JPH02126146A - Gas sensor for controlling introduction of outdoor air of automobile - Google Patents
Gas sensor for controlling introduction of outdoor air of automobileInfo
- Publication number
- JPH02126146A JPH02126146A JP27958288A JP27958288A JPH02126146A JP H02126146 A JPH02126146 A JP H02126146A JP 27958288 A JP27958288 A JP 27958288A JP 27958288 A JP27958288 A JP 27958288A JP H02126146 A JPH02126146 A JP H02126146A
- Authority
- JP
- Japan
- Prior art keywords
- exhaust gas
- sensitivity
- sensor
- gas sensor
- gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000654 additive Substances 0.000 claims abstract description 17
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 6
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 6
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 6
- 229910052747 lanthanoid Inorganic materials 0.000 claims abstract description 6
- 150000002602 lanthanoids Chemical class 0.000 claims abstract description 6
- 229910052745 lead Inorganic materials 0.000 claims abstract description 6
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 5
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 5
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 claims abstract 3
- 150000002739 metals Chemical class 0.000 claims abstract 3
- 230000000996 additive effect Effects 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims 1
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- 230000035945 sensitivity Effects 0.000 abstract description 60
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 abstract description 16
- 238000001514 detection method Methods 0.000 abstract description 6
- 229910052742 iron Inorganic materials 0.000 abstract description 3
- 239000007789 gas Substances 0.000 description 88
- 239000010408 film Substances 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 16
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 230000007423 decrease Effects 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 150000002431 hydrogen Chemical class 0.000 description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
- F02B1/00—Engines characterised by fuel-air mixture compression
- F02B1/02—Engines characterised by fuel-air mixture compression with positive ignition
- F02B1/04—Engines characterised by fuel-air mixture compression with positive ignition with fuel-air mixture admission into cylinder
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
- F02B3/00—Engines characterised by air compression and subsequent fuel addition
- F02B3/06—Engines characterised by air compression and subsequent fuel addition with compression ignition
Abstract
Description
【発明の詳細な説明】 ［発明の利用分野１ この発明は、自動車の外気導入制御に関する。[Detailed description of the invention] [Field of application of the invention 1 The present invention relates to outside air introduction control for automobiles.
［従来技術１
自動車の車外空気の汚染をガスセンサにより検出し、車
室への外気導入を制御することが一群の出願により提案
されている。例えば実公昭５８−３９．２１９号や特公
昭５９−５０，５２８号等は、自動車の外気導入制御装
置の基本原理を提案している。自動車が前方の車両の排
ガス後流に入り込むと、ベンチレータから数十ｐｐｍ程
度のｃｏ等を含んだ汚染空気が吸引される。外気導入制
御装置では、ガスセンサでこれを検出し、外気の導入を
遮断する。このような技術は未だ実用化されていないが
、潜在的には大きな可能性を秘めた技術である。発明者
らは、この装置が将来実用化されることに備え、外気導
入制御用のガスセンサを開発した。[Prior Art 1] A series of applications have proposed detecting pollution of the air outside an automobile using a gas sensor and controlling the introduction of outside air into the passenger compartment. For example, Japanese Utility Model Publication No. 58-39.219 and Japanese Patent Publication No. 59-50,528 propose the basic principle of an outside air intake control device for an automobile. When a car enters the wake of the exhaust gas from the vehicle in front, contaminated air containing about several tens of ppm of CO is sucked in from the ventilator. The outside air introduction control device detects this with a gas sensor and shuts off the introduction of outside air. Although such technology has not yet been put into practical use, it is a technology with great potential. In preparation for the future practical use of this device, the inventors developed a gas sensor for controlling outside air introduction.
発明者がここで直面した問題は、ガソリン排ガスとディ
ーゼル排ガスとへのセンサ感度のアンバランスであった
。即ち通常のガスセンサでは、ディーゼル排ガスへの感
度が、ガソリン排ガスへの感度に比べて低く、ディーゼ
ル排ガスの検出が困難となった。The problem faced by the inventor here was an imbalance in sensor sensitivity to gasoline and diesel exhaust gases. That is, with a normal gas sensor, the sensitivity to diesel exhaust gas is lower than the sensitivity to gasoline exhaust gas, making it difficult to detect diesel exhaust gas.
