JPS6125306B2 - - Google Patents
Info
- Publication number
- JPS6125306B2 JPS6125306B2 JP8341579A JP8341579A JPS6125306B2 JP S6125306 B2 JPS6125306 B2 JP S6125306B2 JP 8341579 A JP8341579 A JP 8341579A JP 8341579 A JP8341579 A JP 8341579A JP S6125306 B2 JPS6125306 B2 JP S6125306B2
- Authority
- JP
- Japan
- Prior art keywords
- gas
- wires
- tin
- present
- platinum
- 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
Links
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 239000000956 alloy Substances 0.000 claims description 8
- 229910045601 alloy Inorganic materials 0.000 claims description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 7
- 239000011135 tin Substances 0.000 claims description 7
- 229910052718 tin Inorganic materials 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 238000001514 detection method Methods 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 235000014692 zinc oxide Nutrition 0.000 claims description 2
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims 1
- 239000007789 gas Substances 0.000 description 23
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 15
- 238000001179 sorption measurement Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- 239000006104 solid solution Substances 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000010953 base metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910002846 Pt–Sn Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000001028 reflection method Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
Landscapes
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Description
【発明の詳細な説明】
本発明は金属線の表面に金属酸化物を緻密に被
覆した被覆線で作られたガス検知素子に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a gas sensing element made of a coated wire in which the surface of the metal wire is densely coated with a metal oxide.
従来の半導体式ガス検知素子は、種々の金属酸
化物より成る混合物の粉末の作成、仮焼、粉砕、
成型、焼成等の工程を踏んで作られるのが一般的
であり、種々の製造工程を経るため、高品質のガ
ス検知素子を作るうえから非常に困難を伴い高価
となる欠点があつた。 Conventional semiconductor gas sensing elements require the preparation, calcination, and pulverization of a powder of a mixture of various metal oxides.
It is generally manufactured through processes such as molding and firing, and because it involves various manufacturing processes, it is extremely difficult and expensive to produce a high-quality gas sensing element.
本発明は上記のような欠点を除去したものであ
つて本発明のガス検知素子は、互いに撚り合わさ
れた２本の線より成り、前記線が白金属元素と
錫、銅又は亜鉛等から成る合金を加熱酸化して表
面に錫、銅又は亜鉛の酸化物を形成していること
を特徴とする。 The present invention eliminates the above-mentioned drawbacks, and the gas sensing element of the present invention is composed of two wires twisted together, and the wires are made of an alloy made of a platinum metal element and tin, copper, zinc, etc. is characterized by being heated and oxidized to form tin, copper or zinc oxides on the surface.
以下図面によつて本発明の実施例を説明する。 Embodiments of the present invention will be described below with reference to the drawings.
一般に二酸化錫は、他の金属酸化物半導体に比
べ、比較的低温において、ガスの吸脱着性に秀
れ、又結晶構造の熱的相変化が見られない等、ガ
スセンサとして安定性のよいことが一般に知られ
ている。 In general, compared to other metal oxide semiconductors, tin dioxide has excellent gas adsorption and desorption properties at relatively low temperatures, and its crystal structure shows no thermal phase change, making it highly stable as a gas sensor. generally known.
本発明においては例えば、錫を0.1〜1wt％含有
する白金基固溶合金（Pt−Sn金属塊）を従来技
術の方法によりダイスを通して線引し、直径の細
い２本の線１，２を用意する。 In the present invention, for example, a platinum-based solid solution alloy (Pt-Sn metal ingot) containing 0.1 to 1 wt% of tin is drawn through a die using a conventional method to prepare two wires 1 and 2 with small diameters. do.
この２本の線１，２を図に示すように互に撚り
合わせてガス吸着部３を形成し、その両端にリー
ド部４〜７を設ける。 These two wires 1 and 2 are twisted together as shown in the figure to form a gas adsorption section 3, and lead sections 4 to 7 are provided at both ends thereof.
しかる後、リード部４，５および６，７を夫々
電気的に接続して線１，２に電流を流し、空気中
で約1000℃に１時間加熱する。 Thereafter, the lead portions 4, 5 and 6, 7 are electrically connected, a current is applied to the wires 1, 2, and the wires are heated to about 1000° C. for 1 hour in air.
この結果、線の表面が純粋な二酸化錫の結晶粒
（空間群はＰ／mnm、格子定数ａp＝4.74、Ｃp＝
3.19Å）で被覆されるようになる。 As a result, the surface of the line is a pure tin dioxide crystal grain (space group P/mnm, lattice constant a p = 4.74, C p =
3.19Å).
