JPH0815198A - Gas sensor - Google Patents
Gas sensorInfo
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- JPH0815198A JPH0815198A JP15126394A JP15126394A JPH0815198A JP H0815198 A JPH0815198 A JP H0815198A JP 15126394 A JP15126394 A JP 15126394A JP 15126394 A JP15126394 A JP 15126394A JP H0815198 A JPH0815198 A JP H0815198A
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- Prior art keywords
- gas sensor
- gas
- sensor
- sensitivity
- electrodes
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- 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.)
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- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はガスセンサのうち特に高
温排気ガス中の窒素酸化物（ＮＯX）を検出するのに適
したガスセンサに関する。The present invention relates to a gas sensor suitable for detecting a particular nitrogen oxides in the hot exhaust gases of the gas sensor (NO X).
【０００２】[0002]
【従来の技術】空気中の酸素、硫化水素、アンモニア、
アミン類及びメルカプタン類等の濃度を検出するガスセ
ンサとして、従来から電圧の変化によって濃度を検出す
る固体電解質タイプと、抵抗の変化によって濃度を検出
する半導体タイプがあり、前者にはＺrＯ2またはＺrＯ2
と酸化触媒を併用したもの、β−Ａl2Ｏ3に硝酸塩複電
極を併用したもの、ＡgＮＯ3等の硝酸塩自体を固体電解
質として使用したものがあり、後者にはフタロシアニン
等の有機物半導体を用いたものと金属酸化物半導体を用
いたものがある。そして、金属酸化物半導体の中には、
ＴiＯ2、ＳnＯ2或いはＷＯ3等の一成分系と、複数成分
からなるペロブスカイト型の金属酸化物半導体を用いた
ガスセンサが知られている。2. Description of the Related Art Oxygen, hydrogen sulfide, ammonia in air,
As gas sensors for detecting the concentration of amines and mercaptans, there are conventionally a solid electrolyte type that detects the concentration by a change in voltage and a semiconductor type that detects the concentration by a change in resistance. The former is ZrO 2 or ZrO 2
And β-Al 2 O 3 combined with a nitrate double electrode, and nitrates such as AgNO 3 used as a solid electrolyte. The latter uses an organic semiconductor such as phthalocyanine. Some of them use a metal oxide semiconductor. And in the metal oxide semiconductor,
A gas sensor using a one-component system such as TiO 2 , SnO 2 or WO 3 and a perovskite type metal oxide semiconductor composed of a plurality of components is known.
【０００３】[0003]
【発明が解決しようとする課題】上述した各種のガスセ
ンサを自動車からの排気ガス中のＮＯXを検出するため
に用いようとすると以下のような課題がある。先ず、Ｚ
rＯ2はＯ2ガスのセンサであり、このＺrＯ2を用いてＮ
ＯXを検出するにはＮＯXから解離したＯ2を検出しなけ
ればならないので、測定は極めて難しく現実的ではな
い。また、自動車の排気ガスの通路の温度は８００〜９
００℃まで上がることがあり、一方、硝酸塩のうちＮa
ＮＯ3の融点は３０７℃、ＫＮＯ3の融点は３３３℃、Ｂ
a(ＮＯ3)2融点は５９２℃であるので、これらを使用す
ることはできない。同様の理由からフタロシアニン等の
有機物半導体を高温の排気ガス中で用いることはできな
い。また、ＴiＯ2、ＳnＯ2或いはＷＯ3はＮＯやＮＯ2に
対する感度は高いものの、耐熱性の点で問題があり、車
載用のガスセンサとして使用することはできない。更
に、ペロブスカイト型の金属酸化物半導体については、
耐熱性及び耐久性については優れているものの、ＮＯや
ＮＯ2に対する感度が低く、複数成分からなるため性能
にバラツキが生じやすく且つコスト的にも不利がある。If the various gas sensors described above are used to detect NO X in the exhaust gas from an automobile, the following problems will occur. First, Z
rO 2 is a sensor for O 2 gas, and this ZrO 2 is used for N
Since detecting the O X must detect the O 2 dissociated from NO X, the measurement is not very difficult practical. Moreover, the temperature of the exhaust gas passage of the automobile is 800 to 9
The temperature may rise to 00 ° C, while Na among the nitrates
NO 3 has a melting point of 307 ° C., KNO 3 has a melting point of 333 ° C., B
Since the melting point of a (NO 3 ) 2 is 592 ° C., they cannot be used. For the same reason, organic semiconductors such as phthalocyanine cannot be used in high-temperature exhaust gas. Further, although TiO 2 , SnO 2 or WO 3 has high sensitivity to NO and NO 2 , it has a problem in heat resistance and cannot be used as a vehicle-mounted gas sensor. Furthermore, regarding the perovskite-type metal oxide semiconductor,
Although it has excellent heat resistance and durability, it has low sensitivity to NO and NO 2 and is composed of a plurality of components, so that the performance tends to vary and there is a cost disadvantage.
