JPH0713609B2 - Oxygen sensor for internal combustion engine - Google Patents
Oxygen sensor for internal combustion engineInfo
- Publication number
- JPH0713609B2 JPH0713609B2 JP62275856A JP27585687A JPH0713609B2 JP H0713609 B2 JPH0713609 B2 JP H0713609B2 JP 62275856 A JP62275856 A JP 62275856A JP 27585687 A JP27585687 A JP 27585687A JP H0713609 B2 JPH0713609 B2 JP H0713609B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst layer
- oxygen
- oxygen sensor
- platinum
- air
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000001301 oxygen Substances 0.000 title claims description 29
- 229910052760 oxygen Inorganic materials 0.000 title claims description 29
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims description 25
- 238000002485 combustion reaction Methods 0.000 title claims description 4
- 239000003054 catalyst Substances 0.000 claims description 42
- 239000010410 layer Substances 0.000 claims description 40
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 40
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 28
- 230000003647 oxidation Effects 0.000 claims description 23
- 238000007254 oxidation reaction Methods 0.000 claims description 23
- 239000000446 fuel Substances 0.000 claims description 21
- 229910052697 platinum Inorganic materials 0.000 claims description 20
- 239000011241 protective layer Substances 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 15
- 239000007784 solid electrolyte Substances 0.000 claims description 10
- 229910044991 metal oxide Inorganic materials 0.000 claims description 9
- 150000004706 metal oxides Chemical class 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052703 rhodium Inorganic materials 0.000 claims description 6
- 239000010948 rhodium Substances 0.000 claims description 6
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 3
- -1 oxygen ion Chemical class 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 description 12
- 150000002430 hydrocarbons Chemical class 0.000 description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 9
- 229910002091 carbon monoxide Inorganic materials 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 238000001514 detection method Methods 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Measuring Oxygen Concentration In Cells (AREA)
Description
【発明の詳細な説明】 〈産業上の利用分野〉 本発明は、内燃機関の排気系に装着して該機関に供給さ
れる混合気の空燃比と密接な関係にある排気中の酸素濃
度を測定し、空燃比フィードバック制御におけるフィー
ドバック信号の供給に用いる酸素センサに関するもので
ある。DETAILED DESCRIPTION OF THE INVENTION <Industrial field of application> The present invention relates to an oxygen concentration in exhaust gas which is mounted on an exhaust system of an internal combustion engine and is closely related to an air-fuel ratio of an air-fuel mixture supplied to the engine. The present invention relates to an oxygen sensor that is used for measuring and supplying a feedback signal in air-fuel ratio feedback control.
〈従来の技術〉 従来、この種の酸素センサとしては、先端部を閉塞した
円筒状のジルコニア（ZrO2）に代表される酸素イオン導
電性の濃淡電池用固体電解質の内外表面の各一部に白金
電極を形成し、外表面にさらに白金を蒸着して酸化触媒
層を形成してなるものがよく知られている（実開昭61−
89160号公報参照）。<Prior Art> Conventionally, as this type of oxygen sensor, a part of the inner and outer surfaces of an oxygen ion conductive solid electrolyte for concentration cells represented by a cylindrical zirconia (ZrO 2 ) with a closed tip is used. It is well known that a platinum electrode is formed and platinum is further vapor-deposited on the outer surface to form an oxidation catalyst layer.
89160 gazette).
かかる酸素センサは、固体電解質の内側空洞に基準空気
として大気が導かれるようにする一方、固体電解質の外
側を機関排気通路に臨ませて機関排気と接触させ、内表
面に接触する大気中の酸素濃度と外表面に接触する排気
中の酸素濃度との比により起電力を電極間に発生させ
て、排気中の酸素濃度を検出するものである。Such an oxygen sensor allows the atmosphere to be guided to the inner cavity of the solid electrolyte as the reference air, while the outside of the solid electrolyte is exposed to the engine exhaust passage to contact the engine exhaust, and oxygen in the atmosphere contacting the inner surface The oxygen concentration in the exhaust gas is detected by generating an electromotive force between the electrodes based on the ratio between the concentration and the oxygen concentration in the exhaust gas that contacts the outer surface.
