JPH0713603B2 - Method for manufacturing gas detection element - Google Patents
Method for manufacturing gas detection elementInfo
- Publication number
- JPH0713603B2 JPH0713603B2 JP61005111A JP511186A JPH0713603B2 JP H0713603 B2 JPH0713603 B2 JP H0713603B2 JP 61005111 A JP61005111 A JP 61005111A JP 511186 A JP511186 A JP 511186A JP H0713603 B2 JPH0713603 B2 JP H0713603B2
- Authority
- JP
- Japan
- Prior art keywords
- gas
- detection element
- gas detection
- temperature
- content
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000001514 detection method Methods 0.000 title claims description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 238000000034 method Methods 0.000 title description 5
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 3
- 238000010304 firing Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 description 50
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 28
- 239000001282 iso-butane Substances 0.000 description 14
- 230000035945 sensitivity Effects 0.000 description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明はイソブタンガス等の可燃性ガスの検知回路に用
いるガス検知素子の製造方法に関する。The present invention relates to a method for manufacturing a gas detection element used in a detection circuit for a flammable gas such as isobutane gas.
（従来の技術） 従来、イソブタンガス等の可燃性ガスのガス検知素子と
して、SnO2を主成分としてこれにAg、Au、Pd、Pt、Rh、
Ru等の貴金属を副成分として添加したものが知られてい
る。(Prior Art) Conventionally, as a gas detection element for a flammable gas such as isobutane gas, SnO 2 as a main component, Ag, Au, Pd, Pt, Rh,
It is known that a noble metal such as Ru is added as an auxiliary component.
しかし上記ガス検知素子はガス検知を行う際ガス検知素
子を350℃以上の高温度で加熱しなければイソブタンガ
ス等の可燃性ガスに対して作動せず、しかもかかる高温
度で長時間に亘って作動させるとガス検知素子内に組込
まれている素子加熱ヒータが次第に劣化して作動温度を
保持出来ず感度が低下してしまい、またかかる高温度で
の作動によってイソブタンガス等の可燃性ガス以外のア
ルコール等の雑ガスをも検知する等の不都合を有してい
る。However, the above gas detection element does not work against flammable gas such as isobutane gas unless the gas detection element is heated at a high temperature of 350 ° C. or higher when performing gas detection, and at such high temperature for a long time. When operated, the element heater built into the gas detection element gradually deteriorates, and the operating temperature cannot be maintained, resulting in a decrease in sensitivity. Also, operation at such a high temperature causes other than flammable gas such as isobutane gas. It also has the disadvantage of detecting miscellaneous gases such as alcohol.
（発明が解決しようとする問題点） 本発明はかかる従来の不都合を解消し、イソブタンガス
等の可燃性ガスに対して200℃ないし250℃の温度下で優
れた感度を有し、安定性および耐久性に優れたガス検知
素子の製造方法を提供することを目的とする。(Problems to be Solved by the Invention) The present invention solves the conventional inconvenience, has excellent sensitivity to a flammable gas such as isobutane gas at a temperature of 200 ° C to 250 ° C, and has stability and stability. An object of the present invention is to provide a method for manufacturing a gas detection element having excellent durability.
（問題点を解決するための手段） 本発明のガス検知素子の製造方法は、SnCl4とSn（SO4）
２との水溶液にアンモニア水を滴下して沈澱生成物を得
た後、該沈澱生成物を乾燥し、焼成したSnO2を主成分と
し、これに▲SO2- 4▼を副成分として0.01ないし５重量
％含有せしめた後、焼成することを特徴とする。(Means for Solving Problems) A method for manufacturing a gas detection element according to the present invention includes SnCl 4 and Sn (SO 4 ).
After obtaining the dropwise aqueous ammonia precipitated product to an aqueous solution of 2, drying the precipitated product, a calcined SnO 2 as a main component, to which ▲ SO 2- 4 ▼ to from 0.01 to as a sub-component It is characterized in that it is baked after containing 5% by weight.
ここで、▲SO2- 4▼の含有量は▲SO2- 4▼をSO4とみな
し、重量％として示すものとする。Here, ▲ SO 2- 4 ▼ content of ▲ SO 2- 4 ▼ is regarded as SO 4, and that shown as weight%.
