JP3402068B2 - Bonding structure of sensor element and heater in oxygen sensor - Google Patents
Bonding structure of sensor element and heater in oxygen sensorInfo
- Publication number
- JP3402068B2 JP3402068B2 JP14957196A JP14957196A JP3402068B2 JP 3402068 B2 JP3402068 B2 JP 3402068B2 JP 14957196 A JP14957196 A JP 14957196A JP 14957196 A JP14957196 A JP 14957196A JP 3402068 B2 JP3402068 B2 JP 3402068B2
- Authority
- JP
- Japan
- Prior art keywords
- sensor element
- heater
- joint
- atmosphere
- joint portion
- 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 - Fee Related
Links
Landscapes
- Measuring Oxygen Concentration In Cells (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】この発明は、例えば内燃機関
の空燃比制御を行うために排気ガス中の酸素濃度を検出
する酸素センサに係り、特に、電解質シートを含む複数
のシートを積層したセンサ素子と、このセンサ素子の特
性を向上させるためにこのセンサ素子を加熱するヒータ
とを備えた積層型酸素センサにおいて、このセンサ素子
にヒータを接合する構造に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an oxygen sensor for detecting the oxygen concentration in exhaust gas for controlling the air-fuel ratio of an internal combustion engine, and more particularly to a sensor element in which a plurality of sheets including electrolyte sheets are laminated. And a heater for heating the sensor element in order to improve the characteristics of the sensor element, the present invention relates to a structure in which a heater is joined to the sensor element.
【０００２】[0002]
【従来の技術】図７に示す従来の積層型酸素センサ（そ
のほか、特開平４ー１５１５５０号公報も参照）におい
ては、ケース１内に保持ユニット２が内蔵され、この保
持ユニット２内でシート状センサ素子３とシート状ヒー
タ４とが互いに重合されて位置決め固定されている。こ
のセンサ素子３及びヒータ４の先端部は、それらの接合
部１９，２０で互いに接合された状態で保持ユニット２
の外側へ突出し、燃焼ガス流入カバー７により覆われて
いる。図示しないが、前記シート状センサ素子３の接合
部１９においては、燃焼ガス雰囲気と接触し得る固体電
解質シートの表面で雰囲気側酸素反応電極が形成され、
燃焼ガス雰囲気と遮断した大気導入孔に面する固体電解
質シートの裏面で大気側酸素反応電極が形成されてい
る。また、前記シート状ヒータ４の接合部２０において
は、センサ素子３の酸素反応電極の近傍に発熱部を有し
ている。2. Description of the Related Art In a conventional laminated oxygen sensor shown in FIG. 7 (see also Japanese Patent Application Laid-Open No. 4-151550), a holding unit 2 is built in a case 1, and a sheet-like shape is formed in the holding unit 2. The sensor element 3 and the sheet-shaped heater 4 are overlapped with each other and positioned and fixed. The tip of the sensor element 3 and the heater 4 are joined together at their joints 19 and 20, and the holding unit 2 is joined.
And is covered with a combustion gas inflow cover 7. Although not shown, in the joint portion 19 of the sheet-shaped sensor element 3, an atmosphere-side oxygen reaction electrode is formed on the surface of the solid electrolyte sheet that can come into contact with the combustion gas atmosphere,
Atmosphere-side oxygen reaction electrode is formed on the back surface of the solid electrolyte sheet facing the atmosphere introduction hole that is shielded from the combustion gas atmosphere. Further, the joint portion 20 of the sheet-shaped heater 4 has a heating portion near the oxygen reaction electrode of the sensor element 3.
【０００３】[0003]
【発明が解決しようとする課題】一般に、前記センサ素
子３はジルコニア（ＺｒＯ2 ）などにより成形され、ヒ
ータ４は窒化けい素（Ｓｉ3 Ｎ4 ）などにより成形され
ている。それらはいずれも焼成体であるため、反りが生
じ易い。しかも、前記保持ユニット２によりセンサ素子
３及びヒータ４を位置決め固定してそれらの先端部を保
持ユニット２の外側へ突出させると、前記反りの発生と
相俟って、それらの先端部で接合部１９と接合部２０と
が完全に離れて隙間Ｓが生じ易くなる。Generally, the sensor element 3 is formed of zirconia (ZrO 2 ) or the like, and the heater 4 is formed of silicon nitride (Si 3 N 4 ) or the like. Since all of them are fired bodies, warpage is likely to occur. Moreover, when the sensor element 3 and the heater 4 are positioned and fixed by the holding unit 2 and their tips are projected to the outside of the holding unit 2, together with the occurrence of the warp, the joining portions are joined at their tips. 19 and the joint portion 20 are completely separated from each other, and a gap S is likely to occur.
【０００４】このような隙間Ｓがあると、ヒータ４から
センサ素子３への熱伝導効率が悪くなり、センサ素子３
の昇温速度及び最終到達温度が低下する。従って、セン
サ素子３の特性（早期活性化や出力安定化など）が悪化
し、内燃機関の空燃比制御上悪影響を及ぼす。また、セ
ンサ素子３の特性を良好な状態に維持するために、ヒー
タ４への供給電力を上げると、ヒータ４の寿命が低下す
る。さらに、使用する酸素センサごとにこの隙間Ｓが異
なると、センサ素子３の特性も変化するため、出力を安
定させる上で好ましくない。そこで、この隙間Ｓをなく
すか、またはこの隙間Ｓの存在を許容しながらも隙間Ｓ
をできる限り小さく抑えて酸素センサごとにほぼ一定に
する必要がある。なお、センサ素子３及びヒータ４の先
端部もホルダ（図示せず）により固定して隙間Ｓをなく
すことも考えられるが、この場合には逆にホルダから熱
が逃げて熱伝導効率が悪くなる。If there is such a gap S, the heat conduction efficiency from the heater 4 to the sensor element 3 becomes poor, and the sensor element 3
The temperature rising rate and the final temperature reached are decreased. Therefore, the characteristics of the sensor element 3 (early activation, output stabilization, etc.) are deteriorated, which adversely affects the air-fuel ratio control of the internal combustion engine. Further, if the electric power supplied to the heater 4 is increased in order to maintain the characteristics of the sensor element 3 in a good state, the life of the heater 4 is shortened. Further, if the gap S differs for each oxygen sensor used, the characteristics of the sensor element 3 also change, which is not preferable for stabilizing the output. Therefore, the gap S is eliminated or the gap S is allowed while allowing the gap S to exist.