このようなデータの１例を第２図に示す。このデータは
、自動車のベンチレータからの外気吹き出し口にガスセ
ンサを取り付け、実際に車両を走行させた際のものであ
る。なおセンサの取り付は技術が未洗練なため、センサ
の感度は見掛は上低く現れている（この点に付いては、
第６図に示した感度を参照のこと）。比較例１のセンサ
はＳｎＯ□系の汎用ガスセンサ（出願人のＴＧＳ ８２
２、ＴＧＳ ８２２は商品名）であり、比較例２のセン
サはＳｎＯ２系の水素センサである。水素センサは、Ｓ
ｎＯ，ガスセンサをシリコーン蒸気で処理し、水素以外
のガスへの感度を失わせたものである（第６回「センサ
の基、礎と応用シンポジウム」、昭和６１年５月３０日
、岡山義昭）。図のＯ印はディーゼル排ガス（バス）へ
の感度を、Δ印はＬＰＧ排ガス（タクシ−）への感度を
、０印はガソリン排ガス（普通乗用車）への感度を、■
印はガソリン排ガス（軽乗用車）への感度を現す。いず
れのガスセンサもディーゼル排ガスへの感度が不十分で
ある。またＬ Ｐ Ｇ排ガスへの感度はガソリン排ガス
への感度と同等で、これらは同様に考えれば良い。セン
サの種類について考えるど、水素選択性センサ（比較例
２）では、ディーゼル排ガスへの感度がほとんどない。An example of such data is shown in FIG. This data was obtained when a gas sensor was attached to the outside air outlet from the car's ventilator and the car was actually driven. Furthermore, due to the unsophisticated technology for mounting the sensor, the sensitivity of the sensor appears to be lower than it appears (with regard to this point,
(See sensitivity shown in Figure 6). The sensor of Comparative Example 1 is a SnO□-based general-purpose gas sensor (applicant's TGS 82
2, TGS 822 is a trade name), and the sensor of Comparative Example 2 is a SnO2-based hydrogen sensor. Hydrogen sensor is S
nO, a gas sensor treated with silicone vapor to lose its sensitivity to gases other than hydrogen (6th ``Fundamentals and Applications of Sensors Symposium'', May 30, 1988, Yoshiaki Okayama) . In the diagram, the O mark indicates the sensitivity to diesel exhaust gas (bus), the Δ mark indicates the sensitivity to LPG exhaust gas (taxi), the 0 mark indicates the sensitivity to gasoline exhaust gas (regular passenger car), and ■
The mark indicates sensitivity to gasoline exhaust gas (light passenger vehicles). Both gas sensors have insufficient sensitivity to diesel exhaust gas. Furthermore, the sensitivity to LPG exhaust gas is equivalent to the sensitivity to gasoline exhaust gas, and these can be considered in the same way. Considering the types of sensors, the hydrogen selectivity sensor (Comparative Example 2) has almost no sensitivity to diesel exhaust gas.
水素の検出は、ディーゼル排ガスの検出には役立たない
。Hydrogen detection is not useful for diesel exhaust detection.
これらのデータが意味するものは、外気導入装置はガソ
リン排ガスに対してのみ反応し、ディーゼル排ガスには
反応しないということである。このような状態は、自動
車の外気導入制御装置を不完全なものにする。What these data mean is that the fresh air inlet device only responds to gasoline exhaust gases, not diesel exhaust gases. Such a condition makes the outside air intake control device of the automobile incomplete.
［発明の課題］
この発明の課題は、ガソリン排ガスとディーゼル排ガス
とへの相対感度をそろえ、ディーゼル排ガスの検出を可
能にすることにある。そしてこの課題が達成されれば、
ガソリン排ガスとディーゼル排ガスの双方に動作する自
動車の外気導入制御装置が得られることになる。[Problem of the Invention] An object of the present invention is to equalize the relative sensitivities to gasoline exhaust gas and diesel exhaust gas, and to enable detection of diesel exhaust gas. And if this task is accomplished,
This results in an automobile outside air intake control device that operates on both gasoline exhaust gas and diesel exhaust gas.
［発明の構成１
この発明の特徴は、自動車の外気導入制御用のガスセン
サとして、膜状のＳｎＯ２に、アルカリ金属、アルカリ
土類金属、原子番号５７〜７２のランタニド、ＳＣ，Ｙ
％ Ｓｂ、Ｂ１５ＰｂＳＡｔ、Ｇａ、Ｚｎ、Ｆｅ５Ｎｂ
、Ｍｏからなる群の少なくとも一員の元素の化合物を添
加したものを、用いることにある（請求項１）。[Configuration 1 of the Invention] The present invention is characterized in that it is used as a gas sensor for controlling the introduction of outside air into an automobile.
% Sb, B15PbSAt, Ga, Zn, Fe5Nb
, Mo (Claim 1).
ここで好ましくはガスセンサとして、ＳｎＯ。Here, SnO is preferably used as the gas sensor.
に、アルカリ金属、アルカリ土類金属、原子番号５７〜
７２のランタニド、Ｓｃ、Ｙ、ＳｂＳ Ｂｉ。, alkali metals, alkaline earth metals, atomic numbers 57~
Lanthanide of 72, Sc, Y, SbS Bi.
Ｐｂからなる群の少なくとも一員の元素の化合物を添加
したものを用いる（請求項２）。これらの添加物は、Ａ
Ｉ、Ｇａ、Ｚｎ、Ｆｅ、Ｎｂ、Ｍｏよりもディーゼル排
ガスへの相対感度を高める。A compound containing at least one member of the group consisting of Pb is used (Claim 2). These additives are A
Increases relative sensitivity to diesel exhaust gas than I, Ga, Zn, Fe, Nb, and Mo.