なお、白金からなる酸化触媒層は、排気中の一酸化炭素
（CO）や炭化水素（HC）を同じく排気中の酸素（O2）と
結合させ二酸化炭素（CO2）と水蒸気（H2O）に変える酸
化反応を促進し、濃混合気で燃焼させたときにその排気
中に残存する低濃度のO2をCOやHCと良好に反応させて残
存酸素濃度をゼロにし、固体電解質内外の酸素濃度比を
大きくして、大きな起電力を発生させることにより、理
論空燃比を境としてリッチ側とリーン側とで起電力を急
変させ、これにより理論空燃比の検出を容易にしてい
る。The platinum oxidation catalyst layer combines carbon monoxide (CO) and hydrocarbons (HC) in the exhaust gas with oxygen (O 2 ) in the exhaust gas as well, and carbon dioxide (CO 2 ) and water vapor (H 2 O 2 ). ) Is promoted, and the low concentration of O 2 remaining in the exhaust gas when it is burned in a rich air-fuel mixture reacts well with CO and HC to reduce the residual oxygen concentration to zero. By increasing the oxygen concentration ratio and generating a large electromotive force, the electromotive force is suddenly changed between the rich side and the lean side with the theoretical air-fuel ratio as a boundary, thereby facilitating detection of the theoretical air-fuel ratio.
〈発明が解決しようとする問題点〉 しかしながら、このような従来の酸素センサにあって
は、排気中の窒素酸化物（NOx）の濃度が高くなると、
排気中の酸素の一部がNOxに変化しているにも拘わら
ず、この酸素を検出できないので、起電力が真の理論空
燃比よりもリーン側で反転するようになり、真の理論空
燃比を検出できないという問題点があった。<Problems to be Solved by the Invention> However, in such a conventional oxygen sensor, when the concentration of nitrogen oxides (NOx) in the exhaust gas becomes high,
Despite the fact that some of the oxygen in the exhaust gas has changed to NOx, this oxygen cannot be detected, so the electromotive force reverses on the lean side of the true stoichiometric air-fuel ratio, and the true stoichiometric air-fuel ratio There was a problem that could not be detected.
本発明は、このような従来の問題点に鑑み、排気中のNO
x濃度に応じて起電力の反転点がリッチ側にシフトして
真の理論空燃比を検出することができ、しかも長期に亘
って検出精度を維持することのできる酸素センサを提供
することを目的とする。In view of the above conventional problems, the present invention provides NO in exhaust gas.
An object of the present invention is to provide an oxygen sensor that can detect the true stoichiometric air-fuel ratio by shifting the reversal point of the electromotive force to the rich side according to the x concentration and can maintain the detection accuracy for a long period of time. And
〈問題点を解決するための手段〉 このため、本発明では、白金からなる酸化触媒層の外側
にチタニア（TiO2）にNOx還元触媒としてのロジウム（R
h）を担持させた還元触媒層を設け、また、少なくとも
酸化触媒層と還元触媒層との間に多孔性の金属酸化物か
らなる保護層を設ける構成とする。<Means for Solving Problems> Therefore, according to the present invention, titania (TiO 2 ) is added to the outside of the oxidation catalyst layer made of platinum, and rhodium (R
A reduction catalyst layer supporting h) is provided, and a protective layer made of a porous metal oxide is provided at least between the oxidation catalyst layer and the reduction catalyst layer.
〈作用〉 上記の構成によれば、ロジウムからなるNOx還元触媒層
はこれに達したNOxをCO,HCと反応させて、酸化触媒層に
達するCO,HCを消費するため、酸化触媒層においてCO,HC
と反応して消費されるO2が減少し、その分だけ固体電解
質に達するO2が増大する。従って、排気中のNOx濃度が
高くなる程、固体電解質の排気側のO2濃度が高くなり、
大気側と排気側のO2濃度差が減少することになって、酸
素センサ出力である起電力の反転点がリッチ側にシフト
して真の理論空燃比にて起電力が反転することになる。
よって、この酸素センサの出力電圧に基づいて空燃比を
フィードバック制御すれば空燃比を真の理論空燃比に制
御することが可能となる。<Operation> According to the above configuration, the NOx reduction catalyst layer made of rhodium reacts NOx reaching this with CO and HC and consumes CO and HC reaching the oxidation catalyst layer. , HC
O 2 consumed by reacting with is decreased, and O 2 reaching the solid electrolyte is increased correspondingly. Therefore, the higher the NOx concentration in the exhaust, the higher the O 2 concentration on the exhaust side of the solid electrolyte,
The difference in O 2 concentration between the atmosphere side and the exhaust side will decrease, and the reversal point of the electromotive force that is the oxygen sensor output will shift to the rich side, and the electromotive force will be reversed at the true stoichiometric air-fuel ratio. .