Should be kept as small as possible and should be kept almost constant for each oxygen sensor. It is also possible to fix the tip portions of the sensor element 3 and the heater 4 with a holder (not shown) to eliminate the gap S. However, in this case, heat radiates from the holder and the heat transfer efficiency deteriorates. .
【０００５】本発明は、上記問題点に鑑み、隙間の管理
を行い易い各種接合構造を提供し、ヒータからセンサ素
子への熱伝導効率を向上させてセンサ素子の昇温速度及
び最終到達温度を改善することを目的にしている。In view of the above-mentioned problems, the present invention provides various bonding structures that facilitate the management of gaps, improves the heat conduction efficiency from the heater to the sensor element, and increases the temperature rising rate and the ultimate temperature of the sensor element. The purpose is to improve.
【０００６】[0006]
【課題を解決するための手段】第一発明、第二発明、第
三発明及び第四発明にかかる酸素センサは、いずれも下
記の共通構成を有している。The oxygen sensors according to the first invention, the second invention, the third invention and the fourth invention all have the following common structure.
【０００７】センサ素子とヒータとを備えている。セン
サ素子においては、燃焼ガス雰囲気と接触し得る固体電
解質シートの雰囲気側面で雰囲気側酸素反応電極を形成
しているとともに、燃焼ガス雰囲気と遮断した大気側に
面する固体電解質シートの大気側面で大気側酸素反応電
極を形成している。ヒータにおいては、センサ素子に設
けた接合部に接合される接合部でセンサ素子の酸素反応
電極の近傍に発熱部を有している。更にセンサ素子とヒ
ータとは、それらの基端部から先端部にわたり互いに重
合され、互いに締め付け固定されていないそれらの先端
部に、センサ素子の接合部及びヒータの接合部がそれぞ
れ設けられている。 A sensor element and a heater are provided. In the sensor element, the atmosphere side oxygen reaction electrode is formed on the atmosphere side of the solid electrolyte sheet that can come into contact with the combustion gas atmosphere, and the atmosphere on the atmosphere side of the solid electrolyte sheet facing the atmosphere side that is shielded from the combustion gas atmosphere Forming a side oxygen reaction electrode. In the heater, a heat generating portion is provided in the vicinity of the oxygen reaction electrode of the sensor element at the joint portion joined to the joint portion provided in the sensor element. In addition, the sensor element and
Data from each other from their base end to their tip.
Their tips that are fitted and not clamped and fixed to each other
The sensor element joint and the heater joint are
It is provided.
【０００８】さらに、上記各発明は、センサ素子とヒー
タとの接合構造を下記のように構成している。第一発明
においては、前記センサ素子の接合部とヒータの接合部
とに凹凸部を形成し、それらを互いに接触して嵌合させ
ている。従って、センサ素子の接合部とヒータの接合部
との接触面積が増大する。Further, in each of the above inventions, the joint structure of the sensor element and the heater is constructed as follows. In the first aspect of the present invention, the concavo-convex portion is formed in the joint portion of the sensor element and the joint portion of the heater, and they are fitted in contact with each other. Therefore, the contact area between the joint portion of the sensor element and the joint portion of the heater increases.
【０００９】第二発明においては、前記センサ素子の接
合部とヒータの接合部とのうち少なくとも一方の接合部
に突起部を形成して他方の接合部に接触させている。従
って、センサ素子の接合部とヒータの接合部とが確実に
接触する。According to the second aspect of the present invention, a protrusion is formed on at least one of the joint portion of the sensor element and the joint portion of the heater and is brought into contact with the other joint portion. Therefore, the joint portion of the sensor element and the joint portion of the heater surely come into contact with each other.
【００１０】第三発明においては、前記センサ素子の接
合部とヒータの接合部とのうち少なくとも一方の接合部
に係合部を形成し、この係合部で両接合部を互いに接触
させるように圧接させている。従って、センサ素子の接
合部とヒータの接合部とが確実に接触する。In the third invention, an engaging portion is formed on at least one of the joint portion of the sensor element and the joint portion of the heater, and both joint portions are brought into contact with each other at the engaging portion. It is pressed. Therefore, the joint portion of the sensor element and the joint portion of the heater surely come into contact with each other.
【００１１】第四発明においては、前記ヒータの接合部
に輻射凹部を形成し、センサ素子の雰囲気側酸素反応電
極をこの輻射凹部により囲っている。そのため、この輻
射凹部の内面の輻射熱面積が増大し、この内面から放射
される輻射熱が雰囲気側酸素反応電極に効率良く伝達さ
れる。In the fourth aspect of the present invention, a radiation recess is formed in the joint of the heater, and the atmosphere-side oxygen reaction electrode of the sensor element is surrounded by the radiation recess. Therefore, the radiant heat area on the inner surface of the radiant recess increases, and the radiant heat radiated from the inner surface is efficiently transferred to the atmosphere-side oxygen reaction electrode.
【００１２】[0012]
〔第一実施形態〕まず、本発明の第一実施形態にかかる
積層型酸素センサを図１〜３を参照して説明する。First Embodiment First, a laminated oxygen sensor according to a first embodiment of the present invention will be described with reference to FIGS.
【００１３】（積層型酸素センサの概略について）図１
（ａ）に示すように、ケース１内に保持ユニット２が内
蔵され、この保持ユニット２内でシート状センサ素子３
とシート状ヒータ４とが互いに接合されてホルダ５やブ
ラケット６ａやタルク６ｂなどにより締め付けられて位
置決め固定されている。このセンサ素子３及びヒータ４
の基端部は、ホルダ５に挿通されて保持ユニット２の外
側へ突出している。このセンサ素子３及びヒータ４の先
端部は、ブラケット６ａに挿通されて保持ユニット２の
外側へ突出し、燃焼ガス流入カバー７により覆われてい
る。(Outline of stacked oxygen sensor) FIG.
As shown in (a), the holding unit 2 is built in the case 1, and the sheet-shaped sensor element 3 is provided in the holding unit 2.