ディーゼル排ガスとガソリン排ガスとを比較すると、汚
染物質の総量、特に可燃性ガスの総量はガソリン排ガス
の方が多い。即ちディーゼル排ガスは相対的にきれいな
排ガスである。しかしディーゼルの排ガスには異臭や刺
激性があり、検出を省略することはできない。次に個別
の成分を見ると、ガソリン排ガスではＣＯやＨ２が多量
に含まれている。一方デイーゼル排ガスではＣＯやＨ２
の含有量は少ない。比較例２の水素センサがディーゼル
感度を示さなかったのは、ディーゼル排ガス中の水素含
有量が僅かであることを示している。Comparing diesel exhaust gas and gasoline exhaust gas, the total amount of pollutants, especially the total amount of combustible gases, is higher in gasoline exhaust gas. That is, diesel exhaust gas is relatively clean exhaust gas. However, diesel exhaust gas has a strange odor and is irritating, so detection cannot be omitted. Next, looking at individual components, gasoline exhaust gas contains large amounts of CO and H2. On the other hand, in diesel exhaust gas, CO and H2
The content of is small. The fact that the hydrogen sensor of Comparative Example 2 did not exhibit diesel sensitivity indicates that the hydrogen content in diesel exhaust gas is small.
ディーゼル排ガスにもガソリン排ガスにもＮＯｘが含ま
れたおり、その総量には大差がない。一方一般にセンサ
は、ＮＯｘと可燃性ガスとに対して逆方向の感度を示す
。従ってディーゼル排ガスの検出には、ＮＯｘ感度の抑
制が必要である。ガソリン排ガスに少なくディーゼル排
ガスに多い成分として、アルデヒド類がある。しかしア
ルデヒド類の含有量は、ディーゼル排ガスでも僅かであ
る。Both diesel exhaust gas and gasoline exhaust gas contain NOx, and there is not much difference in the total amount. On the other hand, sensors generally exhibit opposite sensitivities to NOx and combustible gases. Therefore, detection of diesel exhaust gas requires suppression of NOx sensitivity. Aldehydes are components that are rare in gasoline exhaust gas but abundant in diesel exhaust gas. However, the content of aldehydes is small even in diesel exhaust gas.
これらの条件の基で、ディーゼルとガソリンとへの感度
を調整するには、以下のことが重要となる。Under these conditions, the following is important in adjusting the sensitivity to diesel and gasoline.
（１）ＮＯｘ感度を抑制し、ディーゼル排ガスへの感度
低下を防止する。(1) Suppress NOx sensitivity and prevent a decrease in sensitivity to diesel exhaust gas.
（２）ｃｏやＢ２への感度を減少させ、ガソリン感度を
減少させる。(2) Decrease sensitivity to co and B2 and reduce gasoline sensitivity.
（３）ディーゼルに特有な成分である、アルデヒド類へ
の感度を増す。(3) Increases sensitivity to aldehydes, which are components unique to diesel.
この発明はこれらの条件に沿ったものである。This invention meets these conditions.
ガスセンサを膜状（例えば厚さ５０μｍ以下、より好ま
しくは１５μｍ以下）としたのは、アルデヒド類が易分
解性のガスであるためである。アルデヒドの易分解性の
ため、センサを厚くするとアルデヒドがセンサ内部に拡
散する過程で分解してセンサ内部に到達せず、感度が低
下する。The reason why the gas sensor is made into a membrane (for example, with a thickness of 50 μm or less, more preferably 15 μm or less) is because aldehydes are easily decomposable gases. Because aldehyde is easily decomposed, if the sensor is made thicker, the aldehyde will decompose during the process of diffusing into the sensor and will not reach the inside of the sensor, resulting in a decrease in sensitivity.
次に発明者は、５ｎ０２への各種添加物の影響を調べ、
アルカリ金属、アルカリ土類金属、原子番号５７−７２
のランタニド、Ｓｃ、Ｙ、Ｓｂ。Next, the inventor investigated the effects of various additives on 5n02,
Alkali metal, alkaline earth metal, atomic number 57-72
Lanthanide, Sc, Y, Sb.
Ｂｉ、Ｐｂ、ＡＩ、Ｇａ、Ｚｎｓ Ｆｅ％ Ｎｂ。Bi, Pb, AI, Ga, Zns Fe% Nb.
Ｍｏが、ディーゼル排ガスへの増感作用とガソリン排ガ
スへの感度の抑制作用とを持つことを見出した。なおこ
れらの添加物の内、ディーゼルとガソリンとへの相対感
度をそろえるのに特に有効なものは、アルカリ金属、ア
ルカリ土類金属、原子番号５７−７２のう〉・タニド、
Ｓｃ、Ｙ％ Ｓｂ。It has been found that Mo has an effect of sensitizing diesel exhaust gas and suppressing sensitivity to gasoline exhaust gas. Among these additives, those that are particularly effective in equalizing the relative sensitivity to diesel and gasoline are alkali metals, alkaline earth metals, tanides with atomic numbers 57-72,
Sc, Y% Sb.
Ｂ１、Ｐｂである。これらの物質の添加は、５ｎＯ１膜
への含浸法で行ったので、添加量自体に付いて本質的な
意味のあるデータは得られていない。B1, Pb. Since these substances were added by impregnation into the 5nO1 film, no essentially meaningful data was obtained regarding the amounts added.
