JPS6319549A - Oxygen concentration detector - Google Patents
Oxygen concentration detectorInfo
- Publication number
- JPS6319549A JPS6319549A JP61164939A JP16493986A JPS6319549A JP S6319549 A JPS6319549 A JP S6319549A JP 61164939 A JP61164939 A JP 61164939A JP 16493986 A JP16493986 A JP 16493986A JP S6319549 A JPS6319549 A JP S6319549A
- Authority
- JP
- Japan
- Prior art keywords
- metal oxide
- electrode layer
- porous
- crystal structure
- alkaline earth
- 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
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 18
- 239000001301 oxygen Substances 0.000 title claims abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 30
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 30
- 239000007789 gas Substances 0.000 claims abstract description 25
- 239000013078 crystal Substances 0.000 claims abstract description 15
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 7
- 230000003197 catalytic effect Effects 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 238000002485 combustion reaction Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 230000004043 responsiveness Effects 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 6
- -1 oxygen ion Chemical class 0.000 abstract description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 3
- 230000002093 peripheral effect Effects 0.000 abstract description 3
- 230000001681 protective effect Effects 0.000 abstract description 3
- 238000007740 vapor deposition Methods 0.000 abstract description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract 2
- 230000015556 catabolic process Effects 0.000 abstract 2
- 239000000567 combustion gas Substances 0.000 abstract 2
- 238000006731 degradation reaction Methods 0.000 abstract 2
- 239000003054 catalyst Substances 0.000 abstract 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 abstract 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 238000007751 thermal spraying Methods 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 25
- 229910052717 sulfur Inorganic materials 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical class O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 239000011253 protective coating Substances 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 229910002090 carbon oxide Inorganic materials 0.000 description 2
- 238000007772 electroless plating Methods 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 101100194003 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) rco-3 gene Proteins 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Measuring Oxygen Concentration In Cells (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は例えば、自動車内燃機関の空燃比制御のために
用いられる酸素濃度検出器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 concentration detector used, for example, for controlling the air-fuel ratio of an automobile internal combustion engine.
従来公知のこの種のものとしては、例えば特開昭５３−
３０３８６号公報に記載されているごとく、酸素イオン
伝導性金属酸化物より固体電解質素子の排気ガス側の電
極層の表面にマグネシアアルミナスピネル等の金属酸化
物より成る多孔性保護層を形成し、該保護層により上記
電極層を排気ガスに対し保護する構成の酸素濃度検出器
がある。Conventionally known products of this type include, for example, Japanese Unexamined Patent Application Publication No. 1986-
As described in Japanese Patent No. 30386, a porous protective layer made of a metal oxide such as magnesia alumina spinel is formed on the surface of the electrode layer on the exhaust gas side of the solid electrolyte element than the oxygen ion conductive metal oxide. There is an oxygen concentration detector configured to protect the electrode layer from exhaust gas with a protective layer.
従来のものでは自動車内燃機関に使用した場合、燃料で
あるガソリン中に含まれる鉛、あるいは内燃機関の潤滑
油中に含まれるイオウが排気ガス中に残存しているため
、該鉛、イオウが上記保護層の多孔部を通って排気ガス
側電橿層に到達しやすい。When conventional products are used in automobile internal combustion engines, lead and sulfur contained in the gasoline fuel and sulfur contained in the lubricating oil of the internal combustion engine remain in the exhaust gas. It is easy to reach the exhaust gas side electric layer through the porous portion of the protective layer.
排気ガス側の電極層は白金等の触媒金属で構成されてお
り、上記鉛、イオウがこの電極層と反応して電極層を構
成する白金粒子が凝集し触媒活性が低下するという問題
を有している。The electrode layer on the exhaust gas side is made of a catalytic metal such as platinum, and there is a problem in that the lead and sulfur mentioned above react with this electrode layer, causing the platinum particles that make up the electrode layer to aggregate and reduce the catalytic activity. ing.
また、排気ガス中の未燃焼失化水素、−酸化炭素が上記
電極層の触媒作用によりカーボンを生成し、これが電極
層の白金と反応してグラファイト化し電極層の剥離の原
因となるという問題を有している。In addition, unburned lost hydrogen and carbon oxides in the exhaust gas generate carbon due to the catalytic action of the electrode layer, and this reacts with the platinum of the electrode layer to form graphite, causing the electrode layer to peel off. have.
