くグリーンシート成形不可能と
なる。よってスラリ中への配合割合は１０〜５１チであ
る。If the blending ratio is less than 3%, other manufacturing processes (printing,
If it exceeds 20%, degreasing and dense sintering become difficult and the sintered body warps, making it difficult to obtain a good oxygen pump membrane. An organic solvent, a surfactant, and a plasticizer are added to the ceramic powder and organic binder, and these are uniformly dispersed to prepare a slurry. The organic solvent used here is one that is commonly used, such as methyl ethyl ketone, 1.1.1
-1-Lichloroethane, toluene, xylene, n-butanol, methyl acetate, etc. can be mentioned. The blending ratio in the slurry is 10 to 51.0%. If it is more than 51.0%, defoaming becomes difficult, and if it is less than 10%, it will not form into a slurry or the slurry will have a high viscosity, making it impossible to form a green sheet. Therefore, the mixing ratio in the slurry is 10 to 51 inches.
界面活性剤としては脂肪酸エステル、リン酸エステル、
スルホン酸エステル等がある。スラリ中の配合割合は０
１１〜１０％である。０．１係以下ではセラミック粉末
の粒子が凝集を起しち密な焼結体を得ることができなく
なる。１０％以上ではグリーンシートをポリエチレンフ
ィルムから剥離する際にグリーンシートにき裂を生じて
しまう。Surfactants include fatty acid esters, phosphate esters,
There are sulfonic acid esters, etc. The blending ratio in the slurry is 0
It is 11-10%. If the ratio is less than 0.1, the ceramic powder particles will agglomerate, making it impossible to obtain a dense sintered body. If it exceeds 10%, cracks will occur in the green sheet when it is peeled off from the polyethylene film.
可塑剤としてはアジピン配ジオクチル、ジブチルフタレ
ート、トリブチルホスフェート等がある。Examples of plasticizers include adipine dioctyl, dibutyl phthalate, and tributyl phosphate.
スラリ中の配合割合は０．１〜５チである。０．１ ％
以下ではグリーンシートの柔軟性が失なわれ実用に供せ
なくなる。５％以上ではグリーンシートにき裂を生じて
しまう。セラミック粉末のスラリ中の配合割合は４０〜
８０％である。４０％未満ではち密な焼結体を得ること
ができず、８０％以上ではスラリを得ることが不可能と
なる。混合順序はまずセラミック粉末、界面活性剤、有
機溶媒を所定量調合後、定時間混合する。次に有機バイ
ンダ、可塑剤を所定量加えたのち定時間混合する。The blending ratio in the slurry is 0.1 to 5. 0.1%
Below this, the green sheet loses its flexibility and becomes unusable. If it exceeds 5%, cracks will occur in the green sheet. The mixing ratio of ceramic powder in the slurry is 40~
It is 80%. If it is less than 40%, a dense sintered body cannot be obtained, and if it is more than 80%, it is impossible to obtain a slurry. The mixing order is as follows: Ceramic powder, surfactant, and organic solvent are first prepared in predetermined amounts, and then mixed for a predetermined time. Next, a predetermined amount of an organic binder and a plasticizer are added and then mixed for a predetermined time.
混合順序が異なると均一な分散スラリか得られなくなる
。混合、分散後、得られたスラリに脱泡処理を施し、ス
ラリ中に混在する空気を脱気する。If the mixing order is different, it will not be possible to obtain a uniformly dispersed slurry. After mixing and dispersing, the resulting slurry is subjected to defoaming treatment to remove air mixed in the slurry.
この脱気は後工程で形成するグリーンシート表面の平坦
化およびグリーンシート内部の空孔等の欠陥除去し飽酬
祇粘度を調整する目的で行なうものである。脱気後のス
ラリ粘度は０．１〜１０ Ｐａｓ、好ましくは０．５〜
５ Ｐａｓがよい。This degassing is performed for the purpose of flattening the surface of the green sheet to be formed in a subsequent process, removing defects such as pores inside the green sheet, and adjusting the saturation viscosity. Slurry viscosity after degassing is 0.1-10 Pas, preferably 0.5-10 Pas
5 Pas is good.
この脱気後のスラリを用いてグリーンシートを成形する
。この成形は、たとえばポリエステルフィルムのような
平滑板上でドクターブレード法を適用して行なう。成形
後電磁波による加熱もしくは送風乾燥などにより、成形
シートを乾燥する。A green sheet is formed using this degassed slurry. This molding is carried out, for example, by applying a doctor blade method on a smooth plate such as a polyester film. After forming, the formed sheet is dried by heating using electromagnetic waves or blow drying.