即ちこれらの添加物はＳｎＯ，膜の表面に沈着し、濃度
分布は膜の表面と内部とで均一ではない。また膜厚を変
え、添加物の原子数とＳｎの原子数との比を大きく変え
ても、結果への影響は小さい。That is, these additives are deposited on the surface of the SnO film, and the concentration distribution is not uniform between the surface and inside of the film. Further, even if the film thickness is changed and the ratio between the number of atoms of the additive and the number of Sn atoms is greatly changed, the effect on the results is small.
実験の範囲から添加物の範囲を示すと、添加物の金属原
子とＳｎＯ，中のＳｎ原子との比で、外掛けの０．２２
−５０ａｔ％、より好ましくは０．４〜２Ｑａ Ｌｍ％
か有効である。The range of the additive is shown from the range of the experiment.
-50at%, more preferably 0.4-2Qa Lm%
or is valid.
第６図に、ガソリン排ガスとディーゼル排ガスとへの相
対感度を示す。このデータは排ガスをサンプリングバッ
グでサンプリングし、約０−６％に希釈して、空気中と
の抵抗値の変化を求めたものである。比較例１の汎用ガ
スセンサや比較例２の水素センサでは、ディーゼル感度
が低い。一方単味の５ｎ０２の膜状センサ（膜厚１０μ
ｍ）では、ガソリン感度が低下するが、ディーゼル感度
は増加していない。これは比較例１のセンサ（［１１１
厚５０μｍ）の膜厚を小さくし、センサに含まれていた
貴金属触媒を除いたためで１）る。ＳｎＯ，膜（膜厚１
０μｍ１以下原則として同じ）にＹやＢａ。FIG. 6 shows the relative sensitivity to gasoline exhaust gas and diesel exhaust gas. This data was obtained by sampling exhaust gas with a sampling bag, diluting it to approximately 0-6%, and determining the change in resistance value compared to air. The general-purpose gas sensor of Comparative Example 1 and the hydrogen sensor of Comparative Example 2 have low diesel sensitivity. On the other hand, a simple 5n02 film sensor (film thickness 10μ
In m), gasoline sensitivity decreases, but diesel sensitivity does not increase. This is the sensor of Comparative Example 1 ([111
This is because the film thickness (50 μm) was reduced and the noble metal catalyst contained in the sensor was removed. SnO, film (thickness 1
0μm1 or less (same in principle), Y or Ba.
Ｂｉ等を含浸さゼると、ディーゼル感度が増加する。図
中の添加量は、含浸に用いたＹ等の濃度をｍ ｏ ｌ
／Ｌｉｔｔｅｒ単位で現し添加量はセンサ１個当たり０
、１ ｔｔ ＋−，１ｔｔｅｒである。なおこの添加
量は、０ 、１ ｍ ｏ ｌ ／ＬｉｔｔｅｒＸ ｌ
７１Ｌｉｔｔｅｒで２ｍ０１％の添加量に相当する。When impregnated with Bi or the like, diesel sensitivity increases. The amount added in the figure is the concentration of Y, etc. used for impregnation.
Expressed in units of /Litter, the amount added is 0 per sensor.
, 1 tt +−, 1 tter. Note that this addition amount is 0, 1 mol/Litter
71L corresponds to an addition amount of 2m01%.
第３図〜第５図に、実施例３ （Ｓ ｎ ０２に０．３
ｍ ｏ ｌ ／ＬｉｔｔｅｒのＹ溶液を１／７Ｌ滴下、
含浸）、比較例１、比較例２の各ガスセンサのガス濃度
特性を示す。比較例２のガスセンサでは水素感度のみが
顕著であり、ガソリン感度は高いがディーゼル感度は低
い。実施例３のガスセンサと比較例１のガスセンサとを
比較すると、ＮＯｘ感度を抑制してアルデヒド感度を増
した点、ＣＯやＨ８への感度を減少させた点が異なる。3 to 5 show Example 3 (0.3 in S n 02).
Drop 1/7L of Y solution of mol/Litter,
The gas concentration characteristics of each gas sensor of Comparative Example 1 and Comparative Example 2 are shown. In the gas sensor of Comparative Example 2, only hydrogen sensitivity is significant, gasoline sensitivity is high, but diesel sensitivity is low. Comparing the gas sensor of Example 3 and the gas sensor of Comparative Example 1, the differences are that NOx sensitivity was suppressed and aldehyde sensitivity was increased, and sensitivity to CO and H8 was decreased.
これはＮＯｘ感度の抑制によるディーゼル感度の低下の
防止、ＣＯやＨ！感度の減少によるガソリン感度の減少
、アルデヒド感度の向上によるディーゼルへの増感との
メカニズムと一致する。なおディーゼル感度の向上やガ
ソリン感度の抑制のメカニズムは、他の実施例でも同様
である。またここではアルデヒドを代表するものとして
、ホルムアルデヒドを用いた。This prevents a decrease in diesel sensitivity by suppressing NOx sensitivity, CO and H! This is consistent with the mechanism of a decrease in gasoline sensitivity due to a decrease in sensitivity, and an increase in diesel sensitivity due to an increase in aldehyde sensitivity. Note that the mechanism for improving diesel sensitivity and suppressing gasoline sensitivity is the same in other embodiments. Further, formaldehyde was used here as a representative aldehyde.