本発明は上記の諸問題を解決しようとするものであって
、燃焼排気ガス側の電）重層の表面に、触媒活性を有し
たべＬ７ブスカイト型結晶構造の金勇酸化物とアルカリ
土類炭酸塩とを包含して構成した多孔性被膜を形成した
ものである。The present invention is an attempt to solve the above-mentioned problems, and consists of a metal oxide having a catalytic activity and an alkaline earth carbonate crystal structure, and an alkaline earth carbonate on the surface of the electrolyte layer on the combustion exhaust gas side. A porous film is formed by including salt.
本発明によれば、上記多孔性被膜のペロブスカイト型結
晶構造を有した金属酸化物およびアルカリ土類炭酸塩が
燃焼排気ガス中の鉛、イオウと反応し、鉛を固溶したペ
ロブスカイト金属酸化物を形成し、また硫酸塩を形成す
る。この結果、鉛。According to the present invention, the metal oxide and alkaline earth carbonate having a perovskite-type crystal structure of the porous coating react with lead and sulfur in the combustion exhaust gas to form a perovskite metal oxide containing lead as a solid solution. forms and also forms sulfates. As a result, lead.
イオウは上記被ＩＩＱで捕捉される。Sulfur is captured in the IIQ.
また、上記被膜のペロブスカイト型結晶構造の金属酸化
物の触媒活性によって、炭化水素、−酸化水素の不均化
反応が生じにくいため、カーボンの析出が抑制され、従
ってカーボンと電極層との反応が防止されるのである。In addition, due to the catalytic activity of the metal oxide having a perovskite crystal structure in the above film, disproportionation reactions between hydrocarbons and hydrogen oxides are difficult to occur, so carbon precipitation is suppressed and the reaction between carbon and the electrode layer is suppressed. It is prevented.
このように、本発明によれば、排気ガス中の成分が電極
層と反応することによる電極層の劣化を防止することが
でき、従って従来に比べて応答性の低下を抑えることが
可能となる。As described above, according to the present invention, it is possible to prevent the deterioration of the electrode layer due to the components in the exhaust gas reacting with the electrode layer, and therefore it is possible to suppress the decrease in responsiveness compared to the conventional method. .
以下本発明を具体的実施例により詳細に説明する。 The present invention will be explained in detail below using specific examples.
第１図において、１は酸素イオン伝導性金属酸化物から
なる固体電解質素子で、ＺｒＯ□、Ｃｅ０ｚ等の金属酸
化物７０〜９７モル％に２価又は３価の金属酸化物を３
０〜３モル％固）容させた緻密な焼結体である。この素
子１の燃焼排気ガスにさらされる側の外周面には多孔性
電極層２としてｐｔを蒸着、ペースト焼付、無電解メッ
キ等の方法で付着させである。また酸素標ｔ１ｕガスに
さらされる内周面には、ペースト焼付、無電解メッキ等
の方法で同様にｐｔを付着させた多孔性電極層３を設け
である。さらに、電極層２上には、多孔性保８Ｗ被膜４
が電極保護の目的でＡ６ｚＯ，、ＭｇＯ・ＡＡ２Ｑ、、
、Ｚ ｒＯ，等の耐熱性金属酸化物をプラズマ溶射法等
により付着させである。さらに保護被膜４上には発明の
最も重要なペロブスカイト型結晶構造を有する金属酸化
物例えはＬａｏ、ｅＳｒｏ、ｚＣｏｏｓ、Ｌ ａｏ、、
Ｓ ｒｏ１ＭｎＱ３等をスラリー化し、塗布した多孔性
被膜５を付着させである。保護被膜４は公知の技術であ
るため説明を省くが、本発明の被膜５についてより詳細
に説明する。In FIG. 1, 1 is a solid electrolyte element made of an oxygen ion conductive metal oxide, in which 70 to 97 mol% of a metal oxide such as ZrO□ or Ce0z is mixed with 3 divalent or trivalent metal oxides.
It is a dense sintered body with a solid content of 0 to 3 mol%. PT is deposited as a porous electrode layer 2 on the outer circumferential surface of the element 1 on the side exposed to combustion exhaust gas by a method such as vapor deposition, paste baking, electroless plating, or the like. Further, on the inner peripheral surface exposed to the oxygen standard t1u gas, there is provided a porous electrode layer 3 to which PT is similarly attached by a method such as paste baking or electroless plating. Further, on the electrode layer 2, a porous 8W coating 4 is provided.
is A6zO, MgO・AA2Q, for the purpose of electrode protection.
