JPS59142445A - Durably stable gas detecting element - Google Patents
Durably stable gas detecting elementInfo
- Publication number
- JPS59142445A JPS59142445A JP58015464A JP1546483A JPS59142445A JP S59142445 A JPS59142445 A JP S59142445A JP 58015464 A JP58015464 A JP 58015464A JP 1546483 A JP1546483 A JP 1546483A JP S59142445 A JPS59142445 A JP S59142445A
- Authority
- JP
- Japan
- Prior art keywords
- sintered
- paste
- lanthanoid
- detecting element
- sno2
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Abstract
Description
【発明の詳細な説明】
この発明は、Sn 02焼結型ガス検知素子の改善を行
って経時安定性を向上させた経時安定性ガス検知素子に
関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a time-stable gas sensing element that is an improved Sn 02 sintered gas sensing element and has improved stability over time.
従来から、CH4,LPG、都市ガス、H2。Conventionally, CH4, LPG, city gas, H2.
CO等の可燃性ガスを検知する素子として、接触燃焼式
検知素子あるいは5n02 、Fe702等の金属酸化
物を用いた半導体式検知素子が使用されている。一般に
5n02半導体式検知素子は、一対の電極とこの一対の
電極間に5n02を主成分とし、これに5nC12等の
電導度改良剤。As elements for detecting combustible gases such as CO, catalytic combustion type detection elements or semiconductor type detection elements using metal oxides such as 5n02 and Fe702 are used. Generally, a 5n02 semiconductor type sensing element has a pair of electrodes and 5n02 as a main component between the pair of electrodes, and a conductivity improver such as 5nC12.
5t02 、Al2O3,5i02−A1203等の絶
縁性耐熱材、場合によっては触媒としてPt。Insulating heat-resistant materials such as 5t02, Al2O3, 5i02-A1203, and Pt as a catalyst in some cases.
Pd 、Rh等の貴金属類を含有せしめた焼結体を設け
ている。今、ガス検知素子が可燃性ガスと接触し、焼結
半導体がガスを吸着すると、その電導度は急激に増大す
る。そして可燃性ガスがなくなると焼結半導体はガスを
脱着してその電導度を初期の値に復元する。このガスの
吸着、脱着を敏速に行わせるため、ガス感応体である焼
結半導体は直接または間接に加熱され、一般に300°
C〜450°Cに常時保たれている。A sintered body containing noble metals such as Pd and Rh is provided. Now, when the gas sensing element comes into contact with a flammable gas and the sintered semiconductor adsorbs the gas, its electrical conductivity increases rapidly. When the flammable gas is removed, the sintered semiconductor desorbs the gas and restores its electrical conductivity to its initial value. In order to quickly adsorb and desorb this gas, the sintered semiconductor that is the gas sensitive material is heated directly or indirectly, generally at 300°.
The temperature is constantly maintained between ℃ and 450℃.
上記のように、ガス検知素子は常時通電することにより
燃結半導体部分を300〜450°Cに加熱して使用し
ているため、日時の経過による熱履歴、特に厨房等の高
湿度中での熱履歴により焼結半導体の表面微細構造が変
化し、焼結半導体の電導度を増大させる。したがって、
当初ガスの種類によりそれぞれ適正なガス濃度において
警報を発するよう設定しておいても、使用日時の経過と
使用環境によっては、その設定濃度以下の稀薄なガス状
態であっても警報を発する場合があり、警親器として大
きな問題となっていた。As mentioned above, gas detection elements are used by heating the sintered semiconductor part to 300 to 450°C by constantly energizing it, so the heat history changes over time, especially in high humidity environments such as kitchens. Thermal history changes the surface microstructure of the sintered semiconductor, increasing its electrical conductivity. therefore,
Even if you initially set the alarm to sound at the appropriate gas concentration depending on the type of gas, depending on the date and time of use and the usage environment, the alarm may sound even if the gas is in a dilute state below the set concentration. This was a big problem as a police weapon.
この発明は、上記の点にかんがみなされたもので、5n
02にランタノイド酸化物とTi。This invention was made in view of the above points, and
02 contains lanthanide oxide and Ti.
Zr、Hf、Thの酸化物をそれぞれ0 、01〜20
mo1%の範囲で含有せしめることにより適宜な電導度
を保持し、長期間の使用あるいは高湿度雰囲気における
使用においてもその電導度に変化を少なくして経時安定
性を大幅に改善したガス検知素子を提供するものである
。以下、この発明について説明する。Zr, Hf, and Th oxides are 0 and 01 to 20, respectively.
By containing the gas in the range of 1% by mo, it is possible to maintain an appropriate conductivity, reduce changes in conductivity even during long-term use or use in a high-humidity atmosphere, and significantly improve stability over time. This is what we provide. This invention will be explained below.