得られたガスセンサの、実車走行でのデータを第１図に
示す。図の縦軸は、センサに直列に接続した負荷抵抗（
Ｒ１）への出力を現す。実施例ではディーゼル排ガス（
○印、バスの排ガス）でも、ガソリン排ガス（０印、乗
用車の排ガス）と同等の感度を示すが、比較例ではディ
ーゼル排ガスへの感度は小さなピークとして現れるに過
ぎない。Figure 1 shows the data of the obtained gas sensor during actual vehicle driving. The vertical axis in the figure is the load resistance (
represents the output to R1). In the example, diesel exhaust gas (
The sensitivity to diesel exhaust gas (marked with ○, bus exhaust gas) is the same as that of gasoline exhaust gas (marked with 0, exhaust gas from passenger cars), but in the comparative example, the sensitivity to diesel exhaust gas only appears as a small peak.
［実施例］
ガスセンサの調整
Ｓ ｎ （ＯＣＨｘ）ａｏ （ＣＨ２）３Ｎ Ｈｉ）の
３θｗｔ％イソブタノール溶液をアルミナバイブに滴下
し、１１０°Ｃでイソブタノールを蒸発させた後、５０
０℃でＳ ｒ＋の有機化合物を熱分解し５ｎ０２薄膜と
した。このプロセスを繰り返し、膜厚１０μｍの単味の
Ｓ ｎ Ｏ２膜とした。ＳｎＯ，膜の製造方法は任意で
、他のＳｎの有機金属化合物を材料としても、あるいは
真空蒸着等を用いても良い。[Example] Adjustment of gas sensor A 3θwt% isobutanol solution of S n (OCHx)ao (CH2)3N Hi) was dropped onto an alumina vibe, and the isobutanol was evaporated at 110°C.
The S r+ organic compound was thermally decomposed at 0° C. to form a 5n02 thin film. This process was repeated to obtain a single SnO2 film with a thickness of 10 μm. The method for manufacturing the SnO film is arbitrary, and other organometallic compounds of Sn may be used as the material, or vacuum evaporation or the like may be used.
調整したＳｎＯ□膜に、各種金属元素の有機化合物溶液
、例えばＹの場合、Ｙ（ＯＣｔ（３）ｔ（０（ＣＨｚ：
ｈＮＨ２）のイソブタノール溶液を滴下し、５００°Ｃ
で熱分解した。他の添加物の場合も、類似構造の有機金
属化合物を用いた。滴下量はセンサ１個当たりｌμＬｉ
ｔｔｅｒとし、濃度は金属換算で０．０３〜０．３ｍｏ
ｌ／Ｉ、ｉ ｔ ｔｅｒとした。５ｎＯ８膜の膜厚は
１０μｍ１サブストレートのバイブは直径１．２ｍｍ、
長さ３ｍｍ強で、５ｎＣ）２膜の容積は１．２Ｘｌｏ−
’ｃｃに当ｔこる。これに５ｎＯｚの分子量１５０．６
ｇｒと、比重約７ｇｒ／ ｃ ｃとを加味すると、Ｓｎ
□ｚ膜は５．６μｍｏｌに当たり、金属の添加量は０．
１ｍｏ ｌ／ＬｉｔｔｅｒＸ Ｉ μＬｉｔｔｅｒで外
掛けの約２ｍ０１％に当たる。従って０．０３〜０．３
ｍｏ ］／Ｌｉｔｔｅｒの溶液の滴下は、０．６〜３ｍ
ｏ１％の添加に相当する。なお発明者は５ｎＯｚ膜の膜
厚を１μｍとし、添加液を０．０３−０．２ｍｏ Ｉ／
ＬｉｔｔｅｒＸｌ／７Ｌとして、添加量を６〜４０ｍｏ
１％とすることを試みた。しかし結果は同等で、添加物
濃度の限界は明らかにはならなかった。An organic compound solution of various metal elements, for example, in the case of Y, Y(OCt(3)t(0(CHz:
Add dropwise isobutanol solution of hNH2) and heat at 500°C.
It was thermally decomposed. In the case of other additives, organometallic compounds with similar structures were also used. The dripping amount is lμLi per sensor.
tter, and the concentration is 0.03 to 0.3 mo in terms of metal.
l/I, it ter. The thickness of the 5nO8 film is 10 μm.The diameter of the vibrator for 1 substrate is 1.2 mm.
With a length of just over 3mm, the volume of the 5nC)2 film is 1.2Xlo-
'cc hit. This has a molecular weight of 150.6 at 5 nOz.
gr and the specific gravity of about 7 gr/cc, Sn
□z film is 5.6 μmol, and the amount of metal added is 0.
1 mol/LitterX I μLitter corresponds to approximately 2m01% of the external capacity. Therefore 0.03-0.3
mo]/Litter solution is dropped from 0.6 to 3 m.