Therefore, if the air-fuel ratio is feedback controlled based on the output voltage of the oxygen sensor, the air-fuel ratio can be controlled to the true stoichiometric air-fuel ratio.
また、多孔性の金属酸化物からなる保護層を少なくとも
酸化触媒層と還元触媒層との間に設けることによって、
排気中に含まれることがある鉛が白金からなる酸化触媒
層に到達する前に多孔性の金属酸化物からなる保護層に
吸着されて白金が侵されることを防止でき、また同じく
排気中の炭化水素も多孔性の金属酸化物からなる保護層
によって白金からなる酸化触媒層への到達を阻まれ、酸
化触媒層上へのカーボン析出を防止し、酸化触媒層と還
元触媒層の剥離を免れることができ、これによって、耐
久性の向上と安定した検出精度を得ることができる。Further, by providing a protective layer made of a porous metal oxide at least between the oxidation catalyst layer and the reduction catalyst layer,
Lead that may be contained in the exhaust gas can be prevented from being absorbed by the protective layer made of a porous metal oxide before reaching the oxidation catalyst layer made of platinum, and the platinum can be prevented from being damaged. Hydrogen is also prevented from reaching the oxidation catalyst layer made of platinum by the protective layer made of porous metal oxide, preventing carbon deposition on the oxidation catalyst layer, and avoiding separation of the oxidation catalyst layer and the reduction catalyst layer. This makes it possible to improve durability and obtain stable detection accuracy.
〈実施例〉 以下に本発明の実施例を説明する。<Examples> Examples of the present invention will be described below.
第１図は第１の実施例を示している。先端部を閉塞した
円筒状のジルコニアに代表される酸素イオン導電性の濃
淡電池用固体電解質１の内外表面の各一部に白金電極2,
3を形成し、外表面に白金を蒸着して酸化触媒層４を形
成し、その外表面に、多孔性の金属酸化物としてのアル
ミナ（Al2O3）からなる保護層６を設け、さらにその外
側をチタニアにNOx還元触媒としてのロジウムを担持さ
せた還元触媒層５を形成する。FIG. 1 shows a first embodiment. A platinum electrode 2 is provided on each part of the inner and outer surfaces of the solid electrolyte 1 for oxygen ion conductive concentration battery represented by cylindrical zirconia with the tip closed.
3 is formed, platinum is vapor-deposited on the outer surface to form an oxidation catalyst layer 4, and a protective layer 6 made of alumina (Al 2 O 3 ) as a porous metal oxide is provided on the outer surface, and A reduction catalyst layer 5 is formed on the outside of which titania is loaded with rhodium as a NOx reduction catalyst.
これによれば、ロジウムからなるNOx還元触媒層５はこ
れに達したNOxをCO,HCと反応させて、酸化触媒層４に達
するCO,HCを消費するため、酸化触媒層４においてCO,HC
と反応して消費されるO2が減少し、その分だけ固体電解
質１に達するO2が増大する。従って、排気中のNOx濃度
が高くなる程、固体電解質１の排気側のO2濃度が高くな
り、大気側と排気側のO2濃度差が減少することになっ
て、第３図の起電力特性曲線に示すように、酸素センサ
出力である起電力の反転点がリッチ側にシフトして図示
破線の如く真の理論空燃比にて起電力が反転することに
なる。よって、この酸素センサの出力電圧に基づいて空
燃比をフィードバック制御すれば空燃比を真の理論空燃
比に制御することが可能となる。According to this, the NOx reduction catalyst layer 5 made of rhodium reacts the NOx reaching it with CO, HC and consumes CO, HC reaching the oxidation catalyst layer 4, so that CO, HC in the oxidation catalyst layer 4 is consumed.