(実施例1)
Sn02の所定量を秤取し、これにランクメイド酸化物
およびTi、Zr、Hf、Thの酸化物をそれぞれ所定
比率になるように添加し、水を加えて粉砕、混合してペ
ースト状とする。(Example 1) A predetermined amount of Sn02 was weighed out, a rank-made oxide and oxides of Ti, Zr, Hf, and Th were added to it in predetermined ratios, and water was added, crushed, and mixed. Make a paste.
次に」二記ペーストを裏面に白金発熱体を設けたアルミ
ナ基板の表面に設けた一対の白金電極間に塗布し、80
℃において2時間乾燥し、次いで800″Cにおいて2
時間焼成する(以下この方法を混合法という)。Next, the paste described in "2" was applied between a pair of platinum electrodes provided on the surface of an alumina substrate with a platinum heating element provided on the back surface, and
Dry at 800″C for 2 hours, then dry at 800″C for 2 hours.
(hereinafter this method will be referred to as the mixing method).
(実施例2)
Sn02を水に分散、混合してペースト状とし、上記同
様にアルミナ基板の白金電極間に塗布、乾燥し、400
℃で1時間仮焼し、熱分解により酸化物となるランタノ
イド化合物およびTi、Zr、Hf、Th化合物の混合
水溶液を所定含有量になるように含浸し、乾燥後800
°Cにおいて2時間焼成した(以下この方法を含浸法と
いう)。(Example 2) Sn02 was dispersed and mixed in water to make a paste, and the same was applied between platinum electrodes on an alumina substrate, dried, and
℃ for 1 hour, impregnated with a mixed aqueous solution of Ti, Zr, Hf, and Th compounds and a lanthanoid compound that becomes an oxide by thermal decomposition to a predetermined content, and dried at 800℃.
It was baked at °C for 2 hours (hereinafter this method will be referred to as the impregnation method).
(実施例3)
Sn化合物の水溶液に実施例2に示すランタノイド化合
物およびTi、Zr、Hf、Th化合物の混合水溶液を
所定量添加し、pHを調整してSnを水酸化物として沈
殿させるとき、これらの添加物も同時に共沈させる。次
に沈殿物を分離。(Example 3) When adding a predetermined amount of the mixed aqueous solution of the lanthanoid compound shown in Example 2 and Ti, Zr, Hf, and Th compounds to the aqueous solution of the Sn compound, and adjusting the pH to precipitate Sn as a hydroxide, These additives are also coprecipitated at the same time. Next, separate the precipitate.
乾燥後、実施例1と同様に均一なペースト状とし、アル
ミナ基板の電極間に塗布し、乾燥後8000Cにおいて
2時間焼成した(以下この方法を共沈法という)。After drying, it was made into a uniform paste as in Example 1, and applied between the electrodes of an alumina substrate. After drying, it was fired at 8000C for 2 hours (hereinafter, this method will be referred to as coprecipitation method).
次に、実施例1(混合法)、実施例?(含浸法)、実施
例3(共沈法)により製作された焼結半導体を有するガ
ス検知素子を200時間通電して使用状態に保った後、
H2: 11000pp 。Next, Example 1 (mixed method), Example? (impregnation method) and Example 3 (co-precipitation method) After the gas sensing element having the sintered semiconductor was energized for 200 hours and kept in a working state,
H2: 11000pp.
CH4: 11000pP 、C2Hs OH: 11
000ppのそれぞれのガスに接触させ、その電気抵抗
値を測定し、これを初期抵抗値とした。その後、使用状
態を保って、その感ガス特性の経時変化を測定した。CH4: 11000pP, C2Hs OH: 11
000 pp of each gas, the electrical resistance was measured, and this was taken as the initial resistance. Thereafter, the device was kept in use and its gas sensitivity characteristics were measured over time.
その各種ガス検知素子における測定結果を第1表に示し
、第1表中の種類2において時間に対するH2の感度(
初期値比)の特性を図面に示す。Table 1 shows the measurement results for the various gas detection elements.
The characteristics of (initial value ratio) are shown in the drawing.
第1表または図面かられかるように、無添加の場合と、
この発明による添加の場合とでは、この発明によるもの
が経時安定性が向上している。As can be seen from Table 1 or the drawings, the case without additives,
Compared to the case of addition according to this invention, the one according to this invention has improved stability over time.
なお、SnO□に対するランタノイド酸化物およびIV
a族酸化物のmo1%は0.01〜20の範囲で有効で
あることが実験上確かめられた。In addition, lanthanide oxide and IV for SnO□
It has been experimentally confirmed that mo1% of group a oxide is effective in the range of 0.01 to 20.