Corresponds to addition of o1%. In addition, the inventor set the film thickness of the 5nOz film to 1 μm, and added the additive solution to 0.03-0.2mo I/
Addition amount is 6 to 40 mo as LitterXl/7L
An attempt was made to make it 1%. However, the results were comparable and no limits on additive concentration were apparent.
得られたＳｎＯ，膜に一対の電極を接続し、サブストレ
ートのアルミナパイプにはヒータコイルを挿入して、ガ
スセンサとした。このセンサの形状は比較例１や比較例
２のものと同等で、ヒータを用いセンサを３８０°Ｃに
加熱し、特性を評価した。A pair of electrodes was connected to the obtained SnO film, and a heater coil was inserted into the alumina pipe of the substrate to prepare a gas sensor. The shape of this sensor was the same as that of Comparative Example 1 and Comparative Example 2, and the sensor was heated to 380° C. using a heater to evaluate its characteristics.
ガスセンサの感度
得られたガスセンサ用いて、第１図〜第６図のデータを
採取した。第１図、第２図は実車走行でのデータで、第
３図〜第５図は用いたガスセンサのガス濃度特性である
。第６図に、約０．６％に希釈したガソリンとディーゼ
ルの排ガスへの感度を示す。なお図の下部の記号は、含
浸させた金属元素と含浸時の濃度（ｍ ｏ ｌ ／Ｌｉ
ｔｔｅｒ単位）を示す。Sensitivity of the gas sensor The data shown in FIGS. 1 to 6 were collected using the obtained gas sensor. Figures 1 and 2 show data from actual vehicle running, and Figures 3 to 5 show gas concentration characteristics of the gas sensor used. Figure 6 shows the sensitivity to exhaust gas of gasoline and diesel diluted to about 0.6%. The symbols at the bottom of the figure indicate the impregnated metal elements and the concentration at the time of impregnation (mol/Li
tter unit).
各種添加物の影響を表１に示す。Table 1 shows the effects of various additives.
表１
添加物 濃度
（ｍ ｏ ｌ ／Ｉｘ ｌ μＬ）
比較例３ ５ｎ０２単味
実施例
１Ｙ０．０３
２Ｙ０．１
３Ｙ０．３
感 度
ガソリン ディーゼル
６．２ ２．４
５．２
５．１
６．０
２．８
３．６
４．３
４ Ｂａ０．１
５ Ｍｇ０．０３
６ Ｍｇ０．１
７ ＭｇＯ，３
８Ｃａ０．３
９ Ｓｒ０．１
５．２
６．２
５．８
５．２
６．８
５．６
３．８
３゜３
３．４
５．２
３．８
３．２
１０ Ｋ Ｏ，１
１１Ｎａ０．１
５．６
５．４
４．２
３．８
１２ Ｌａ０．０３
１３ Ｌａ０．１
１４ Ｌａ０．２８
５．４
４．６
３．５
３．４
３．５
２．７
Ｐ ｒ Ｏ，０３
Ｎｄｏ、０３
Ｎｄ０．ｌ
Ｎｄ０．３
Ｇｄ０．２７
Ｄｙ０．Ｉ
Ｅ ｒ Ｏ，ｌ
Ｈｆ０．１
表
１ 統さ
３．８
４．９
４．２
５．０
５．２
６．０
６．４
４．８
２．９
３．０
３．４
３．４
４．４
４．０
４．２
４．２
ＳｃＯ，１
４，２
３，６
Ｓ ｂ Ｏ，０３
Ｂｉｏ、１
Ｐｂ０．１
４．７
５．２
４．０
３．４
４．５
３．４
ＡＩｏ、ｌ
Ｇａ０．ｌ
ＺｎＯ，３
ＦｅＯ，Ｌ
Ｎｂ０．ｌ
Ｍｏ０．１
３．９
４．０
４．２
４．５
６．２
４．１
２．７
２．８
３．０
２．８
３．１
２．９
表 １ 続き
比較例
４ ＷＯ，ｌ ５．０ ２．１５
ＮｉＯ，ｌ ８．４ ３．０６
Ｃｒ０．１ １．６ １．２７
ｖＯ，ｌ ３．４ ２．３８ Ｔ
ａＯ，１６，６３−２
９Ｃｏ０．１ １５ ３．１０ Ｉｎ
Ｏ，ｌ ４．８ ２．６１ １ｎ０．３
４．８ ２．５２ ＭｎＯ，ｌ
４．３ ２．１３ ＺｒＯ，ｌ
６．２ ２．４４ ＴｉＯ，ｌ ６．
０ ２．７５ ＣｕＯ，ｌ ４．６
２．４１６ Ｂ Ｏ，１６，２２，６
１７ＳｉＯ，１６，２２，８
１８Ｐ Ｏ，１６，８２，６
＊ センサはいずれもＳｎＯ２系（膜厚１０μｍ）、添
加物は含浸法で添加、ガス感度は空気中とガス中との抵
抗値の比を現す。Table 1 Additive Concentration (mol / Ix l μL) Comparative Example 3 5n02 Single Example 1Y0.03 2Y0.1 3Y0.3 Sensitivity Gasoline Diesel 6.2 2.4 5.2 5.1 6.0 2.8 3.6 4.3 4 Ba0.1 5 Mg0.03 6 Mg0.1 7 MgO,3 8Ca0.3 9 Sr0.1 5.2 6.2 5.8 5.2 6.8 5.6 3.8 3゜3 3.4 5.2 3.8 3.2 10 K O,1 11Na0.1 5.6 5.4 4.2 3.8 12 La0.03 13 La0.1 14 La0.28 5.4 4.6 3.5 3.4 3.5 2.7 P r O, 03 Ndo, 03 Nd0. l Nd0.3 Gd0.27 Dy0. I E r O,l Hf0.1 Table 1 Coordination 3.8 4.9 4.2 5.0 5.2 6.0 6.4 4.8 2.9 3.0 3.4 3.4 4 .4 4.0 4.2 4.2 ScO,1 4,2 3,6 S b O,03 Bio, 1 Pb0.1 4.7 5.2 4.0 3.4 4.5 3.4 AIo , l Ga0. l ZnO, 3 FeO, L Nb0. l Mo0.1 3.9 4.0 4.2 4.5 6.2 4.1 2.7 2.8 3.0 2.8 3.1 2.9 Table 1 Continued Comparative Example 4 WO,l 5 .0 2.15
NiO,l 8.4 3.06
Cr0.1 1.6 1.27
vO,l 3.4 2.38 T
aO,16,63-2 9Co0.1 15 3.10 In
O, l 4.8 2.61 1n0.3
4.8 2.52 MnO,l
4.3 2.13 ZrO,l
6.2 2.44 TiO,l 6.