第１図は主成分SnO2に対し副成分▲SO2- 4▼を種々の量
で含有させて得られたガス検知素子の250℃温度下にお
ける該各▲SO2- 4▼の含有量（重量％）の空気中におけ
る電気抵抗値（以下単に抵抗値と称す）RA並びにイソブ
タンガス濃度1800ppmの雰囲気中における抵抗値RGとの
関係を示すもので、図中曲線Ａは空気中における抵抗値
RAを、曲線Ｂはイソブタンガス雰囲気中における抵抗値
RGを夫々示す。The content of each of ▲ SO 2- 4 ▼ under 250 ° C. the temperature of the gas detection element obtained by incorporating the first figure the relative principal component SnO 2 subcomponent ▲ SO 2- 4 ▼ varying amounts ( (% By weight) shows the relationship between the electric resistance value (hereinafter simply referred to as resistance value) RA in air and the resistance value RG in an atmosphere having an isobutane gas concentration of 1800 ppm. Curve A in the figure shows the resistance value in air.
RA and curve B are resistance values in an isobutane gas atmosphere
RG is shown respectively.
第１図に示すようにガス検知素子の空気中における抵抗
値RA（曲線Ａ）は▲SO2- 4▼の含有量の増加に従い上昇
傾向となりその含有量が0.5重量％で最大値に達し、更
に含有量が増加するに従い下降傾向となりその含有量が
10重量％を超えると横這い傾向を示す。またガス検知素
子のイソブタンガス雰囲気中における抵抗値RG（曲線
Ｂ）は▲SO2- 4▼の含有量の増加に従い下降傾向となり
その含有量が0.5重量％で最小値に達し、更に含有量が
増加するに従い上昇傾向となりその含有量が５重量％を
超えると横這い傾向を示す。Resistance in air of a gas sensing element as shown in FIG. 1 RA (curve A) is ▲ SO content thereof becomes upward trend with increasing content of 2-4 ▼ reaches a maximum at 0.5% by weight, As the content further increases, it tends to decrease and the content
If it exceeds 10% by weight, it tends to level off. The resistance value in the isobutane gas atmosphere of the gas sensing element RG (curve B) is ▲ SO 2-4 content thereof becomes a downward trend with increasing content of ▼ reaches a minimum at 0.5% by weight, more content When the content exceeds 5% by weight, it tends to rise as it increases, and it tends to level off.
また主成分SnO2に対し副成分▲SO2- 4▼を種々の量で含
有させて得たガス検知素子につき200℃の温度下で、該
各▲SO2- 4▼含有量（重量％）と空気中における抵抗値R
A並びにイソブタンガス濃度1800ppm雰囲気における抵抗
値RGを測定した場合も250℃温度下の場合と同様の結果
が得られた。Also the relative principal component SnO 2 subcomponent ▲ SO 2- 4 ▼ at a temperature of 200 ° C. per gas detection element obtained by incorporating various amounts, respective ▲ SO 2- 4 ▼ content (wt%) And resistance R in air
When the resistance value RG was measured in the atmosphere of A and isobutane gas concentration of 1800 ppm, the same result as that at the temperature of 250 ° C. was obtained.
従って主成分SnO2に対する副成分▲SO2- 4▼の含有量は
0.01重量％以上にすることによって検知ガスに対する感
度向上効果が得られる。Subcomponent therefore based on the main component SnO 2 ▲ SO 2- 4 ▼ content of
When the amount is 0.01% by weight or more, the effect of improving the sensitivity to the detection gas can be obtained.
またガスの検知素子は主成分SnO2に対し含有すべき副成
分▲SO2- 4▼の量の上限は空気中抵抗値RAとイソブタン
ガス雰囲気中抵抗値RGとの差異が明確に現れている範囲
すなわち５重量％となる。The sensing element of the gas difference between subcomponent ▲ SO 2- 4 ▼ amount upper limit air resistance RA and isobutane gas atmosphere resistance RG should contain to the main component SnO 2 are clearly appeared The range is 5% by weight.