And the sheet-shaped heater 4 are joined to each other, and are fixedly positioned by being tightened by the holder 5, the bracket 6a, the talc 6b, and the like. The sensor element 3 and the heater 4
The base end portion of is inserted into the holder 5 and protrudes to the outside of the holding unit 2. The tip ends of the sensor element 3 and the heater 4 are inserted into the bracket 6a, protrude outside the holding unit 2, and are covered with the combustion gas inflow cover 7.
【００１４】図１（ｂ）に示すように、前記シート状セ
ンサ素子３は、固体電解質シート８と大気導入孔シート
９と基底材シート１０とを互いに積層したものである。
固体電解質シート８の先端部において燃焼ガス雰囲気と
接触し得る雰囲気側面（表面）で雰囲気側酸素反応電極
１１が形成され、この雰囲気側酸素反応電極１１に接続
されたリード部１２が固体電解質シート８の基端部まで
延設されている。基底材シート１０と固体電解質シート
８との間で大気導入孔シート９の内側空間には、燃焼ガ
ス雰囲気と遮断された大気導入孔１３が形成されてい
る。固体電解質シート８の先端部において大気導入孔１
３に面する大気側面（裏面）で大気側酸素反応電極１４
が形成され、この大気側酸素反応電極１４に接続された
リード部１５が固体電解質シート８の基端部まで延設さ
れている。なお、前記固体電解質シート８は、酸素イオ
ン導電性ジルコニア（ＺｒＯ2 ）とイットリア（Ｙ2 Ｏ
3）とからなる原料により成形されている。前記電極１
１，１４及びリード部１２，１５は白金（Ｐｔ）からな
る。As shown in FIG. 1B, the sheet-shaped sensor element 3 is formed by laminating a solid electrolyte sheet 8, an air introduction hole sheet 9 and a base material sheet 10 on each other.
At the tip of the solid electrolyte sheet 8, an atmosphere-side oxygen reaction electrode 11 is formed on the atmosphere side surface (surface) that can come into contact with the combustion gas atmosphere, and the lead portion 12 connected to this atmosphere-side oxygen reaction electrode 11 has the solid electrolyte sheet 8. Has been extended to the base end. An air introduction hole 13 is formed between the base material sheet 10 and the solid electrolyte sheet 8 in the inner space of the air introduction hole sheet 9 so as to be shielded from the combustion gas atmosphere. Atmosphere introducing hole 1 at the tip of solid electrolyte sheet 8
At the atmospheric side surface (back side) facing the No. 3 atmosphere side oxygen reaction electrode 14
And the lead portion 15 connected to the atmosphere-side oxygen reaction electrode 14 is extended to the base end portion of the solid electrolyte sheet 8. The solid electrolyte sheet 8 is composed of oxygen ion conductive zirconia (ZrO 2 ) and yttria (Y 2 O).
3 ) Molded from the raw material consisting of The electrode 1
1, 14 and the lead portions 12, 15 are made of platinum (Pt).
【００１５】前記シート状ヒータ４の内部において、そ
の先端部には発熱部１６が前記センサ素子３の酸素反応
電極１１，１４の近傍に埋設され、この発熱部１６に接
続された二本のリード部１７が基端部まで延設されてい
る。なお、このシート状ヒータ４は窒化けい素（Ｓｉ3
Ｎ4 ）またはアルミナ（Ａｌ2 Ｏ3 ）からなる。Inside the sheet-shaped heater 4, a heat-generating portion 16 is embedded in the tip of the heater near the oxygen reaction electrodes 11 and 14 of the sensor element 3, and two leads connected to the heat-generating portion 16 are provided. The portion 17 extends to the base end portion. The sheet-shaped heater 4 is made of silicon nitride (Si 3
N 4) or formed of alumina (Al 2 O 3).
【００１６】前記センサ素子３及びヒータ４の基端部に
おいて、その各リード部１２，１５，１７にそれぞれタ
ーミナル１８が接続されている。
（前記センサ素子３とヒータ４との接合構造について）
前記シート状センサ素子３の基底材シート１０の全体と
シート状ヒータ４の片面全体とが、それらの基端部から
先端部にわたり互いに重合されている。特に、ヒータ４
の先端部とセンサ素子３の先端部において相対向する接
合部１９，２０が形成されている。図１（ｂ）または図
１（ｃ）または図２（ａ）または図２（ｂ）に示すよう
に、これらの接合部１９，２０には凹凸部２１，２２が
センサ素子３の酸素反応電極１１，１４及びヒータ４内
の発熱部１６に対応して形成され、互いに接触して嵌合
されている。At the base ends of the sensor element 3 and the heater 4, terminals 18 are connected to the respective lead portions 12, 15, 17 thereof. (Regarding the joint structure between the sensor element 3 and the heater 4)
The entire base material sheet 10 of the sheet-shaped sensor element 3 and the entire one surface of the sheet-shaped heater 4 are overlapped with each other from the base end portion to the tip end portion thereof. In particular, the heater 4
Joint portions 19 and 20 facing each other are formed at the tip of the sensor element 3 and the tip of the sensor element 3. As shown in FIG. 1 (b), FIG. 1 (c), FIG. 2 (a), or FIG. 2 (b), the concavo-convex portions 21 and 22 are formed on the joint portions 19 and 20 of the oxygen reaction electrode of the sensor element 3. 11, 14 and the heating portion 16 in the heater 4 are formed so as to be in contact with each other and fitted.
【００１７】この凹凸部２１，２２は、いずれも基端側
から先端側へ波形状に延設され、互いに等間隔で平行に
並設された複数の歯部２１ａ，２２ａと、それらの間の
溝部２１ｂ，２２ｂとから形成されている。そして、セ
ンサ素子３の凹凸部２１の歯部２１ａがヒータ４の凹凸
部２２の溝部２２ｂに嵌合されているとともに、ヒータ
４の凹凸部２２の歯部２２ａがセンサ素子３の凹凸部２
１の溝部２１ｂに嵌合されている。各歯部２１ａ，２２
ａ及び各溝部２１ｂ，２２ｂの形状としては、例えば、
図１（ｂ）（ｃ）に示すように半円弧形状にしたもの、
図２（ａ）に示すように矩形状にしたもの、図２（ｂ）
に示すように三角形状にしたものなどが考えられ、いず
れも接触面積の増大が図られている。The concavo-convex portions 21 and 22 each extend in a wave shape from the base end side to the tip end side and are arranged in parallel at equal intervals, and a plurality of tooth portions 21a and 22a between them are provided. It is formed of groove portions 21b and 22b. The tooth portion 21a of the uneven portion 21 of the sensor element 3 is fitted into the groove portion 22b of the uneven portion 22 of the heater 4, and the tooth portion 22a of the uneven portion 22 of the heater 4 is formed in the uneven portion 2 of the sensor element 3.