【０００４】[0004]
【課題を解決するための手段】上記課題を解決すべく本
発明は、ガスセンサの材料としてＮb2Ｏ5またはＮb2Ｏ5
とＲu（ルテニウム）を用いるようにした。ここで、金
属ＲuはＮＯの分子軌道に有るπ電子を受容する性質が
あるため、Ｒuを添加することにより構成成分は増加す
るするもののＮＯX感度は高まる。但し、Ｒuの添加割合
が０．１wt%未満であるとＮＯXガス選択感度の効果が薄
れ、また１．０wt%を越えるとＮb2Ｏ5自身のＮＯXガス
感受性を阻害する傾向が現れるため、Ｒuの添加割合は
０．１wt%以上１．０wt%以下とするのが好ましい。In order to solve the above problems, the present invention provides Nb 2 O 5 or Nb 2 O 5 as a material for a gas sensor.
And Ru (ruthenium) were used. Here, since the metal Ru has a property of accepting π electrons in the molecular orbital of NO, the addition of Ru increases the number of constituent components but increases the NO x sensitivity. However, if the addition ratio of Ru is less than 0.1 wt%, the effect of the NO x gas selective sensitivity is weakened, and if it exceeds 1.0 wt%, the tendency of Nb 2 O 5 itself to inhibit the NO x gas sensitivity appears. , Ru is preferably added in the range of 0.1 wt% or more and 1.0 wt% or less.
【０００５】[0005]
【作用】Ｎb2Ｏ5にＮＯXが接触すると、Ｎb2Ｏ5の半導
性（ｎ型、ｐ型）に応じて電気伝導度（抵抗）が変化
し、この変化を電気的に検出し、検出値からＮＯXを割
り出す。[Action] When the NO X is in contact with the Nb 2 O 5, semiconducting of Nb 2 O 5 (n-type, p-type) electrical conductivity (resistance) varies in accordance with, electrically detecting the change , NO x is calculated from the detected value.
【０００６】[0006]
【実施例】以下に本発明の実施例を添付図面に基づいて
説明する。ここで、図１は本発明に係るガスセンサのう
ちバルク法によって作製したガスセンサの斜視図、図２
は同ガスセンサのうち厚膜法によって作製したものの斜
視図、図３は同ガスセンサの設置箇所の一例を示した排
気管の斜視図である。Embodiments of the present invention will be described below with reference to the accompanying drawings. Here, FIG. 1 is a perspective view of a gas sensor manufactured by a bulk method among the gas sensors according to the present invention, and FIG.
FIG. 3 is a perspective view of the gas sensor manufactured by the thick film method, and FIG. 3 is a perspective view of an exhaust pipe showing an example of the installation location of the gas sensor.
【０００７】バルク法によって作製したガスセンサ１
は、円盤形状に成形されたＮb2Ｏ5またはＮb2Ｏ5とＲu
からなる焼結体２の表面にＡuまたはＰtペーストを塗布
してなる電極３，３を形成し、この電極３，３にＰtか
らなるリード線４，４を接続している。Gas sensor 1 manufactured by the bulk method
Is a disk-shaped Nb 2 O 5 or Nb 2 O 5 and Ru
Electrodes 3 and 3 formed by applying Au or Pt paste are formed on the surface of a sintered body 2 of Pt, and lead wires 4 and 4 of Pt are connected to the electrodes 3 and 3.