, ZrO, or the like is deposited by plasma spraying or the like. Further, on the protective coating 4, metal oxides having a perovskite type crystal structure, which is the most important for the invention, such as Lao, eSro, zCoos, Lao, etc.
S ro1MnQ3 and the like are made into a slurry and the porous film 5 is applied thereto. Since the protective coating 4 is a well-known technique, its explanation will be omitted, but the coating 5 of the present invention will be explained in more detail.
本発明のペロブスカイト型金属酸化物は、例えはＣＯ（
Ｎ ０ｓ）ｚ ・６１（ｚｏ、 Ｌ ａ （ＮＯｚ）
３・６Ｈ２０，Ｓｒ （ＮＯ３）２を水に溶かし混合
水ｍ ｉ’ｌＩを準備する。この水）８液に過剰量のＮ
ａ ２ＣＯ。The perovskite metal oxide of the present invention is, for example, CO(
N 0s)z ・61(zo, L a (NOz)
3.6H20, Sr (NO3)2 is dissolved in water to prepare mixed water mi'lI. Excess amount of N in this water) 8 liquid
a2CO.
を加えた水）８液を少しずつ滴下させて共沈物を得る。Add water) 8 solution little by little to obtain a coprecipitate.
この時、Ｃｏ （ＯＨ） ３． Ｌ ａ （ＯＨ）
３． Ｓ ｒＣＯ３の共沈物が得られるため、この共
／；を物を濾過しよく洗浄する。次に、この共沈物を真
空凍結乾燥させ、６００°Ｃ程度の温度で仮焼成し粉砕
後、さらｇこ８００〜９００°Ｃ程度で焼成し、ＬａＯ
，！ｌ５ｒｏ、ｚＣｏＯ：＋の粉末を得る。この粉末に
対して１０ｗｔ％のアルカリ土類炭酸塩である５ｒＣＯ
ｓを混合し、この混合粉末をアルミナゾル、硝酸アルニ
ミウム又は硝酸ランタンを添加した水に溶かし泥漿化し
、厚さ１０〜３０μ程度上記の被膜４の表面に彷布する
。その後乾燥し、７００〜８００℃程度で焼付で被膜と
する。At this time, Co (OH) 3. L a (OH)
3. Since a coprecipitate of S rCO3 is obtained, this coprecipitate is filtered and washed thoroughly. Next, this coprecipitate is vacuum freeze-dried, pre-calcined at a temperature of about 600°C, crushed, and then calcined at a temperature of about 800 to 900°C on a dry cloth.
，! l5ro, zCoO:+ powder is obtained. 10 wt% alkaline earth carbonate 5rCO to this powder
This mixed powder is dissolved in water to which alumina sol, aluminum nitrate, or lanthanum nitrate has been added to form a slurry, and the slurry is spread on the surface of the coating 4 to a thickness of about 10 to 30 μm. It is then dried and baked at about 700 to 800°C to form a film.
次に、耐久実験結果について説明をする。Next, the durability test results will be explained.
６気筒２．８１のエンジンを用いて、これを４３０Ｏｒ
＋ｐ＋ｍで運転し、検出器温度７５０℃、空燃比（Ａ／
Ｆ）１２．ガソリン中のＰｂ量１００ｍｇ／Ｕ、Ｓ、Ｇ
の劣化加速条件にて４００時間まで実施した。この耐久
条件後、６気筒２．８１のエンジンを用い１５００ｒ、
ｐ、ｍで運転し、検出器温度４００℃、空燃比をλ０．
９→１．１に変化させた際の応答時間を第２図に、また
内部抵抗を第３図に示す。Using a 6 cylinder 2.81 engine, this is 430 Or
+p+m, detector temperature 750℃, air fuel ratio (A/
F)12. Pb amount in gasoline 100mg/U, S, G
The test was carried out for up to 400 hours under accelerated deterioration conditions. After this endurance condition, 1500r using a 6 cylinder 2.81 engine,
p, m, the detector temperature was 400°C, and the air-fuel ratio was λ0.
FIG. 2 shows the response time when changing from 9 to 1.1, and FIG. 3 shows the internal resistance.