It is fitted in the first groove portion 21b. Each tooth 21a, 22
Examples of the shape of a and the groove portions 21b and 22b include, for example,
A semicircular shape as shown in FIGS. 1 (b) and (c),
A rectangular shape as shown in FIG. 2A, FIG.
As shown in (3), a triangular shape is conceivable, and the contact area is increased in each case.
【００１８】図１（ｃ）に示すものは、図１（ｂ）に示
すものと比較して、センサ素子３の凹凸部２１とヒータ
４の凹凸部２２との間に接着剤２３（無機接着剤等）が
埋め込まれている点で異なる。従って、各歯部２１ａ，
２２ａと各溝部２１ｂ，２２ｂとが互いに合致しない場
合でも、センサ素子３の凹凸部２１とヒータ４の凹凸部
２２とが接着剤２３を介して確実に接触する。1C is different from that shown in FIG. 1B in that an adhesive 23 (inorganic adhesive) is provided between the uneven portion 21 of the sensor element 3 and the uneven portion 22 of the heater 4. The difference is that the drug etc.) is embedded. Therefore, each tooth 21a,
Even when the groove 22a and the grooves 21b and 22b do not coincide with each other, the concavo-convex portion 21 of the sensor element 3 and the concavo-convex portion 22 of the heater 4 surely contact each other via the adhesive 23.
【００１９】なお、前記凹凸部２１，２２は、型による
シート成形時に同時に形成したり、シート成形後に機械
加工により形成したりすることが考えられる。第一実施
形態は下記（イ）の特徴を有する。It is conceivable that the concavo-convex portions 21 and 22 may be formed at the same time when the sheet is formed by the mold, or may be formed by machining after the sheet is formed. The first embodiment has the following characteristics (a).
【００２０】（イ） センサ素子３の接合部１９とヒー
タ４の接合部２０とには、互いに接触して嵌合される凹
凸部２１，２２を形成したので、それらの接触面積が増
大し、ヒータ４からセンサ素子３への熱伝導効率が向上
する。ちなみに、図３（ａ）に示すようにセンサ素子３
が７００℃まで昇温する時間と、図３（ｂ）に示すよう
にセンサ素子３の最終到達温度とを、図７に示した従来
のものとこの第一実施形態のものとで比較すると、いず
れも第一実施形態のものが明らかに改善されていること
が分かる。従って、センサ素子３の特性（早期活性化や
出力安定化など）が良好になり、内燃機関の空燃比制御
上好影響を及ぼす。また、ヒータ４への供給電力も少な
くなり、ヒータ４の寿命を長くすることができる。(A) Since the concavo-convex portions 21 and 22 are formed in the joint portion 19 of the sensor element 3 and the joint portion 20 of the heater 4 so as to be in contact with each other, the contact area between them is increased, The heat conduction efficiency from the heater 4 to the sensor element 3 is improved. By the way, as shown in FIG.
When the temperature rises up to 700 ° C. and the final temperature reached by the sensor element 3 as shown in FIG. 3 (b) are compared between the conventional one shown in FIG. 7 and this first embodiment, It can be seen that in both cases, the first embodiment is clearly improved. Therefore, the characteristics of the sensor element 3 (early activation, output stabilization, etc.) are improved, which has a favorable effect on the air-fuel ratio control of the internal combustion engine. Further, the electric power supplied to the heater 4 is reduced, and the life of the heater 4 can be extended.
【００２１】〔第二実施形態〕次に、本発明の第二実施
形態にかかる積層型酸素センサを図４及び図５を参照し
て説明する。この第二実施形態は、前記第一実施形態と
下記の点で異なる。Second Embodiment Next, a laminated oxygen sensor according to a second embodiment of the present invention will be described with reference to FIGS. 4 and 5. The second embodiment differs from the first embodiment in the following points.
【００２２】図４（ａ）（ｂ）に示すように、シート状
センサ素子３の固定電解質シート８の全体とシート状ヒ
ータ４の片面全体とがそれらの基端部から先端部にわた
り互いに重合されている。ヒータ４の先端部で接合部２
０に突起部２４（例えば半球形状）が形成されている。
センサ素子３の先端部でヒータ４の接合部２０に相対向
する接合部１９において、固定電解質シート８の雰囲気
側酸素反応電極１１にヒータ４の突起部２４が圧接され
ているとともに、この両接合部１９，２０間に僅かな間
隙２５が形成されている。As shown in FIGS. 4A and 4B, the entire fixed electrolyte sheet 8 of the sheet-shaped sensor element 3 and the entire one surface of the sheet-shaped heater 4 are superposed on each other from their base end portions to their tip portions. ing. Joining part 2 at the tip of heater 4
A protrusion 24 (for example, a hemispherical shape) is formed at 0.
At the joint portion 19 facing the joint portion 20 of the heater 4 at the tip of the sensor element 3, the protrusion portion 24 of the heater 4 is pressed against the atmosphere-side oxygen reaction electrode 11 of the fixed electrolyte sheet 8, and both of these joints are joined. A slight gap 25 is formed between the parts 19 and 20.
【００２３】図５（ａ）（ｂ）に示す固定電解質シート
８は、互いに重合された表側固定電解質シート８ａと裏
側固定電解質シート８ｂとからなり、接合部１９におい
て突起部２６（例えば半球形状）が形成されている。こ
の突起部２６に雰囲気側酸素反応電極１１が形成されて
ヒータ４の接合部２０に圧接されているとともに、この
両接合部１９，２０間に僅かな間隙２５が形成されてい
る。The fixed electrolyte sheet 8 shown in FIGS. 5 (a) and 5 (b) is composed of a front fixed electrolyte sheet 8a and a back fixed electrolyte sheet 8b which are polymerized with each other, and the protrusion 26 (for example, hemispherical shape) at the joint portion 19. Are formed. The atmosphere-side oxygen reaction electrode 11 is formed on the protrusion 26 and pressed against the joint 20 of the heater 4, and a slight gap 25 is formed between the joints 19 and 20.