O 2 consumed by reacting with is decreased, and O 2 reaching the solid electrolyte 1 is increased correspondingly. Therefore, the higher the NOx concentration in the exhaust gas, the higher the O 2 concentration on the exhaust side of the solid electrolyte 1, and the difference in the O 2 concentration between the atmosphere side and the exhaust side decreases. As shown in the characteristic curve, the reversal point of the electromotive force, which is the oxygen sensor output, shifts to the rich side, and the electromotive force is inverted at the true stoichiometric air-fuel ratio as shown by the broken line in the figure. Therefore, if the air-fuel ratio is feedback controlled based on the output voltage of the oxygen sensor, the air-fuel ratio can be controlled to the true stoichiometric air-fuel ratio.
また、排気中の鉛が白金からなる酸化触媒層４に到達す
る前にアルミナ保護層６により吸着されて白金が侵され
ることを防止でき、また炭化水素もアルミナ保護層６に
よって白金触媒層４への到達を阻まれ、白金からなる酸
化触媒層４上へのカーボン析出を防止することができ
る。なお、アルミナ保護層を設けたものとそうでないも
のとの走行距離による性能比較では、第４図に示すよう
に、保護層ありのものは理論空燃比検出点の変化量Δλ
が小さく、はるかに耐久性が向上したことがわかる。Further, it is possible to prevent platinum in the exhaust gas from being adsorbed by the alumina protective layer 6 before the lead in the exhaust gas reaches the oxidation catalyst layer 4 made of platinum and attacking platinum, and hydrocarbons are also transferred to the platinum catalyst layer 4 by the alumina protective layer 6. It is possible to prevent the precipitation of carbon on the oxidation catalyst layer 4 made of platinum. As shown in FIG. 4, the comparison of the performance with the alumina protective layer and that without the alumina protective layer shows that the protective layer has the theoretical air-fuel ratio detection point change amount Δλ.
It can be seen that is small and the durability is much improved.
第２図に示す第２の実施例は、アルミナ保護層６を酸化
触媒層４と還元触媒層５との間と還元触媒層６のさらに
外側の両方に設けた場合であり、このようにしても同様
の効果が得られる。The second embodiment shown in FIG. 2 is a case where the alumina protective layer 6 is provided both between the oxidation catalyst layer 4 and the reduction catalyst layer 5 and further outside the reduction catalyst layer 6, and thus, Also has the same effect.
〈発明の効果〉 以上説明したように、本発明によれば、排気側の面に、
白金からなる酸化触媒層を形成すると共に、その外側に
チタニアにNOx還元触媒としてのロジウムを担持させた
還元触媒層を形成したので、排気中のNOx濃度に応じて
起電力の反転点がリッチ側にシフトして真の理論空燃比
を検出することができる。また、多孔性の金属酸化物か
らなる保護層を少なくとも酸化触媒層と還元触媒層との
間に設けるので、排気中の鉛が白金からなる酸化触媒層
に到達する前に多孔性の金属酸化物からなる保護層によ
り吸着され、白金が侵されることを防止でき、また炭化
水素も多孔性の金属酸化物からなる保護層によって白金
からなる酸化触媒層への到達を阻まれ、酸化触媒層上へ
のカーボン析出を防止することができ、これによって、
耐久性の向上と安定した検出精度を得ることができる。<Effects of the Invention> As described above, according to the present invention, on the exhaust side surface,
In addition to forming an oxidation catalyst layer made of platinum, a reduction catalyst layer was formed on the outer side of which titania was loaded with rhodium as a NOx reduction catalyst, so the reversal point of the electromotive force was richer depending on the NOx concentration in the exhaust gas. The true stoichiometric air-fuel ratio can be detected by shifting to. Further, since the protective layer made of a porous metal oxide is provided at least between the oxidation catalyst layer and the reduction catalyst layer, the porous metal oxide is formed before lead in the exhaust reaches the oxidation catalyst layer made of platinum. It is possible to prevent the platinum from being attacked by being adsorbed by the protective layer made of platinum, and also the hydrocarbons are prevented from reaching the oxidation catalyst layer made of platinum by the protective layer made of the porous metal oxide, so that hydrocarbons are prevented from reaching the oxidation catalyst layer. It is possible to prevent the carbon precipitation of
It is possible to improve durability and obtain stable detection accuracy.