以上説明したように、この発明はS n02焼結型ガス
検知素子の5n02焼結体に、ランタノイti1.l
麦
ド酸化物の少なくとも一種をo、oi〜20mo1%、
およびIVa族金属酸化物の少なくとも一種を0、O1
〜20mo1%とを含有せしめたので、適宜な電導度を
保持し、長期間の使用あるいは高湿度雰囲気における使
用においてもその電導度の変化を少なくし、優れた経時
安定性を有する5n02焼結型ガス検知素子が得られる
利点を有する。As explained above, the present invention uses lanthanoid ti1. l
At least one type of malt oxide is o, oi ~ 20 mo1%,
and at least one type of group IVa metal oxide.
The 5N02 sintered type contains ~20 mo1%, so it maintains appropriate conductivity, reduces changes in conductivity even when used for long periods of time or in high humidity environments, and has excellent stability over time. This has the advantage that a gas sensing element can be obtained.
図面は5n02にLa2030.5mo1%。
Hf021mo1%添加した場合の時間に対するH2の
感度(初期値比)の特性図である。
一時間
手続補正書(自発)
昭和59年3月13日
特許庁長官殿
1、事件の表示 特願昭58−0154E!4号2、発
明の名称 経時安定性ガス検知素子3、補正をする者
事件との関係 特許出願人
住所 大阪府大阪市淀川区三津屋中2丁目5番4号名称
新コスモス電機株式会社
代表者 笠原 理一部
4、代 理 人〒150
東京都渋谷区桜丘町31番16号 奥の松ビル6階小林
特許事務所電話03 (496) 1256番5、補正
の対象
明細書の発明の詳細な説明の欄
6、補正の内容
(1)明細書第2頁17行の「当初ガス」を、「当初、
ガス」と補正する。
(2)同じく第3頁8行の「電導度に変化」を、「電導
度およびガス感度の変化」と補正する。
(3)同じく第5頁12行の「感度」を、「感度変化」
と補正する。
以上The drawing shows 5n02 and La2030.5mo1%. It is a characteristic diagram of H2 sensitivity (initial value ratio) with respect to time when Hf021mo1% is added. One-hour procedural amendment (spontaneous) March 13, 1980 Dear Commissioner of the Japan Patent Office 1, Indication of the case Patent application 1982-0154E! No. 4 No. 2, Title of the invention Time-stable gas detection element 3, Relationship to the case of the person making the amendment Patent applicant address 2-5-4 Mitsuya Naka, Yodogawa-ku, Osaka-shi, Osaka Name Shin-Cosmos Electric Co., Ltd. Representative Kasahara Department of Science 4, Agent: Kobayashi Patent Office, 6th floor, Okunomatsu Building, 31-16 Sakuragaoka-cho, Shibuya-ku, Tokyo 150, Japan Telephone: 03 (496) 1256-5, Detailed explanation of the invention in the specification subject to amendment Column 6, Contents of amendment (1) “Initial gas” on page 2, line 17 of the specification has been changed to “initially,
"Gas" is corrected. (2) Similarly, "Change in conductivity" on page 3, line 8 is corrected to "Change in conductivity and gas sensitivity." (3) Also, change “sensitivity” on page 5, line 12 to “sensitivity change”.
and correct it. that's all
Claims (1)
イド酸化物の少なくとも一種を0.01〜20mo1%
、およびIVa族金属酸化物の少なくとも一種を0.0
1〜20mo1%含有せしめたことを特徴とする経時安
定性ガス検知素子。In the tin oxide sintered gas sensing element, at least one type of rank-made oxide is added to tin oxide in an amount of 0.01 to 20 mo1%.
, and at least one type of group IVa metal oxide at 0.0
A time-stable gas detection element characterized by containing 1 to 20 mo1%.
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP58015464A JPS59142445A (en) | 1983-02-03 | 1983-02-03 | Durably stable gas detecting element |
KR1019830006122A KR870001325B1 (en) | 1982-12-28 | 1983-12-22 | Gas detecting sensor |
DE8484300573T DE3476270D1 (en) | 1983-02-03 | 1984-01-30 | Gas sensor |
EP19840300573 EP0115953B1 (en) | 1983-02-03 | 1984-01-30 | Gas sensor |
CA000446558A CA1208424A (en) | 1983-02-03 | 1984-02-01 | Gas sensor |
US06/575,629 US4592967A (en) | 1983-02-03 | 1984-02-24 | Gas sensor of mixed oxides |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP58015464A JPS59142445A (en) | 1983-02-03 | 1983-02-03 | Durably stable gas detecting element |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS59142445A true JPS59142445A (en) | 1984-08-15 |
JPH0224461B2 JPH0224461B2 (en) | 1990-05-29 |
Family
ID=11889514
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP58015464A Granted JPS59142445A (en) | 1982-12-28 | 1983-02-03 | Durably stable gas detecting element |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS59142445A (en) |
-
1983
- 1983-02-03 JP JP58015464A patent/JPS59142445A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPH0224461B2 (en) | 1990-05-29 |
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