【００２４】そのほか、図示しないが、前記センサ素子
３の接合部１９とヒータ４の接合部２０とにそれぞれ前
記突起部２４，２６を形成して互いに圧接させてもよ
い。なお、ヒータ４の突起部２４やセンサ素子３の突起
部２６は、型によるシート成形時に同時に形成したり、
シート成形後に機械加工により形成したりすることが考
えられる。In addition, although not shown, the protrusions 24 and 26 may be formed on the joint portion 19 of the sensor element 3 and the joint portion 20 of the heater 4, and they may be pressed against each other. The protrusions 24 of the heater 4 and the protrusions 26 of the sensor element 3 are formed at the same time when the sheet is formed by the mold,
It is considered that the sheet is formed by machining after the sheet is formed.
【００２５】第二実施形態は下記（イ）の特徴を有す
る。
（イ） いずれの場合にも、保持ユニット２内において
センサ素子３とヒータ４とがそれらの上部で互いに接合
されて締め付け固定されると、センサ素子３の接合部１
９とヒータ４の接合部２０とが突起部２４，２６の高さ
だけ互いに押し広げられ、僅かな間隙２５をおいて圧接
される。そのため、両接合部１９，２０が確実に接触
し、ヒータ４からセンサ素子３への熱伝導効率が向上す
る。しかも、間隙２５を介して放射される輻射熱も加わ
る。その結果、センサ素子３の昇温速度及び最終到達温
度を従来のものに比較して改善することができる。従っ
て、センサ素子３の特性（早期活性化や出力安定化な
ど）が良好になり、内燃機関の空燃比制御上好影響を及
ぼす。また、ヒータ４への供給電力も少なくなり、ヒー
タ４の寿命を長くすることができる。The second embodiment has the following characteristics (a). (A) In any case, when the sensor element 3 and the heater 4 are joined to each other in the upper portion of the holding unit 2 and tightened and fixed, the joint portion 1 of the sensor element 3 is formed.
9 and the joint portion 20 of the heater 4 are pushed apart from each other by the height of the protrusions 24 and 26, and pressed against each other with a slight gap 25. Therefore, the joint portions 19 and 20 are surely brought into contact with each other, and the heat conduction efficiency from the heater 4 to the sensor element 3 is improved. Moreover, radiant heat radiated through the gap 25 is also added. As a result, it is possible to improve the temperature rising rate and the final temperature of the sensor element 3 as compared with the conventional one. Therefore, the characteristics of the sensor element 3 (early activation, output stabilization, etc.) are improved, which has a favorable effect on the air-fuel ratio control of the internal combustion engine. Further, the electric power supplied to the heater 4 is reduced, and the life of the heater 4 can be extended.
【００２６】〔第三実施形態〕次に、本発明の第三実施
形態にかかる積層型酸素センサを図６（ａ）（ｂ）を参
照して説明する。この第三実施形態は、前記第一実施形
態と下記の点で異なる。[Third Embodiment] Next, a stacked oxygen sensor according to a third embodiment of the present invention will be described with reference to FIGS. 6 (a) and 6 (b). The third embodiment differs from the first embodiment in the following points.
【００２７】ヒータ４の接合部２０において、鉤状の係
合部２７が屈曲されて形成され、この鉤状係合部２７内
に係合溝２８が形成さている。センサ素子３の接合部１
９が、この係合溝２８に係入された状態で、ヒータ４の
接合部２０に接触して圧接されている。このセンサ素子
３の接合部１９にある固定電解質シート８の雰囲気側酸
素反応電極１１を燃焼ガス雰囲気に開放するようにガス
流入凹所２９がヒータ４の接合部２０に形成されてい
る。At the joint portion 20 of the heater 4, a hook-shaped engaging portion 27 is formed by bending, and an engaging groove 28 is formed in the hook-shaped engaging portion 27. Joint part 1 of sensor element 3
9 is engaged with the engagement groove 28 and is in pressure contact with the joint portion 20 of the heater 4. A gas inflow recess 29 is formed in the joint 20 of the heater 4 so as to open the atmosphere-side oxygen reaction electrode 11 of the fixed electrolyte sheet 8 at the joint 19 of the sensor element 3 to the combustion gas atmosphere.
【００２８】第三実施形態は下記（イ）〜（ハ）の特徴
を有する。
（イ） 保持ユニット２内においてセンサ素子３とヒー
タ４とがそれらの上部で互いに接合されて締め付け固定
されるとともに、センサ素子３の接合部１９がヒータ４
の接合部２０で鉤状係合部２７内の係合溝２８に係入さ
れると、この両接合部１９，２０が互いに圧接される。
そのため、両接合部１９，２０が確実に接触し、ヒータ
４からセンサ素子３への熱伝導効率が向上する。しか
も、ガス流入凹所２９を介して放射される輻射熱も加わ
る。その結果、センサ素子３の昇温速度及び最終到達温
度を従来のものに比較して改善することができる。従っ
て、センサ素子３の特性（早期活性化や出力安定化な
ど）が良好になり、内燃機関の空燃比制御上好影響を及
ぼす。また、ヒータ４への供給電力も少なくなり、ヒー
タ４の寿命を長くすることができる。The third embodiment has the following characteristics (a) to (c). (A) In the holding unit 2, the sensor element 3 and the heater 4 are joined and fastened to each other at their upper portions, and the joint portion 19 of the sensor element 3 is joined to the heater 4.
When the joint portion 20 is engaged with the engagement groove 28 in the hook-shaped engagement portion 27, the joint portions 19 and 20 are pressed against each other.
Therefore, the joint portions 19 and 20 are surely brought into contact with each other, and the heat conduction efficiency from the heater 4 to the sensor element 3 is improved. Moreover, radiant heat radiated through the gas inflow recess 29 is also added. As a result, it is possible to improve the temperature rising rate and the final temperature of the sensor element 3 as compared with the conventional one. Therefore, the characteristics of the sensor element 3 (early activation, output stabilization, etc.) are improved, which has a favorable effect on the air-fuel ratio control of the internal combustion engine. Further, the electric power supplied to the heater 4 is reduced, and the life of the heater 4 can be extended.