このようにしてグリーンシートを得ることができる。A green sheet can be obtained in this way.
上記グリーンシール上に所定の大きさを有する酸素通過
電極（ｐｔ等）を印刷後、所定の大きさに打ちぬき、１
５００℃〜１６５０℃の温度範囲で焼成する。１５００
℃以下ではち密な焼結が困難であり、１６５０℃以上で
は焼結体にふくれ、発泡が生じてしまう。従来は円柱状
の焼結体を切断、研磨していたが、本発明では可塑性を
有するグリーンシートの加工でこれに代えることができ
る。したがって切断、研磨にくらべ同時に多数測置るこ
とができ、研磨に伴なう割れを防ぐことができる。After printing an oxygen passing electrode (PT, etc.) having a predetermined size on the green seal, punch it out to a predetermined size.
Calcinate at a temperature range of 500°C to 1650°C. 1500
If the temperature is below 1650°C, it is difficult to achieve dense sintering, and if the temperature is above 1650°C, the sintered body will swell and foam. Conventionally, a cylindrical sintered body was cut and polished, but in the present invention, this can be replaced by processing a green sheet having plasticity. Therefore, compared to cutting and polishing, a large number of pieces can be measured and placed at the same time, and cracks caused by polishing can be prevented.
上記の酸素ポンプ膜を前述したアルミナ多層配基板上に
ガラス、ガラスセラミクス等で封着し酸素センサを得る
ことができる。An oxygen sensor can be obtained by sealing the oxygen pump membrane described above onto the alumina multilayer circuit board described above with glass, glass ceramics, or the like.
（実施例）
以下、実施例および比較例をあげ本発明をさらに詳述す
る。(Examples) Hereinafter, the present invention will be further explained in detail by giving Examples and Comparative Examples.
１）酸素センサ
第１図（ａｌは本発明酸素センサの断面図であり、同図
（ｂ）は平面図である。１キャンプ部はヒータ内蔵アル
ミナ多層基板でアルミナグリーンシート上にヒータをＰ
ｔペーストで印刷し、アルミナグリーンシートと同組成
の誘電ペーストをその上に絶縁層として印刷後基板中央
に５０μｍの５小孔をあけ１５５０℃で２時間保持し焼
成する。焼結後の基板寸法は５ Ｘ ５ （ｍ＋）であ
る。次に表１に示す１゜２．３組成の６安定化ジルコニ
アから得た１００μｍ厚のグリーンシート上ｌこ直径２
５ｍｍの円形の８白金カソード電極、９白金アノード電
極を表裏が一致するよう印刷する。1) Oxygen sensor FIG.
After printing, a dielectric paste having the same composition as the alumina green sheet was used as an insulating layer on top of the dielectric paste, and after printing, five small holes of 50 μm were made in the center of the substrate, and the substrate was held at 1550° C. for 2 hours and fired. The dimensions of the substrate after sintering are 5×5 (m+). Next, on a 100 μm thick green sheet obtained from 6-stabilized zirconia with a 1°2.3 composition shown in Table 1, a diameter of 2.
8 platinum cathode electrodes and 9 platinum anode electrodes each having a diameter of 5 mm are printed so that their front and back sides match.
次に上記グリーンシートを成極の同心円上に直径３前の
大きさの円に打ち抜き、１５８０℃で２時間焼成し、１
０酸素ポンプ膜を得た。前記１キヤツプおよび８酸素ポ
ンプ膜に１１アノード用成甑（ｐｉ ）を印刷し、さら
にその上に１２封着用ガラスを印刷する。Next, the above green sheet was punched out into a circle with a diameter of 3 mm on the concentric circle of polarization, and fired at 1580°C for 2 hours.
A zero oxygen pump membrane was obtained. 11 Anode preparation (pi) is printed on the 1 cap and 8 oxygen pump membranes, and 12 sealing glass is further printed thereon.