【０００８】一方、厚膜法によって作製したガスセンサ
１は、矩形状に成形されたアルミナ基板５上に櫛歯状電
極３，３をプリントし、この電極３，３を覆うようにア
ルミナ基板５上にＮb2Ｏ5またはＮb2Ｏ5とＲuからなる
焼結体２を層状に形成している。On the other hand, in the gas sensor 1 manufactured by the thick film method, the comb-teeth-shaped electrodes 3 are printed on an alumina substrate 5 formed in a rectangular shape, and the alumina substrate 5 is covered so as to cover the electrodes 3, 3. Further, a sintered body 2 made of Nb 2 O 5 or Nb 2 O 5 and Ru is formed in layers.
【０００９】また、本発明に係るガスセンサの設置箇所
としては、図３に示すように排気管の途中等が考えられ
る。即ち、エンジンにつながる上流側の排気管１１と触
媒ボックス１３との間にセンサボックス１２を設け、こ
のセンサボックス１２内に前記したガスセンサ１を設置
し、ガスセンサ１による検出値に応じて燃焼の制御を行
う。尚、触媒ボックス１３の下流端には下流側の排気管
１４が接続され、この下流側の排気管１４の下流端にマ
フラ１５が接続されている。Further, as an installation location of the gas sensor according to the present invention, as shown in FIG. That is, the sensor box 12 is provided between the exhaust pipe 11 on the upstream side connected to the engine and the catalyst box 13, and the gas sensor 1 described above is installed in the sensor box 12, and combustion control is performed according to the detection value of the gas sensor 1. I do. A downstream exhaust pipe 14 is connected to the downstream end of the catalyst box 13, and a muffler 15 is connected to the downstream end of the downstream exhaust pipe 14.
【００１０】次に、センサ材料としてＮb2Ｏ5を用いバ
ルク法によってガスセンサ１を作製する方法を述べる。
純度９９．９％のＮb2Ｏ5試薬（粒度数μｍ）にエタノ
ールを加えた後、遊星型ボールミルで３００rpm×３時
間粉砕を行った。粉砕後の粒度はレーザ型粒度分布計で
平均１μｍであった。次いで、上記によって得られた粉
体を油圧プレス機にて４００kgf/cm2で５分間プレス
し、直径１０mm、厚み２〜３mmのペレットを作製した。
続いて、上記ペレットを大気炉にて８００℃×３時間の
本焼成を行い、Ｐt（又はＡu）をスパッタ蒸着して電極
を形成し、リード線と電極とをＡg−Ｐd導電ペーストを
用いて接合することで、図１に示す構造のガスセンサを
得た。ここで、本焼成の時間や温度を変えることで粒径
が上記よりも大きくても焼結させることはできるので、
粉砕条件については上記に限定されるものではない。ま
たプレス条件についても同様である。Next, a method of manufacturing the gas sensor 1 by the bulk method using Nb 2 O 5 as a sensor material will be described.
After adding ethanol to a Nb 2 O 5 reagent (particle size: several μm) having a purity of 99.9%, it was pulverized with a planetary ball mill at 300 rpm for 3 hours. The particle size after pulverization was 1 μm on average with a laser type particle size distribution meter. Next, the powder obtained as described above was pressed with a hydraulic press machine at 400 kgf / cm 2 for 5 minutes to prepare pellets having a diameter of 10 mm and a thickness of 2 to 3 mm.
Subsequently, the pellets were subjected to main firing at 800 ° C. for 3 hours in an air furnace, Pt (or Au) was sputter-deposited to form electrodes, and lead wires and electrodes were formed using Ag-Pd conductive paste. By joining, the gas sensor having the structure shown in FIG. 1 was obtained. Here, by changing the time and temperature of the main firing, it is possible to sinter even if the particle size is larger than the above,
The grinding conditions are not limited to the above. The same applies to the pressing conditions.
【００１１】一方、厚膜法によるガスセンサの作製方法
は、純度９９．９％のＮb2Ｏ5試薬から粉体を調製する
までの工程は同じである。この後、粉体に水を加え、ペ
ースト状にした後にアルミナ基板に塗布乾燥させる。続
いて大気炉にて８００℃×３時間の本焼成を行い厚膜化
し、図２に示す構造のガスセンサを得た。On the other hand, in the method of manufacturing a gas sensor by the thick film method, the steps up to the preparation of powder from Nb 2 O 5 reagent having a purity of 99.9% are the same. Then, water is added to the powder to form a paste, which is then applied to an alumina substrate and dried. Subsequently, a main calcination was performed in an atmospheric furnace at 800 ° C. for 3 hours to form a thick film, and a gas sensor having the structure shown in FIG.