【００２９】（ロ） センサ素子３の接合部１９におい
て鉤状係合部２７内の係合溝２８（被冠部）に係入され
る部分が、この鉤状係合部２７で部分的に囲まれる。従
って、センサ素子３の接合部１９と燃焼ガスとの接触を
少なくしてこの接合部１９の温度低下を防止するととも
に、センサ素子３の接合部１９とヒータ４の接合部２０
との接触面積を増大させてヒータ４からセンサ素子３へ
の熱伝導効率を向上させることができる。その結果、セ
ンサ素子３の昇温速度及び最終到達温度をより一層改善
することができる。(B) A portion of the joint portion 19 of the sensor element 3 which is engaged with the engaging groove 28 (crowned portion) in the hook-like engaging portion 27 is partially formed by the hook-like engaging portion 27. Be surrounded. Therefore, the contact between the joint portion 19 of the sensor element 3 and the combustion gas is reduced to prevent the temperature of the joint portion 19 from decreasing, and the joint portion 19 of the sensor element 3 and the joint portion 20 of the heater 4 are prevented.
It is possible to increase the contact area with and to improve the heat conduction efficiency from the heater 4 to the sensor element 3. As a result, it is possible to further improve the temperature rising rate and the final reached temperature of the sensor element 3.
【００３０】（ハ） 保持ユニット２内のホルダ５でセ
ンサ素子３に対する若干の緩みを持たせてセンサ素子３
の反りを許容すれば、センサ素子３の接合部１９を鉤状
係合部２７内の係合溝２８に係入してヒータ４の接合部
２０に対し確実に接触させることができる。(C) The holder 5 in the holding unit 2 is slightly loosened with respect to the sensor element 3, and the sensor element 3
If the warp is allowed, the joint portion 19 of the sensor element 3 can be engaged with the engagement groove 28 in the hook-shaped engagement portion 27 and surely brought into contact with the joint portion 20 of the heater 4.
【００３１】なお、図示しないが、センサ素子３の接合
部１９に鉤状係合部を形成してこの鉤状係合部内の係合
溝にヒータ４の接合部２０を係入したり、これらの接合
部１９，２０にそれぞれ係合部を形成して互いに係合さ
せたりしてもよい。Although not shown, a hook-shaped engaging portion is formed in the joint portion 19 of the sensor element 3 and the joint portion 20 of the heater 4 is engaged in an engaging groove in the hook-shaped engaging portion. Engagement portions may be formed in the joint portions 19 and 20 of the above to engage with each other.
【００３２】〔第四実施形態〕次に、本発明の第四実施
形態にかかる積層型酸素センサを図６（ｃ）を参照して
説明する。この第四実施形態は、前記第一実施形態と下
記の点で異なる。[Fourth Embodiment] Next, a laminated oxygen sensor according to a fourth embodiment of the present invention will be described with reference to FIG. The fourth embodiment differs from the first embodiment in the following points.
【００３３】ヒータ４の接合部２０にはセンサ素子３の
接合部１９で固定電解質シート８の雰囲気側酸素反応電
極１１を囲う輻射凹部３０が形成され、この輻射凹部３
０の内面と雰囲気側酸素反応電極１１との間に輻射熱空
間３１を有している。図示しないが、この輻射凹部３０
は雰囲気側酸素反応電極１１を燃焼ガス雰囲気に開放す
るように開放されている。この輻射凹部３０の内面に対
する垂線が雰囲気側酸素反応電極１１を通るように、焼
成前または焼成後に輻射凹部３０を機械加工により形成
している。At the joint portion 20 of the heater 4, there is formed a radiation concave portion 30 which surrounds the atmosphere side oxygen reaction electrode 11 of the fixed electrolyte sheet 8 at the joint portion 19 of the sensor element 3, and the radiation concave portion 3 is formed.
A radiant heat space 31 is provided between the inner surface of No. 0 and the atmosphere-side oxygen reaction electrode 11. Although not shown, this radiation recess 30
Are opened so as to open the atmosphere-side oxygen reaction electrode 11 to the combustion gas atmosphere. The radiation recess 30 is formed by machining before or after firing so that the perpendicular to the inner surface of the radiation recess 30 passes through the atmosphere-side oxygen reaction electrode 11.
【００３４】第四実施形態は下記（イ）の特徴を有す
る。
（イ） ヒータ４からセンサ素子３への熱伝導は主とし
て輻射によるものであることに鑑み、センサ素子３の雰
囲気側酸素反応電極１１を輻射熱空間３１を介して輻射
凹部３０により囲っている。そのため、この輻射凹部３
０の内面の輻射熱面積が増大し、この内面から垂直に放
射される輻射熱を雰囲気側酸素反応電極１１に集中して
効率良く伝達することができ、ヒータ４からセンサ素子
３への熱伝導効率が向上する。その結果、センサ素子３
の昇温速度及び最終到達温度を従来のものに比較して改
善することができる。従って、センサ素子３の特性（早
期活性化や出力安定化など）が良好になり、内燃機関の
空燃比制御上好影響を及ぼす。また、ヒータ４への供給
電力も少なくなり、ヒータ４の寿命を長くすることがで
きる。The fourth embodiment has the following characteristics (a). (A) Considering that the heat conduction from the heater 4 to the sensor element 3 is mainly due to radiation, the atmosphere-side oxygen reaction electrode 11 of the sensor element 3 is surrounded by the radiation concave portion 30 via the radiation heat space 31. Therefore, this radiation recess 3
The radiant heat area of the inner surface of 0 increases, and the radiant heat vertically radiated from the inner surface can be concentrated and efficiently transferred to the atmosphere-side oxygen reaction electrode 11, and the heat conduction efficiency from the heater 4 to the sensor element 3 can be improved. improves. As a result, the sensor element 3
It is possible to improve the temperature rising rate and the final temperature reached in comparison with the conventional one. Therefore, the characteristics of the sensor element 3 (early activation, output stabilization, etc.) are improved, which has a favorable effect on the air-fuel ratio control of the internal combustion engine. Further, the electric power supplied to the heater 4 is reduced, and the life of the heater 4 can be extended.