尚、ガス検知素子に対する信頼性、安定性および経済上
の観点から主成分SnO2に対して副成分▲SO2- 4▼の含有
範囲を0.1重量％ないし３重量％とすることが好まし
い。Incidentally, reliability of the gas sensing element, it is preferable that the to with respect to the main component of SnO 2 in terms of stability and economic 0.1 wt% to the auxiliary component ▲ SO 2- 4 ▼ content range of 3 wt%.
（実施例） 次に実施例、比較例について詳しく説明する。(Example) Next, an Example and a comparative example are described in detail.
実施例 SnCl4とSn（SO4）２との重量比1:1の水溶液にアンモニ
ア水を滴下して沈澱生成物を得、この沈澱生成物を濾過
して乾燥後粉砕し、これを温度570℃で３時間焼成後、
再び粉砕してSnO2に対し▲SO2- 4▼が0.5重量％含有され
たガス検知素子原料を得た。得られた原料に純水を加え
てペースト状にし、大きさ縦2.5mm、横3.5mm、厚さ1.0m
mの形状に成形し電極を兼ねた素子加熱ヒータを埋め込
んで、温度600℃で１時間焼成してガス検知素子KAを得
た。Example Ammonia water was added dropwise to an aqueous solution of SnCl 4 and Sn (SO 4 ) 2 in a weight ratio of 1: 1 to obtain a precipitation product. The precipitation product was filtered, dried and pulverized, and the temperature was adjusted to 570. After firing at ℃ for 3 hours,
To SnO 2 ▲ SO 2- 4 ▼ got gas sensing element material is contained 0.5 wt% and pulverized again. Pure water is added to the obtained raw material to make a paste, and the size is 2.5 mm long, 3.5 mm wide, 1.0 m thick.
A gas detecting element KA was obtained by molding the element into a shape of m and embedding an element heater that also serves as an electrode, and baking at a temperature of 600 ° C. for 1 hour.
比較例 SnCl4のみの水溶液にアンモニア水を滴下して沈澱生成
物を得、焼成後▲SO2- 4▼が無含有の原料である以外は
前記実施例と同様にしてガス検知素子KBを得た。It was added dropwise aqueous ammonia to an aqueous solution of only Comparative Example SnCl 4 to give the precipitated product, other firing after ▲ SO 2- 4 ▼ is non-containing raw material to obtain a gas sensing element KB in the same manner as in Example It was
得られたガス検知素子KAおよびKBを温度200℃より400℃
までの間において各温度に保持しながら、空気中におけ
る抵抗値RA並びにイソブタンガス1800ppm雰囲気中にお
ける抵抗値RGについて夫々測定し、空気中における抵抗
値RAを、イソブタンガス雰囲気中における抵抗値RGで除
した値の対数値［l0g（RA/RG）］を検知ガスに対する感
度とし、この感度と各温度との関係すなわち感度変化を
求めた。その結果を第２図に示す。図中曲線Ｃは▲SO2-
4▼を含有するガス検知素子KAの感度変化、曲線Ｄは▲S
O2- 4▼が無含有のガス検知素子KBの感度変化を夫々示
す。Temperature of the obtained gas detection elements KA and KB from 200 ℃ to 400 ℃
Resistance values RA in the air and resistance value RG in the atmosphere of isobutane gas of 1800 ppm are measured respectively while maintaining each temperature up to, and the resistance value RA in the air is divided by the resistance value RG in the isobutane gas atmosphere. The logarithmic value [ 10 g (RA / RG)] of the measured value was taken as the sensitivity to the detection gas, and the relationship between this sensitivity and each temperature, that is, the sensitivity change was obtained. The results are shown in FIG. Curve C in the figure is ▲ SO 2-
4 Sensitivity change of gas detection element KA containing ▼, curve D is ▲ S
O 2-4 ▼ shows each change in sensitivity of the gas detecting element KB of free content.