第１図は本発明の第１の実施例を示す酸素センサの断面
図、第２図は第２の実施例を示す酸素センサの断面図、
第３図は酸素センサの起電力特性図、第４図はアルミナ
からなる保護層を設けた場合とそうでない場合の走行距
離による耐久性比較を示す図である。 １……固体電解質、2,3……電極、４……酸化触媒層、
５……還元触媒層、６……アルミナ保護層1 is a sectional view of an oxygen sensor showing a first embodiment of the present invention, FIG. 2 is a sectional view of an oxygen sensor showing a second embodiment,
FIG. 3 is a diagram showing electromotive force characteristics of the oxygen sensor, and FIG. 4 is a diagram showing a comparison of durability according to the traveled distance with and without the protective layer made of alumina. 1 ... solid electrolyte, 2,3 ... electrode, 4 ... oxidation catalyst layer,
5 ... Reduction catalyst layer, 6 ... Alumina protective layer
Claims (1)
電解質の両面にそれぞれ電極を形成し、一方の面を基準
空気側に配し、他方の面を排気中に配して、排気中の酸
素濃度を介して機関に吸入される混合気の空燃比を検出
する内燃機関の酸素センサにおいて、 排気側の面に、白金からなる酸素触媒層を形成すると共
に、その外側にチタニアに窒素酸化物還元触媒としての
ロジウムを担持させた還元触媒層を形成し、また、少な
くとも前記酸化触媒層と還元触媒層との間に多孔性の金
属酸化物からなる保護層を設けたことを特徴とする内燃
機関の酸素センサ。1. An electrode is formed on each side of a solid electrolyte for a concentration battery having oxygen ion conductivity, one surface is arranged on the reference air side, and the other surface is arranged in the exhaust gas, In an oxygen sensor for an internal combustion engine that detects the air-fuel ratio of the air-fuel mixture that is drawn into the engine via the oxygen concentration, an oxygen catalyst layer made of platinum is formed on the exhaust side surface and nitrogen oxide is added to titania on the outside of the layer. An internal combustion characterized by forming a reduction catalyst layer supporting rhodium as a reduction catalyst, and providing a protective layer made of a porous metal oxide between at least the oxidation catalyst layer and the reduction catalyst layer. The oxygen sensor of the engine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62275856A JPH0713609B2 (en) | 1987-11-02 | 1987-11-02 | Oxygen sensor for internal combustion engine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62275856A JPH0713609B2 (en) | 1987-11-02 | 1987-11-02 | Oxygen sensor for internal combustion engine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01119755A JPH01119755A (en) | 1989-05-11 |
| JPH0713609B2 true JPH0713609B2 (en) | 1995-02-15 |
Family
ID=17561384
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62275856A Expired - Lifetime JPH0713609B2 (en) | 1987-11-02 | 1987-11-02 | Oxygen sensor for internal combustion engine |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0713609B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0344659U (en) * | 1989-09-07 | 1991-04-25 | ||
| US6117393A (en) * | 1997-01-16 | 2000-09-12 | Cts Corporation | Multilayered gas sensor |
| US5779980A (en) * | 1997-01-16 | 1998-07-14 | Cts Corporation | Gas sensor having a compounded catalytic structure |
| JP5394796B2 (en) * | 2009-03-31 | 2014-01-22 | トヨタ自動車株式会社 | Hot top for continuous casting and continuous casting method |
| CN111480070B (en) * | 2017-12-28 | 2023-07-18 | 日本特殊陶业株式会社 | Gas sensor elements and gas sensors |
| CN113227774B (en) * | 2018-12-28 | 2023-08-11 | 日本特殊陶业株式会社 | Gas sensor element and gas sensor |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51126890A (en) * | 1975-04-25 | 1976-11-05 | Nissan Motor Co Ltd | Air fuel ratio detector |
| JPS61241657A (en) * | 1985-04-19 | 1986-10-27 | Nissan Motor Co Ltd | Oxygen sensor element |
-
1987
- 1987-11-02 JP JP62275856A patent/JPH0713609B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01119755A (en) | 1989-05-11 |
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