【００３５】[0035]
【発明の効果】本発明にかかる積層型酸素センサにおい
ては、ヒータからセンサ素子への熱伝導効率を向上させ
てセンサ素子の昇温速度及び最終到達温度を改善するこ
とができる。In the laminated oxygen sensor according to the present invention, the efficiency of heat transfer from the heater to the sensor element can be improved to improve the temperature rising rate and final temperature of the sensor element.
【図１】 （ａ）は第一実施形態にかかる積層型酸素セ
ンサの全体を示す縦断面図であり、（ｂ）は（ａ）の部
分拡大断面図であり、（ｃ）は第一実施形態の第一別例
を示す部分拡大断面図である。FIG. 1A is a vertical cross-sectional view showing an entire laminated oxygen sensor according to a first embodiment, FIG. 1B is a partially enlarged cross-sectional view of FIG. 1A, and FIG. It is a partial expanded sectional view showing the first example of a form.
【図２】 （ａ）は第一実施形態の第二別例を示す部分
拡大断面図であり、（ｂ）は第一実施形態の第三別例示
す部分拡大断面図である。FIG. 2A is a partially enlarged sectional view showing a second alternative example of the first embodiment, and FIG. 2B is a partially enlarged sectional view showing a third alternative example of the first embodiment.
【図３】 （ａ）は第一実施形態にかかる積層型酸素セ
ンサと従来の積層型酸素センサについてセンサ素子の昇
温速度を比較したグラフであり、（ｂ）は同じくセンサ
素子の最終到達温度を比較したグラフである。FIG. 3A is a graph comparing the temperature rising rates of the sensor elements of the laminated oxygen sensor according to the first embodiment and a conventional laminated oxygen sensor, and FIG. 3B is the final reached temperature of the sensor element. It is the graph which compared.
【図４】 （ａ）は第二実施形態にかかる積層型酸素セ
ンサの全体を示す縦断面図であり、（ｂ）は（ａ）の部
分拡大断面図である。FIG. 4A is a vertical cross-sectional view showing the entire laminated oxygen sensor according to the second embodiment, and FIG. 4B is a partially enlarged cross-sectional view of FIG. 4A.
【図５】 （ａ）は第二実施形態の別例にかかる積層型
酸素センサの全体を示す縦断面図であり、（ｂ）は
（ａ）の部分拡大断面図である。5A is a vertical cross-sectional view showing an entire laminated oxygen sensor according to another example of the second embodiment, and FIG. 5B is a partially enlarged cross-sectional view of FIG. 5A.
【図６】 （ａ）は第三実施形態にかかる積層型酸素セ
ンサの全体を示す縦断面図であり、（ｂ）は（ａ）の部
分拡大断面図であり、（ｃ）は第四実施形態にかかる積
層型酸素センサにおいてその部分拡大断面図である。FIG. 6A is a vertical cross-sectional view showing the entire stacked oxygen sensor according to the third embodiment, FIG. 6B is a partially enlarged cross-sectional view of FIG. 6A, and FIG. It is a partial expanded sectional view in the laminated oxygen sensor concerning a form.
【図７】 従来の積層型酸素センサの全体を示す縦断面
図である。FIG. 7 is a vertical cross-sectional view showing the entire conventional stacked oxygen sensor.
３…センサ素子、４…ヒータ、８…固体電解質シート、
１１…雰囲気側酸素反応電極、１４…大気側酸素反応電
極、１６…発熱部、１９…接合部、２０…接合部、２
１，２２…凹凸部、２４，２６…突起部、２７…係合
部、３０…輻射凹部。3 ... Sensor element, 4 ... Heater, 8 ... Solid electrolyte sheet,
11 ... Atmosphere side oxygen reaction electrode, 14 ... Atmosphere side oxygen reaction electrode, 16 ... Exothermic part, 19 ... Joining part, 20 ... Joining part, 2
1, 22 ... Concavo-convex portion, 24, 26 ... Projection portion, 27 ... Engaging portion, 30 ... Radiation concave portion.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) G01N 27/409 G01N 27/41 G01N 27/419 ─────────────────────────────────────────────────── ─── Continuation of the front page (58) Fields surveyed (Int.Cl. 7 , DB name) G01N 27/409 G01N 27/41 G01N 27/419
Claims (4)
シートの雰囲気側面で雰囲気側酸素反応電極を形成し、
燃焼ガス雰囲気と遮断した大気側に面する固体電解質シ
ートの大気側面で大気側酸素反応電極を形成したセンサ
素子と、 このセンサ素子に設けた接合部に接合される接合部でセ
ンサ素子の酸素反応電極の近傍に発熱部を有するヒータ
とを備えるとともに、 前記センサ素子と前記ヒータとを、それらの基端部から
先端部にわたり互いに重合させるとともに、互いに締め
付け固定されていないそれらの先端部に、前記センサ素
子の接合部及び前記ヒータの接合部をそれぞれ設け た酸
素センサにおいて、 前記センサ素子の接合部とヒータの接合部とには、互い
に接触して嵌合される凹凸部を形成したことを特徴とす
る酸素センサにおけるセンサ素子とヒータとの接合構
造。1. An atmosphere-side oxygen reaction electrode is formed on the atmosphere side surface of a solid electrolyte sheet that can come into contact with a combustion gas atmosphere,
The oxygen reaction of the sensor element at the sensor element with the oxygen reaction electrode on the atmosphere side formed on the atmosphere side of the solid electrolyte sheet facing the atmosphere side, which is cut off from the combustion gas atmosphere, and at the joint that is joined to the joint provided on this sensor element Rutotomoni a heater having a heat generating portion in the vicinity of the electrodes, and the said sensor element heater, from their base ends
Overlap each other over the tips and tighten them together
The sensor element is attached to those tips that are not attached and fixed.
In an oxygen sensor provided with a joint portion of a child and a joint portion of the heater, the joint portion of the sensor element and the joint portion of the heater are formed with an uneven portion which is fitted in contact with each other. Structure for joining a sensor element and a heater in an oxygen sensor that operates.