なお、第２図中、従来例は本発明の被ＩＦＪ５を備えな
いものである。第２図かられかるように、本発明は応答
性が掻めて安定しており、初期値を４００ＨＩも維持し
ている。ここで従来の２００時間までの応答性低下は、
ｐｂもしくはエンジンオイル中のＳ、排気ガス中のＩ
ＣもしくはＣがＰＬ電極層と反応し凝集が進行すること
による一見ガス応答性が速くなることによる。しかし電
極層の劣化は進んでいるため、内部抵抗が増加している
。In addition, in FIG. 2, the conventional example does not include the IFJ 5 of the present invention. As can be seen from FIG. 2, the responsiveness of the present invention is excellent and stable, and the initial value is maintained at 400 HI. Here, the conventional decrease in responsiveness up to 200 hours is
PB or S in engine oil, I in exhaust gas
This is because C or C reacts with the PL electrode layer and aggregation progresses, which seemingly makes the gas response faster. However, as the electrode layer continues to deteriorate, the internal resistance increases.
しかし、２００時間以後はさらに凝集による劣化が進行
し、７Ｓ極層の触媒活性機能が低下すること、付着物（
Ｐｂ、Ｐ、Ｓ、Ｃａ、Ｚｎ等の化合物）の堆積による電
極層の保護被膜の目詰まり等により応答性が遅くなるこ
とをあられしている。一方、本発明のものは、電極層が
ｐｂ、 Ｓ、 １４Ｃ，Ｃ等と反応するのをペロプス
カイト型金属酸化物により防止される。また、このペロ
プスカイト型金属酸化物より成る被膜は前記の保護被膜
４よりｌオーダ大きい細孔容積を有しているため、この
保３ｉ被膜４の目詰りを生じることなく、ガス拡散を阻
害することもない。However, after 200 hours, deterioration due to aggregation further progresses, the catalytic activity of the 7S electrode layer decreases, and deposits (
It has been reported that the response becomes slow due to clogging of the protective coating of the electrode layer due to the accumulation of compounds (such as Pb, P, S, Ca, Zn, etc.). On the other hand, in the case of the present invention, the perovskite metal oxide prevents the electrode layer from reacting with PB, S, 14C, C, etc. In addition, since this coating made of perovskite metal oxide has a pore volume that is an order of magnitude larger than that of the protective coating 4, gas diffusion is inhibited without causing clogging of the protective coating 4. Not at all.
次に、前記被膜５にアルカリ土類炭酸塩が含まれている
ことによる効果を説明する。検出器の構成は前述したと
おりであり、被膜の構成としては化学式のＬ ａ ６．
＋＋ Ｓ ｒ ６．ｚｃ６０３のペロプスカイト型結晶
構造の金属酸化物とこれに対しｌＱｗｔ％の５ｒＣＣｈ
とを含むものである。Next, the effect of containing alkaline earth carbonate in the coating 5 will be explained. The structure of the detector is as described above, and the structure of the film is the chemical formula La6.
++ S r 6. Zc603 metal oxide with perovskite crystal structure and lQwt% 5rCCh
This includes:
また、上記の３ｒＣＯ，を含まない上記化学式ペロプス
カイト型結晶構造の金属酸化物で一構成した被膜を備え
た検出器を比較例として用意した。In addition, a detector provided with a coating made of a metal oxide having the above-mentioned chemical formula perovskite crystal structure that does not contain the above-mentioned 3rCO was prepared as a comparative example.
耐久条件は次のようである。即ち、２．６１６気筒エン
ジンを１６０ Ｏｒ、ｐ、ｍで理論空燃比で運転し、検
出器温度８５０℃で５０時間まで実施した。使用したガ
ソリンは１．２ ｍｇ／ ｌのｐｂを含むものである。The durability conditions are as follows. That is, a 2.616-cylinder engine was operated at a stoichiometric air-fuel ratio of 160 Or, p, m, and the test was carried out for up to 50 hours at a detector temperature of 850°C. The gasoline used contained 1.2 mg/l of PB.
結果を第１表に示す。The results are shown in Table 1.
第 １ 表
□
□□□山
第１表から理解されるごとく、アルカリ土類炭酸塩を含
むものではｓ、ｐｂの捕捉効果が大きいことがわかる。Table 1 □ □□□ Mountain As can be understood from Table 1, those containing alkaline earth carbonates have a large s and pb trapping effect.