【００１２】上記方法により作製したバルク素子、厚膜
素子共に、一辺が約３０cmのボックス内にセットし、所
望のガス感度を測定した。測定方法は、素子をボックス
底部に断熱板を介して配置したセラミックスヒータ上に
置き、４００℃に加熱するとともに、ボックス上部に設
けたガス導入口よりＮ2ガスをパージする。数分間パー
ジを継続し、素子抵抗が安定化したところでバルブを閉
じる。そして、次に注射器によって所定量のＮＯガスを
サンプリングし、ボックス上部のシリコーンゴム膜の部
分を介してボックス内に注入する。図４は上記した作製
方法のうちバルク法にて作製したガスセンサのＮＯ濃度
と検出感度との関係を示すグラフであり、ガス感度
（％）＝（初期抵抗−抵抗）×１００／初期抵抗であ
る。このグラフからも明らかなように、Ｎb2Ｏ5及びＮb
2Ｏ5＋Ｒu何れもＮＯの検出感度に優れることが分る。Both the bulk device and the thick film device manufactured by the above method were set in a box having a side of about 30 cm, and the desired gas sensitivity was measured. As the measuring method, the element is placed on a ceramics heater arranged at the bottom of the box via a heat insulating plate, heated to 400 ° C., and N 2 gas is purged from a gas inlet provided at the top of the box. Continue purging for several minutes and close the valve when the element resistance stabilizes. Then, a predetermined amount of NO gas is sampled by a syringe and injected into the box through the silicone rubber film on the top of the box. FIG. 4 is a graph showing the relationship between the NO concentration and the detection sensitivity of the gas sensor manufactured by the bulk method among the above-described manufacturing methods, and gas sensitivity (%) = (initial resistance−resistance) × 100 / initial resistance. . As is clear from this graph, Nb 2 O 5 and Nb
It can be seen that both 2 O 5 + Ru have excellent NO detection sensitivity.
【００１３】また、図５（ａ）はＮb2Ｏ5のＮＯと妨害
ガスの感度を示すグラフ、（ｂ）はＮb2Ｏ5＋ＲuのＮＯ
と妨害ガスの感度を示すグラフ、（ｃ）はＲuの代りに
０．５wt%Ｐtを添加した場合のＮＯと妨害ガスの感度を
示すグラフ、（ｄ）は同様に０．５wt%Ｐdを添加した場
合のＮＯと妨害ガスの感度を示すグラフであり、Ｎb2Ｏ
5及びＮb2Ｏ5＋Ｒuについては、バルク法によって作製
した方が検出感度が高いこと、また作製方法がバルク法
或いは厚膜法のいずれであってもＮＯガスの検出選択性
に優れていることが分る。一方、Ｐt又はＰdを添加して
作製したセンサは、ＮＯガスの検出選択性及び感度が劣
る。Further, FIG. 5A is a graph showing the sensitivity of NO of Nb 2 O 5 and interfering gas, and FIG. 5B is the NO of Nb 2 O 5 + Ru.
And (c) is a graph showing the sensitivity of NO and interfering gas when 0.5 wt% Pt is added instead of Ru, (d) is the same as 0.5 wt% Pd. 2 is a graph showing the sensitivities of NO and interfering gas in the case of Nb 2 O
5 and Nb 2 O 5 + Ru have higher detection sensitivity when manufactured by the bulk method, and have excellent NO gas detection selectivity regardless of whether the manufacturing method is the bulk method or the thick film method. I understand. On the other hand, the sensor produced by adding Pt or Pd is inferior in NO gas detection selectivity and sensitivity.