0 2.75 CuO,l 4.6
2.416 B O,16,22,6 17SiO,16,22,8 18P O,16,82,6 * All sensors are SnO2 type (film thickness 10 μm), additives are added by impregnation method, gas sensitivity is Represents the ratio of resistance values in air and gas.
次に、５ｎ０２膜の厚さと感度との関係を表２に示す。Next, Table 2 shows the relationship between the thickness of the 5n02 film and the sensitivity.
試料として、ＳｎＯ２膜（膜厚１μｍ）に０．０３−０
．２ｍｏ ｌ／ＬｉｔｔｅｒのＹ溶液を１μｍＬ滴下し
、熱分解したものを用いｊ；ｏ他の試料として、ＳｎＯ
，粉体に外掛けで２ｍｏ １％濃度となるようにＹ溶液
を含浸させ５００°Ｃで熱分解した後、４０ｐｍ厚の膜
状と３００μｍ厚のチップ状とに成型したものとを用い
た。As a sample, 0.03-0 was applied to the SnO2 film (film thickness 1 μm)
．． 1 μmL of 2 mol/Litter Y solution was added dropwise and thermally decomposed. As another sample, SnO
The powder was impregnated with a Y solution to a concentration of 2 mo 1%, thermally decomposed at 500° C., and then molded into a film with a thickness of 40 pm and a chip with a thickness of 300 μm.
表 ２
試 料 ガソリン感度
単味 １μｍ ６．４
同Ｙ０．０３ｍｏｌ／Ｌ ５．８
同Ｙ０．１ｍｏｌ／Ｌ ５．４
同Ｙ０．２ｍｏｌ／Ｌ ５．２
ディーゼル感度
２．８
４．２
４．２
４．６
単味 ４０μｍ ７．０
同Ｙ２ｍｏ １％ ５．８
２．８
３．６
単味 ３００μｍ
同Ｙ２ｍｏ １％
５．２
４．２
１．８
２．４
表２から明らかなように、膜厚の増加はディーゼルへの
相対感度に不利な影響を及ぼず。しかし薄膜のガスセン
サは被毒を受は易いので、薄膜が必ずしも有利であると
は限らない。これらのことを加味すると、センサの好ま
しい膜厚は５０μｍ以下、より好ましくは５０Ａ以上〜
１５μｍ以下となる。Table 2 Sample Gasoline sensitivity single 1 μm 6.4 Y0.03mol/L 5.8 Y0.1mol/L 5.4 Y0.2mol/L 5.2 Diesel sensitivity 2.8 4.2 4.2 4.6 Plain 40 μm 7.0 Same Y2mo 1% 5.8 2.8 3.6 Plain 300 μm Same Y2mo 1% 5.2 4.2 1.8 2.4 As is clear from Table 2, the film The increase in thickness does not adversely affect the relative sensitivity to diesel. However, thin film gas sensors are susceptible to poisoning, so thin films are not necessarily advantageous. Taking these things into account, the preferred film thickness of the sensor is 50 μm or less, more preferably 50 A or more.
It becomes 15 μm or less.
なおＳｎＯ２ガスセンサの添加物には、これ以外に経時
変化の抑制剤、温湿度依存性の抑制剤等の種々のものが
知られている。そこでこの発明の添加物は単独ではなく
、これらのものと共に添加しても良い。Note that various other additives for SnO2 gas sensors are known, such as inhibitors of changes over time, inhibitors of temperature and humidity dependence, and the like. Therefore, the additives of this invention may not be added alone, but may be added together with these additives.