なお、本発明は、次のごとき変形が可能である。Note that the present invention can be modified as follows.
（１１触媒活性を有したペロプスカイト型結晶構造の金
属酸化物としては、化学式
％式％
０．５であり、ＭはＣｏ、Ｎｉ、Ｍｎより選ばれた少な
くとも一種である）で表わされるものが用いられる。(11 Metal oxides with a perovskite crystal structure having catalytic activity are those represented by the chemical formula % 0.5, where M is at least one selected from Co, Ni, and Mn). used.
（２）アルカリ土類金属炭酸塩としては、Ｓ ｒ ＣＯ
ｚの他にＢａＣ０，、ＣａＣ０，、ＭｇＣ０，、ＢｅＣ
０゜でもよい。(2) As the alkaline earth metal carbonate, S r CO
In addition to z, BaC0,, CaC0,, MgC0,, BeC
It may be 0°.
（３）固体電解質素子は一端が開口し他端が閉じたコツ
プ形状に限らず、円板形状等でもよい。(3) The solid electrolyte element is not limited to a cup shape with one end open and the other end closed, but may also be a disk shape or the like.
第１図は本発明の一実施例を示す断面図、第２図および
第３図は本発明の詳細な説明に供する特性図である。
１・・・固体電解質素子、２．３・・・電極層、４・・
・保護被膜、５・・・多孔性被膜。
＾ 区
Ｆ 〜 の 寸 の
○ Ｏ
埒 郷
Ｏ
手続補正書
昭和６１年 ７月ンλ日
３補正をする者
事件との関係 特許出願人
愛知県刈谷市昭和町１丁目１番地
（４２６）日本電装株式会社
〒４４８ 愛知県刈谷市昭和町１丁目１番地日本電装株
式会社内
（７４７７）弁理士 間部 隆
（Ｔｉｔ＜０５６６＞２２−３３１１） “５補正
の対象
６ 補正の内容
明細書を次のとおり訂正する。
（１）特許請求の範囲を別紙のとおり訂正する。
（２）第４真第５行ないし第６行の「とを包含して構成
した」を「を含む」に訂正する。
（３）第４真第１５行ないし第１６行の「−酸化水素」
を「−酸化炭素」に訂正する。
（４）第６頁第４行の「発明の」を「本発明において」
に訂正する。
（５）第６頁第１Ｏ行ないし第１１行の「例えは」を「
例えば」に訂正する。
（６）第７頁第４行のｒ３０μＪをｒ ３０ ｕｍＪに
訂正する。
（７）第７頁第６行の「・・・被膜とする。」の後に次
の文を追加する。
「なお、アルカリ土類金属炭酸塩は０．１ないし２０ｗ
ｔ％、好ましくは１．０〜ｌＱｗｔ％含まれるのが好ま
しい。Ｑ、ｌ ｗ ｔ％以下ではＳのトラップ効果が低
下し、２０ｗｔ％以上になるとペロブスカイト型金属酸
化物の触媒活性が低下する。」（８）第７頁第９行の「
ｒ、ρ、ｍｌをｒｒ、ｐ、ｍ、Ｊに訂正する。
（９）第７頁第１３行のｒｒ＋ｐ＋ｍ Ｊをｒｒ、ｐ、
ｍ、Ｊに訂正する。
ＧＯ）第７頁第２０行の「応答性低下」を「応答性向上
」に訂正する。
αＢ第８頁第１行の「排気ガス中のＨＣＪを「排気ガス
中のＰｂ、ＨＣＪに訂正する。
（２）第９頁第７行のｒｒ、ｐ、ｍ Ｊ”をｒｒ、ｐ、
ｍ、Ｊに訂正する。
０争第１０頁第４行のｒＬａ １−ｘＳｒ ｘＭＯｉ
ＪをｒＬａ＋−ｘ Ｓ ｒＭＯ３Ｊに訂正する。
２、特許請求の範囲
（１）酸素イオン伝導性金属酸化物より成る固体電解質
素子と、該素子の一方の側の酸素標準ガスと接触する表
面に設けた多孔性電極層と、前記素子の他方の側の燃焼
排気ガスと接触する表面に設けた多孔性電極層と、該排
気ガス側の電極層の表面に形成され、触媒活性を有した
ペロブスカイト型結晶構造の金属酸化物およびアルカリ
土類炭酸塩を含む多孔性被膜−奎、包含したことを特徴
とする酸素濃度検出器。
（２）前記ペロブスカイト型結晶構造の金属酸化物は、
化学式がｌ、 ａ １−Ｘ Ｓ ｒＸＭＯ，であり、式
中Ｘは０．１ないし０．５であって、Ｍは、Ｃｏ、 Ｎ
ｉ。
Ｍｎより選ばれた少なくとも一種であり、前記アルカリ
土類炭酸塩は５ｒＣＯ，であることを特徴とする特許請
求の範囲第１項記載の酸素濃度検出器。
（３）前記ペロブスカイト型結晶構造の金属酸化物は化
学式Ｌ ａｏ、ｓ Ｓ ｒＯ，Ｚ Ｃ６０３であり、前
記ＳｒＣＯ３はＬａ６．ｓ Ｓｒ、ｚ ｃｏｏ、に対し
１１〜２０ｗｔ％添加されていることを特徴とする特許
請求の範囲第２項記載の酸素濃度検出器。FIG. 1 is a sectional view showing one embodiment of the present invention, and FIGS. 2 and 3 are characteristic diagrams for explaining the present invention in detail. 1... Solid electrolyte element, 2.3... Electrode layer, 4...