【００１４】[0014]
【発明の効果】以上に説明したように本発明によれば、
ガスセンサの材料としてＮb2Ｏ5またはＮb2Ｏ5とＲu
（ルテニウム）を用いることで、耐熱性及び耐薬品性に
優れ、また構成成分が少ないために品質が安定し、更に
Ｏ2、ＣＯ及びＣＨ4等の他のガスの検出感度を抑えつつ
及びＮＯXの検出感度に優れたガスセンサとすることが
できる。したがって、自動車の排気ガス中のＮＯX濃度
を検出するガスセンサ、特にリーンバーン（希薄燃焼）
エンジンからの排気ガス中のＮＯX濃度を検出するガス
センサとして極めて好適である。更にＲu（ルテニウ
ム）の添加割合を０．１wt%以上１．０wt%以下とするこ
とで、ＮＯX検出に優れた特性を発揮する。According to the present invention as described above,
Nb 2 O 5 or Nb 2 O 5 and Ru as gas sensor materials
By using (ruthenium), the heat resistance and chemical resistance are excellent, the quality is stable because there are few constituents, and the detection sensitivity of other gases such as O 2 , CO and CH 4 is suppressed, and NO The gas sensor can have excellent X detection sensitivity. Accordingly, a gas sensor for detecting the concentration of NO X exhaust gas of an automobile, especially lean-burn
It is extremely suitable as a gas sensor for detecting the NO X concentration in the exhaust gas from the engine. Further, by setting the addition ratio of Ru (ruthenium) to 0.1 wt% or more and 1.0 wt% or less, excellent characteristics for NO x detection are exhibited.
【図１】本発明に係るガスセンサのうちバルク法によっ
て作製したガスセンサの斜視図FIG. 1 is a perspective view of a gas sensor manufactured by a bulk method among gas sensors according to the present invention.
【図２】本発明に係るガスセンサのうち厚膜法によって
作製したガスセンサの斜視図FIG. 2 is a perspective view of a gas sensor manufactured by a thick film method among the gas sensors according to the present invention.
【図３】本発明に係るガスセンサの設置箇所の一例を示
した排気管の斜視図FIG. 3 is a perspective view of an exhaust pipe showing an example of an installation location of a gas sensor according to the present invention.
【図４】本発明に係るガスセンサのＮＯ濃度と検出感度
との関係を示すグラフFIG. 4 is a graph showing a relationship between NO concentration and detection sensitivity of the gas sensor according to the present invention.
【図５】（ａ）〜（ｄ）はそれぞれＮb2Ｏ5、Ｎb2Ｏ5と
Ｒu、Ｐt及びＰdのＮＯと妨害ガスの感度を示すグラフ5 (a) to (d) are graphs showing the sensitivities of Nb 2 O 5 , Nb 2 O 5 and Ru, Pt and Pd to NO and interfering gases, respectively.
１…ガスセンサ、２…Ｎb2Ｏ5またはＮb2Ｏ5とＲuから
なる金属酸化物半導体、３…電極、４…リード線、５…
基板。1 ... Gas sensor, 2 ... Metal oxide semiconductor composed of Nb 2 O 5 or Nb 2 O 5 and Ru, 3 ... Electrode, 4 ... Lead wire, 5 ...
substrate.
Claims (3)
する半導体タイプのガスセンサにおいて、このガスセン
サはＮb2Ｏ5をセンサ材料としていることを特徴とする
ガスセンサ。1. A semiconductor-type gas sensor whose resistance changes according to the concentration of a gas in contact with the gas sensor, wherein the gas sensor uses Nb 2 O 5 as a sensor material.
する半導体タイプのガスセンサにおいて、このガスセン
サはＮb2Ｏ5とＲu（ルテニウム）をセンサ材料としてい
ることを特徴とするガスセンサ。2. A semiconductor-type gas sensor whose resistance changes according to the concentration of a gas in contact with the gas sensor, wherein the gas sensor is made of Nb 2 O 5 and Ru (ruthenium).
前記Ｒuの添加量は０．１wt%以上１．０wt%以下である
ことを特徴とするガスセンサ。3. The gas sensor according to claim 2,
A gas sensor, wherein the amount of Ru added is 0.1 wt% or more and 1.0 wt% or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15126394A JP3415676B2 (en) | 1994-07-01 | 1994-07-01 | Gas sensor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15126394A JP3415676B2 (en) | 1994-07-01 | 1994-07-01 | Gas sensor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0815198A true JPH0815198A (en) | 1996-01-19 |
| JP3415676B2 JP3415676B2 (en) | 2003-06-09 |
Family
ID=15514846
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15126394A Expired - Fee Related JP3415676B2 (en) | 1994-07-01 | 1994-07-01 | Gas sensor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3415676B2 (en) |
-
1994
- 1994-07-01 JP JP15126394A patent/JP3415676B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP3415676B2 (en) | 2003-06-09 |
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