第２図から実施例のガス検知素子KAは比較例のガス検知
素子KBに比して温度200℃ないし250℃の範囲において感
度に顕著な差があり、主成分SnO2に対して副成分として
▲SO2- 4▼を含有させることによりイソブタンガスに対
して200℃ないし250℃の温度下で極めて優れた感度を示
すことが確認された。As shown in FIG. 2, the gas detection element KA of the embodiment has a significant difference in sensitivity in the temperature range of 200 ° C. to 250 ° C. as compared with the gas detection element KB of the comparative example, and as a subsidiary component with respect to the main component SnO 2 . ▲ SO 2- 4 ▼ 200 to ° C. against isobutane gas by containing a to exhibit excellent sensitivity at a temperature of 250 ° C. was confirmed.
また本発明の製造方法で得られたガス検知素子は従来品
における温度350℃以上のような高温度ではなく、温度2
00℃ないし250℃のような低温度で作動させることが出
来るので、ガス検知素子内の素子加熱ヒーターが劣化す
ることがないため安定性があり耐久性に優れる。Further, the gas detection element obtained by the manufacturing method of the present invention does not have a high temperature such as a temperature of 350 ° C. or higher in the conventional product, but a temperature of 2
Since it can be operated at a low temperature such as 00 ° C to 250 ° C, the element heating heater in the gas detection element does not deteriorate, so it has stability and excellent durability.
（発明の効果） このように本発明方法で得られたガス検知素子は、主成
分SnO2に対し副成分▲SO2- 4▼を0.01ないし５重量％含
有しているために、イソブタンガス等の可燃性ガスを20
0℃ないし250℃の温度下で検知出来、低温度で作動させ
るため安定性および耐久性に優れる等の効果を有する。(Effect of the Invention) gas sensing element obtained in this manner, the present invention method, the relative principal component SnO 2 subcomponent ▲ SO 2- 4 ▼ to contain 5 wt% 0.01, isobutane gas or the like 20 flammable gases
It can be detected at a temperature of 0 ° C to 250 ° C, and since it operates at a low temperature, it has effects such as excellent stability and durability.
第１図は主成分SnO2に対する副成分▲SO2- 4▼含有量と
各抵抗値RA、RGとの関係を示す図、第２図は▲SO2- 4▼
を含有せるガス検知素子および▲SO2- 4▼無含有のガス
検知素子の各温度における感度変化を示す図である。Figure 1 is subcomponent ▲ SO 2- 4 ▼ content relative to the main component SnO 2 and the resistance value RA, diagram showing the relationship between the RG, FIG. 2 ▲ SO 2- 4 ▼
Which is a graph showing the sensitivity change at each temperature of the gas sensing element and ▲ SO 2- 4 ▼-free gas sensing element to contain.
Claims (1)
ア水を滴下して沈澱生成物を得た後、該沈澱生成物を乾
燥し、焼成したSnO2を主成分とし、これに▲SO2- 4▼を
副成分として0.01ないし５重量％含有せしめた後、焼成
することを特徴とするガス検知素子の製造方法。After 1. A yield the SnCl 4 and Sn (SO 4) precipitated product by dropwise addition of aqueous ammonia to an aqueous solution of 2, drying the precipitated product, a calcined SnO 2 as a main component, which ▲ SO 2- 4 ▼ the after 0.01 to the additional inclusion 5 wt% as an auxiliary component, the manufacturing method of the gas detection element and firing to.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61005111A JPH0713603B2 (en) | 1986-01-16 | 1986-01-16 | Method for manufacturing gas detection element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61005111A JPH0713603B2 (en) | 1986-01-16 | 1986-01-16 | Method for manufacturing gas detection element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62163956A JPS62163956A (en) | 1987-07-20 |
| JPH0713603B2 true JPH0713603B2 (en) | 1995-02-15 |
Family
ID=11602240
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61005111A Expired - Lifetime JPH0713603B2 (en) | 1986-01-16 | 1986-01-16 | Method for manufacturing gas detection element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0713603B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107831269B (en) * | 2017-10-19 | 2020-03-27 | 上海纳米技术及应用国家工程研究中心有限公司 | Method for improving stability of hydrogen sulfide sensitive tin dioxide gas sensitive material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58200153A (en) * | 1982-05-17 | 1983-11-21 | Matsushita Electric Ind Co Ltd | gas detection element |
-
1986
- 1986-01-16 JP JP61005111A patent/JPH0713603B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62163956A (en) | 1987-07-20 |
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