- Protective film, 5... porous film. ^ Ward F ~ Dimensions of ○ O Nigo O Procedural Amendment Document July 1986 3 Relationship with the case of the person making the amendment Patent applicant Nippon Denso, 1-1 Showa-cho (426), Kariya City, Aichi Prefecture Nippondenso Co., Ltd. (7477) 1-1 Showacho, Kariya City, Aichi Prefecture, Japan 448 Japan Patent Attorney Takashi Mabe (Tit<0566>22-3311) (1) The scope of the claims is corrected as shown in the attached sheet. (2) In the fourth sentence, lines 5 and 6, "consisting of" is corrected to "includes." (3) “-Hydrogen oxide” in the 4th true, lines 15 and 16
Correct it to "-carbon oxide." (4) In the 4th line of page 6, change “of the invention” to “in the present invention”
Correct. (5) On page 6, line 1O to line 11, replace “analogue” with “
For example, correct it to ``. (6) Correct r30 μJ on page 7, line 4 to r 30 umJ. (7) On page 7, line 6, add the following sentence after "...as a film." ``In addition, alkaline earth metal carbonates are 0.1 to 20w.
t%, preferably 1.0 to 1Qwt%. When Q,l wt% or less, the S trapping effect decreases, and when it exceeds 20 wt%, the catalytic activity of the perovskite metal oxide decreases. ” (8) Page 7, line 9 “
Correct r, ρ, ml to rr, p, m, J. (9) rr+p+m J on page 7, line 13 as rr, p,
m, correct to J. GO) Correct "decreased responsiveness" to "improved responsiveness" on page 7, line 20. αB, page 8, line 1, “HCJ in exhaust gas” is corrected to “Pb, HCJ in exhaust gas.” (2) Page 9, line 7, “rr, p, m J” is changed to rr, p,
m, correct to J. 0 contest, page 10, line 4 rLa 1-xSr xMOi
Correct J to rLa+-x S rMO3J. 2. Claims (1) A solid electrolyte element made of an oxygen ion conductive metal oxide, a porous electrode layer provided on the surface of one side of the element that comes into contact with an oxygen standard gas, and the other side of the element. A porous electrode layer provided on the surface that comes into contact with the combustion exhaust gas on the exhaust gas side, and a metal oxide and alkaline earth carbonate having a perovskite crystal structure and having catalytic activity formed on the surface of the electrode layer on the exhaust gas side. An oxygen concentration detector comprising a porous film containing salt. (2) The metal oxide with the perovskite crystal structure is
The chemical formula is l, a 1-X S rXMO, where X is 0.1 to 0.5, and M is Co, N
i. 2. The oxygen concentration detector according to claim 1, wherein the alkaline earth carbonate is at least one selected from Mn and the alkaline earth carbonate is 5rCO. (3) The metal oxide having the perovskite crystal structure has the chemical formula Lao, s S rO, Z C603, and the SrCO3 has the chemical formula La6. 3. The oxygen concentration detector according to claim 2, wherein s Sr and z coo are added in an amount of 11 to 20 wt%.