上記処理をした１キヤツプに１０酸素ポンプ膜をのせ１
０００℃、１０分で封着熱処理をした。最後に１０安定
化ジルコニアデイスク上の８白金カソードおよび１１白
金アノード用電極に１３カソードリード線、１４アノー
ドリード線、１キヤツプの１５ヒータリード線を配線し
、酸素ポンプを得た。Place 10 oxygen pump membranes on 1 cap treated above.
Sealing heat treatment was performed at 000°C for 10 minutes. Finally, 13 cathode lead wires, 14 anode lead wires, and 1 cap of 15 heater lead wires were wired to electrodes for 8 platinum cathodes and 11 platinum anodes on 10 stabilized zirconia disks to obtain an oxygen pump.
空気中で酸素ポンプの試験を行ない実施例１と比較例２
０の結果を表２に示す。比較例は第２図に示す従来の酸
素センサである。表２より本発明酸素センサはキャップ
外側底部における温度、ヒータ消費電力も小さくなって
いる。Testing the oxygen pump in air: Example 1 and Comparative Example 2
The results for 0 are shown in Table 2. A comparative example is a conventional oxygen sensor shown in FIG. Table 2 shows that the oxygen sensor of the present invention has a lower temperature at the outer bottom of the cap and lower heater power consumption.
２） 酸素ポンプ膜用グリーンシート
実施例４〜８
てラミックス粉末は平均粒径０．３〜０．５μｍの第１
表に示す１，２および３組成の安定化ジルコニアを使用
した。2) Examples 4 to 8 of green sheets for oxygen pump membranes
Stabilized zirconia of compositions 1, 2 and 3 shown in the table were used.
このセラミックス粉末に対して第３表に示すとおりの割
合で界面活性剤、有機溶剤を加え８ｈ’ｉ＝合後、第３
表の割合で有機バインダ、可塑剤を添加し１２ｈ混合し
、スラリを調整した。混合時の粘度は０．２ＰａＳであ
った。その後このスラリを脱泡し、さらにスラリ中に混
在する空気を脱気した。To this ceramic powder, a surfactant and an organic solvent were added in the proportions shown in Table 3.
An organic binder and a plasticizer were added in the proportions shown in the table and mixed for 12 hours to prepare a slurry. The viscosity during mixing was 0.2 PaS. Thereafter, this slurry was defoamed, and air mixed in the slurry was further degassed.
この時の粘度は１．８ Ｐａｓであった。このスラリを
用いてドクターブレード法により厚さ１００μｍのグリ
ーンシートを製造した。その後赤外線により加熱し、乾
燥させた。このグリーンシートを用いて酸素センサを前
記した通りに形成した。The viscosity at this time was 1.8 Pas. Using this slurry, a green sheet with a thickness of 100 μm was manufactured by a doctor blade method. Thereafter, it was heated and dried using infrared rays. This green sheet was used to form an oxygen sensor as described above.
比較例２３〜
表１に示すセラミックス組成物を、表３の割合でスラリ
に調整した。他の方法は実施例と同じである。実施例お
よび比較例を表３に示す。比較例として従来法による酸
素ポンプ膜作成も行なった。Comparative Example 23 ~ The ceramic composition shown in Table 1 was prepared into a slurry in the proportions shown in Table 3. Other methods are the same as in the examples. Examples and comparative examples are shown in Table 3. As a comparative example, an oxygen pump membrane was also fabricated using a conventional method.
表１の安定化ジルコニア粉末にポリビニルアルコールを
上記セラミック粉末の０．５重量％加えたのち乾燥させ
た。この粉末を直径３瓢の金型を用い、圧力１０００＃
／ｃｕｔで２００ｍの棒状に成形した。上記成形体を１
５８０℃、２時間で焼成し、１００μｍ厚に切断後、厚
さが７０μｍとなるよう研磨を行なった。実施例７と比
較例３１を表４に示す。Polyvinyl alcohol was added to the stabilized zirconia powder shown in Table 1 in an amount of 0.5% by weight based on the ceramic powder, and then dried. Using a mold with a diameter of 3 gourds, apply this powder to a pressure of 100#.