シートの雰囲気側面で雰囲気側酸素反応電極を形成し、
燃焼ガス雰囲気と遮断した大気側に面する固体電解質シ
ートの大気側面で大気側酸素反応電極を形成したセンサ
素子と、 このセンサ素子に設けた接合部に接合される接合部でセ
ンサ素子の酸素反応電極の近傍に発熱部を有するヒータ
とを備えるとともに、 前記センサ素子と前記ヒータとを、それらの基端部から
先端部にわたり互いに重合させるとともに、互いに締め
付け固定されていないそれらの先端部に、前記センサ素
子の接合部及び前記ヒータの接合部をそれぞれ設け た酸
素センサにおいて、 前記センサ素子の接合部とヒータの接合部とのうち少な
くとも一方の接合部には、他方の接合部に接触する突起
部を形成したことを特徴とする酸素センサにおけるセン
サ素子とヒータとの接合構造。2. An atmosphere-side oxygen reaction electrode is formed on the atmosphere side surface of a solid electrolyte sheet that can come into contact with a combustion gas atmosphere,
The oxygen reaction of the sensor element at the sensor element with the oxygen reaction electrode on the atmosphere side formed on the atmosphere side of the solid electrolyte sheet facing the atmosphere side, which is cut off from the combustion gas atmosphere, and at the joint that is joined to the joint provided on this sensor element Rutotomoni a heater having a heat generating portion in the vicinity of the electrodes, and the said sensor element heater, from their base ends
Overlap each other over the tips and tighten them together
The sensor element is attached to those tips that are not attached and fixed.
In the oxygen sensor provided with the joint portion of the child and the joint portion of the heater, at least one joint portion of the joint portion of the sensor element and the joint portion of the heater is provided with a protrusion that contacts the other joint portion. A bonded structure of a sensor element and a heater in an oxygen sensor characterized by being formed.
シートの雰囲気側面で雰囲気側酸素反応電極を形成し、
燃焼ガス雰囲気と遮断した大気側に面する固体電解質シ
ートの大気側面で大気側酸素反応電極を形成したセンサ
素子と、 このセンサ素子に設けた接合部に接合される接合部でセ
ンサ素子の酸素反応電極の近傍に発熱部を有するヒータ
とを備えるとともに、 前記センサ素子と前記ヒータとを、それらの基端部から
先端部にわたり互いに重合させるとともに、互いに締め
付け固定されていないそれらの先端部に、前記センサ素
子の接合部及び前記ヒータの接合部をそれぞれ設け た酸
素センサにおいて、 前記センサ素子の接合部とヒータの接合部とのうち少な
くとも一方の接合部には、この両接合部を互いに接触さ
せるように圧接する係合部を形成したことを特徴とする
酸素センサにおけるセンサ素子とヒータとの接合構造。3. An atmosphere-side oxygen reaction electrode is formed on the atmosphere side surface of the solid electrolyte sheet that can come into contact with a combustion gas atmosphere,
The oxygen reaction of the sensor element at the sensor element with the oxygen reaction electrode on the atmosphere side formed on the atmosphere side of the solid electrolyte sheet facing the atmosphere side, which is cut off from the combustion gas atmosphere, and at the joint that is joined to the joint provided on this sensor element Rutotomoni a heater having a heat generating portion in the vicinity of the electrodes, and the said sensor element heater, from their base ends
Overlap each other over the tips and tighten them together
The sensor element is attached to those tips that are not attached and fixed.
In an oxygen sensor provided with a joint portion of a child and a joint portion of the heater, at least one joint portion of the joint portion of the sensor element and the joint portion of the heater is configured so that both joint portions are in contact with each other. A joint structure of a sensor element and a heater in an oxygen sensor, characterized in that an engaging portion for press contact is formed.
シートの雰囲気側面で雰囲気側酸素反応電極を形成し、
燃焼ガス雰囲気と遮断した大気側に面する固体電解質シ
ートの大気側面で大気側酸素反応電極を形成したセンサ
素子と、 このセンサ素子に設けた接合部に接合される接合部でセ
ンサ素子の酸素反応電極の近傍に発熱部を有するヒータ
とを備えるとともに、 前記センサ素子と前記ヒータとを、それらの基端部から
先端部にわたり互いに重合させるとともに、互いに締め
付け固定されていないそれらの先端部に、前記センサ素
子の接合部及び前記ヒータの接合部をそれぞれ設け た酸
素センサにおいて、 前記ヒータの接合部には、センサ素子の雰囲気側酸素反
応電極を囲う輻射凹部を形成したことを特徴とする酸素
センサにおけるセンサ素子とヒータとの接合構造。4. An atmosphere-side oxygen reaction electrode is formed on the atmosphere side surface of the solid electrolyte sheet that can come into contact with a combustion gas atmosphere,
The oxygen reaction of the sensor element at the sensor element with the oxygen reaction electrode on the atmosphere side formed on the atmosphere side of the solid electrolyte sheet facing the atmosphere side, which is cut off from the combustion gas atmosphere, and at the joint that is joined to the joint provided on this sensor element Rutotomoni a heater having a heat generating portion in the vicinity of the electrodes, and the said sensor element heater, from their base ends
Overlap each other over the tips and tighten them together
The sensor element is attached to those tips that are not attached and fixed.
An oxygen sensor having a child joint and a heater joint , wherein the heater joint has a radiation recess surrounding the atmosphere-side oxygen reaction electrode of the sensor element. Bonding structure of element and heater.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14957196A JP3402068B2 (en) | 1996-06-11 | 1996-06-11 | Bonding structure of sensor element and heater in oxygen sensor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14957196A JP3402068B2 (en) | 1996-06-11 | 1996-06-11 | Bonding structure of sensor element and heater in oxygen sensor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09329573A JPH09329573A (en) | 1997-12-22 |
| JP3402068B2 true JP3402068B2 (en) | 2003-04-28 |
Family
ID=15478107
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14957196A Expired - Fee Related JP3402068B2 (en) | 1996-06-11 | 1996-06-11 | Bonding structure of sensor element and heater in oxygen sensor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3402068B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4693304B2 (en) * | 2001-08-30 | 2011-06-01 | 京セラ株式会社 | Oxygen sensor |
| CN1327201C (en) * | 2005-01-14 | 2007-07-18 | 清华大学 | Temperature sensor based on ordered multi-wall carbon nano-tube bundle and metal heterojunction |
| CN1327202C (en) * | 2005-01-14 | 2007-07-18 | 清华大学 | Temperature sensor based on disordered multi-wall carbon nano-tube and metal heterojunction |
-
1996
- 1996-06-11 JP JP14957196A patent/JP3402068B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09329573A (en) | 1997-12-22 |
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