Claims (3)
素子と、該素子の一方の側の酸素標準ガスと接触する表
面に設けた多孔性電極層と、前記素子の他方の側の燃焼
排気ガスと接触する表面に設けた多孔性電極層と、該排
気ガス側の電極層の表面に形成され、触媒活性を有した
ペロブスカイト型結晶構造の金属酸化物およびアルカリ
土類炭酸塩を含む多孔性被膜とを包含したことを特徴と
する酸素濃度検出器。(1) A solid electrolyte element made of an oxygen ion-conducting metal oxide, a porous electrode layer provided on a surface in contact with oxygen standard gas on one side of the element, and combustion exhaust gas on the other side of the element. a porous electrode layer provided on the surface in contact with the exhaust gas side, and a porous coating formed on the surface of the electrode layer on the exhaust gas side and containing a metal oxide having a catalytic activity and a perovskite crystal structure and an alkaline earth carbonate. An oxygen concentration detector comprising:
化学式がＬａｌ−ｘＳｒｘＭＯ＿３であり、式中ｘは０
．１ないし０．５であって、Ｍは、Ｃｏ，Ｎｉ，Ｍｎよ
り選ばれた少なくとも一種であり、前記アルカリ土類炭
酸塩はＳｒＣＯ＿３であることを特徴とする特許請求の
範囲第１項記載の酸素濃度検出器。(2) The metal oxide with the perovskite crystal structure is
The chemical formula is Lal-xSrxMO_3, where x is 0
．． 1 to 0.5, M is at least one selected from Co, Ni, and Mn, and the alkaline earth carbonate is SrCO_3. Oxygen concentration detector.
学式Ｌａ＿０＿．＿８Ｓｒ＿０＿．＿２Ｃ＿０Ｏ＿３で
あり、前記ＳｒＣＯ＿３はＬａ＿０＿．＿８Ｓｒ＿０＿
．＿２Ｃ＿０Ｏ＿３に対し１０ｗｔ％添加されているこ
とを特徴とする特許請求の範囲第２項記載の酸素濃度検
出器。(3) The metal oxide having the perovskite crystal structure has the chemical formula La_0_. _8Sr_0_. _2C_0O_3, and the SrCO_3 is La_0_. _8Sr_0_
．． The oxygen concentration detector according to claim 2, wherein 10 wt% of _2C_0O_3 is added.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61164939A JPH0668479B2 (en) | 1986-07-14 | 1986-07-14 | Oxygen concentration detector |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61164939A JPH0668479B2 (en) | 1986-07-14 | 1986-07-14 | Oxygen concentration detector |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6319549A true JPS6319549A (en) | 1988-01-27 |
| JPH0668479B2 JPH0668479B2 (en) | 1994-08-31 |
Family
ID=15802715
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61164939A Expired - Lifetime JPH0668479B2 (en) | 1986-07-14 | 1986-07-14 | Oxygen concentration detector |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0668479B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6005037A (en) * | 1994-10-31 | 1999-12-21 | Hoechst Ag | Molding material for processing sinterable polymers |
| JP2006511806A (en) * | 2002-12-23 | 2006-04-06 | ローベルト ボツシユ ゲゼルシヤフト ミツト ベシユレンクテル ハフツング | Measuring sensor |
| JP2010038600A (en) * | 2008-08-01 | 2010-02-18 | Nippon Soken Inc | Gas sensor element |
| CN103529102A (en) * | 2013-10-25 | 2014-01-22 | 郑龙华 | Multi-layer composite protective layer of oxygen sensor and manufacturing method thereof |
-
1986
- 1986-07-14 JP JP61164939A patent/JPH0668479B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6005037A (en) * | 1994-10-31 | 1999-12-21 | Hoechst Ag | Molding material for processing sinterable polymers |
| JP2006511806A (en) * | 2002-12-23 | 2006-04-06 | ローベルト ボツシユ ゲゼルシヤフト ミツト ベシユレンクテル ハフツング | Measuring sensor |
| US7998327B2 (en) | 2002-12-23 | 2011-08-16 | Robert Bosch Gmbh | Measuring sensor |
| JP2010038600A (en) * | 2008-08-01 | 2010-02-18 | Nippon Soken Inc | Gas sensor element |
| CN103529102A (en) * | 2013-10-25 | 2014-01-22 | 郑龙华 | Multi-layer composite protective layer of oxygen sensor and manufacturing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0668479B2 (en) | 1994-08-31 |
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