/cut into a 200 m rod shape. The above molded body is 1
It was fired at 580° C. for 2 hours, cut into 100 μm thick pieces, and then polished to a thickness of 70 μm. Example 7 and Comparative Example 31 are shown in Table 4.
以上に述べたとおり本発明方法は外部への放熱やヒータ
消費電力が少なくまた製造工程において切り出しや研磨
の不要な酸素センサおよびその製造が可能である。As described above, the method of the present invention allows for the production of an oxygen sensor with less heat dissipation to the outside, less heater power consumption, and no need for cutting or polishing in the manufacturing process.
よってその工業的価値は極めて大である。Therefore, its industrial value is extremely large.
第１図（ａｌ酸素センサの断面図、第１図（ｂｌは酸素
センサの平面図、第２図は従来のセンサの断面図、第３
図は１送圧特性図。
１・・・キャップ、３・・・ヒータ、５・・・小孔、６
・・・安定化ジルコニア、８・・・白金カソード電極、
９・・・白金アノード電極、１０・・・酸素ポンプ膜、
１１・・・アノード用剋極、１２・・・封着用ガラス、
１３・・・カソードリード線、１４・・・アノードリー
ド線、１５・・・ヒータリード線。
第４表 実施例および比較例
代理人 弁理士 則 近 息 佑
同 竹 花 喜久男
第 １ 図
該 ２ 図
電 圧
第 ３ 図Figure 1 (al) is a cross-sectional view of the oxygen sensor, Figure 1 (bl is a plan view of the oxygen sensor, Figure 2 is a cross-sectional view of a conventional sensor,
The figure is a 1-pressure characteristic diagram. 1...Cap, 3...Heater, 5...Small hole, 6
... Stabilized zirconia, 8... Platinum cathode electrode,
9... Platinum anode electrode, 10... Oxygen pump membrane,
11... Anode electrode, 12... Sealing glass,
13... Cathode lead wire, 14... Anode lead wire, 15... Heater lead wire. Table 4 Examples and Comparative Examples Agent Patent Attorney Rule Yudo Chika Kikuo Takehana Figure 1 Figure 2 Voltage Figure 3
Claims (2)
有する安定化ジルコニア製の酸素ポンプ膜とから構成す
ることを特徴とする酸素センサ。(1) An oxygen sensor comprising an alumina multilayer substrate with a built-in heater and an oxygen pump membrane made of stabilized zirconia and having electrodes on both sides.
したセラミックグリーンシートから得られた酸素ポンプ
膜を用いることを特徴とした特許請求の範囲第１項記載
の酸素センサ。(2) The oxygen sensor according to claim 1, which uses an oxygen pump membrane obtained from a ceramic green sheet in which ceramic powder made of stabilized zirconia is dispersed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61160816A JPS6318262A (en) | 1986-07-10 | 1986-07-10 | Oxygen sensor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61160816A JPS6318262A (en) | 1986-07-10 | 1986-07-10 | Oxygen sensor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6318262A true JPS6318262A (en) | 1988-01-26 |
Family
ID=15723040
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61160816A Pending JPS6318262A (en) | 1986-07-10 | 1986-07-10 | Oxygen sensor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6318262A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010501866A (en) * | 2006-08-29 | 2010-01-21 | フラウンホッファー−ゲゼルシャフト・ツァー・フォデラング・デル・アンゲワンテン・フォーシュング・エー．ファウ． | Process for the production of catalytically active components for thermal ionization detectors for the detection of halogen-containing compounds and oxide ceramic materials for the components |
-
1986
- 1986-07-10 JP JP61160816A patent/JPS6318262A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010501866A (en) * | 2006-08-29 | 2010-01-21 | フラウンホッファー−ゲゼルシャフト・ツァー・フォデラング・デル・アンゲワンテン・フォーシュング・エー．ファウ． | Process for the production of catalytically active components for thermal ionization detectors for the detection of halogen-containing compounds and oxide ceramic materials for the components |
| US8618018B2 (en) | 2006-08-29 | 2013-12-31 | Fraunhofer-Gesellschaft Zur Forderung Der Angewandten Forschung E.V. | Catalytically active component for thermal ionization detectors for the detection of halogen-containing compounds and process for producing an oxide-ceramic material for the component |
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