［発明の効果］
この発明では、ディーゼル排ガスとガソリン排ガスへの
ガスセンサの感度をそろえる。この結果、自動車の外気
導入制御装置の問題点である、ディーゼル排ガスへの感
度不足を解消することができる。[Effects of the Invention] In this invention, the sensitivities of the gas sensors to diesel exhaust gas and gasoline exhaust gas are made the same. As a result, it is possible to solve the problem of insufficient sensitivity to diesel exhaust gas, which is a problem with the outside air intake control device of a car.
第１図は実施例のガスセンサの特性図、第２図は従来例
のガスセンサの特性図、第３図は実施例の特性図、第４
図、第５図は従来例の特性図、第６図は実施例の特性図
である。Fig. 1 is a characteristic diagram of the gas sensor of the embodiment, Fig. 2 is a characteristic diagram of the conventional gas sensor, Fig. 3 is a characteristic diagram of the embodiment, and Fig. 4 is a characteristic diagram of the gas sensor of the conventional example.
5 is a characteristic diagram of a conventional example, and FIG. 6 is a characteristic diagram of an embodiment.
Claims (2)
外気の導入を制御するようにした自動車の外気導入制御
用のガスセンサにおいて、 前記ガスセンサを、膜状のＳｎＯ＿２に、アルカリ金属
、アルカリ土類金属、原子番号５７〜７２のランタニド
、Ｓｃ、Ｙ、Ｓｂ、Ｂｉ、Ｐｂ、Ａｌ、Ｇａ、Ｚｎ、Ｆ
ｅ、Ｎｂ、Ｍｏからなる群の少なくとも一員の元素の化
合物を添加したものとしたことを特徴とする、自動車の
外気導入制御用のガスセンサ。(1) In a gas sensor for controlling the introduction of outside air into a vehicle cabin, which detects pollution of outside air by exhaust gas and controls the introduction of outside air into the vehicle interior, the gas sensor is made of a film of SnO_2 coated with an alkali metal, an alkali, etc. Earth metals, lanthanides with atomic numbers 57-72, Sc, Y, Sb, Bi, Pb, Al, Ga, Zn, F
1. A gas sensor for controlling outside air introduction into an automobile, characterized in that the compound is added with a compound of at least one member of the group consisting of e, Nb, and Mo.
属、原子番号５７〜７２のランタニド、Ｓｃ、Ｙ、Ｓｂ
、Ｂｉ、Ｐｂからなる群の少なくとも一員の元素の化合
物としたことを特徴とする、請求項１に記載の自動車の
外気導入制御用のガスセンサ。(2) The additive may be an alkali metal, an alkaline earth metal, a lanthanide with an atomic number of 57 to 72, Sc, Y, or Sb.
2. The gas sensor for controlling outside air introduction into an automobile according to claim 1, wherein the gas sensor is a compound of at least one member of the group consisting of , Bi, and Pb.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27958288A JPH02126146A (en) | 1988-11-04 | 1988-11-04 | Gas sensor for controlling introduction of outdoor air of automobile |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27958288A JPH02126146A (en) | 1988-11-04 | 1988-11-04 | Gas sensor for controlling introduction of outdoor air of automobile |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02126146A true JPH02126146A (en) | 1990-05-15 |
Family
ID=17612990
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27958288A Pending JPH02126146A (en) | 1988-11-04 | 1988-11-04 | Gas sensor for controlling introduction of outdoor air of automobile |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02126146A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03118459A (en) * | 1989-09-30 | 1991-05-21 | Toyota Central Res & Dev Lab Inc | Exhaust gas sensor |
| WO1996035115A1 (en) * | 1995-04-29 | 1996-11-07 | I.T.V.I. International Techno Venture Invest Aktiengesellschaft | Sensor assembly for controlling the ventilation of indoor spaces |
| US6287475B1 (en) | 1996-10-15 | 2001-09-11 | Citizen Watch Co., Ltd. | Magnetic head slider manufacturing method |
| JP2007147655A (en) * | 2007-03-09 | 2007-06-14 | Ngk Spark Plug Co Ltd | Gas sensor element |
| CN103063705A (en) * | 2012-12-25 | 2013-04-24 | 华中农业大学 | Trimethylamine gas sensor and preparation method thereof |
-
1988
- 1988-11-04 JP JP27958288A patent/JPH02126146A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03118459A (en) * | 1989-09-30 | 1991-05-21 | Toyota Central Res & Dev Lab Inc | Exhaust gas sensor |
| WO1996035115A1 (en) * | 1995-04-29 | 1996-11-07 | I.T.V.I. International Techno Venture Invest Aktiengesellschaft | Sensor assembly for controlling the ventilation of indoor spaces |
| US6287475B1 (en) | 1996-10-15 | 2001-09-11 | Citizen Watch Co., Ltd. | Magnetic head slider manufacturing method |
| JP2007147655A (en) * | 2007-03-09 | 2007-06-14 | Ngk Spark Plug Co Ltd | Gas sensor element |
| JP4603001B2 (en) * | 2007-03-09 | 2010-12-22 | 日本特殊陶業株式会社 | Gas sensor element |
| CN103063705A (en) * | 2012-12-25 | 2013-04-24 | 华中农业大学 | Trimethylamine gas sensor and preparation method thereof |
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