即ち、上記の工程により前記白金基固溶合金の
選択酸化によつて、その一成分である錫の酸化物
が白金基固溶合金の表面に現われてくる。これは
電子線回析反射法によつて結晶学的に証明でき
る。 That is, through the selective oxidation of the platinum-based solid solution alloy in the above steps, tin oxide, which is one of its components, appears on the surface of the platinum-based solid solution alloy. This can be demonstrated crystallographically by electron beam diffraction reflection method.
白金基固溶合金の表面に生成した二酸化錫の結
晶粒のサイズは、加熱温度、加熱時間等に依存す
るが、前記条件の場合、100〜1000Åの範囲内で
あり、この表面に生成した二酸化錫の層は、地金
への接着状態が非常に良好であつて、機械的、熱
的にも秀れた強度を示し、前記地金の表面から剥
離することがない。 The size of the tin dioxide crystal grains formed on the surface of the platinum-based solid solution alloy depends on the heating temperature, heating time, etc., but under the above conditions, it is within the range of 100 to 1000 Å. The tin layer has very good adhesion to the base metal, exhibits excellent mechanical and thermal strength, and does not peel off from the surface of the base metal.
以上は錫を含有する白金基固溶合金から二酸化
錫で被覆された被覆線を製造する方法について説
明したが、パラヂユームおよびパラヂユームと白
金の合金等を基台とし、亜鉛又は銅等の金属を含
有した合金からも同様な方法によつて被覆線を製
造でき得る。 The above has described a method for manufacturing a coated wire coated with tin dioxide from a platinum-based solid solution alloy containing tin. A coated wire can also be manufactured from the alloy by a similar method.
本発明においては以上の方法により、その表面
が例えば二酸化錫の金属酸化物半導体層（図示せ
ず）（以下誘電体層という）で覆われた線１，２
が互に撚り合わされて成るガス検知素子を得るこ
とができる。尚線１，２間は低電圧領域では絶縁
性を有している。 In the present invention, by the above method, the wires 1 and 2 whose surfaces are covered with a metal oxide semiconductor layer (not shown) (hereinafter referred to as a dielectric layer) of, for example, tin dioxide.
It is possible to obtain a gas sensing element made by twisting each other together. Note that the wires 1 and 2 have insulation properties in the low voltage region.
図は線１，２の撚り合わさつた状態を拡大して
示したが、実施例ではガス吸着部３は、全長が２
〜３mm程度であり、撚り回数も10〜20回である。 Although the figure shows an enlarged state in which the wires 1 and 2 are twisted together, in the embodiment, the gas adsorption part 3 has a total length of 2
The length is about 3 mm, and the number of twists is 10 to 20 times.
本発明ガス検知素子は以上のような構成である
ので、ガス吸着部３にガスが触れると、ガス吸着
部３における二酸化錫の誘電体層の誘電率がガス
濃度に比例して変化するので、その誘電率の変化
を測定すればガス濃度を知ることができる。 Since the gas detection element of the present invention has the above configuration, when gas comes into contact with the gas adsorption section 3, the dielectric constant of the tin dioxide dielectric layer in the gas adsorption section 3 changes in proportion to the gas concentration. Gas concentration can be determined by measuring the change in dielectric constant.
従つて、リード部６，７間に電源を接続し、リ
ード部４，５間にガス指示機構（図示せず）を接
続し、更にリード部５，６の間に加熱用電源（図
示せず）を接続し、ガス吸着部３を約200〜250℃
に加熱すればガス検知器を構成することができ
る。 Therefore, a power supply is connected between the lead parts 6 and 7, a gas indicating mechanism (not shown) is connected between the lead parts 4 and 5, and a heating power supply (not shown) is connected between the lead parts 5 and 6. ) and heat the gas adsorption section 3 to approximately 200 to 250℃.
A gas detector can be constructed by heating it to .
以上説明したように、本発明は、ガス吸着部３
における線１，２間が100〜1000Åという薄い二
酸化錫の誘電体層で覆われているので、希薄なガ
スに対して高い感度を示すことができると共に、
従来の製造工程における工程を十分に少なくする
ことができ、バラツキの少ない高品質の半導体式
ガス検知素子を得ることができる等その作用効果
が極めて大きい利益がある。 As explained above, the present invention provides the gas adsorption section 3
Since the area between lines 1 and 2 is covered with a thin dielectric layer of tin dioxide with a thickness of 100 to 1000 Å, it can exhibit high sensitivity to dilute gases, and
The advantages of this method are that the number of steps in the conventional manufacturing process can be sufficiently reduced, and that high-quality semiconductor gas sensing elements with little variation can be obtained.
図は本発明ガス検知素子の説明図である。
１，２……線、３……ガス吸着部、４〜７……
リード部。
The figure is an explanatory diagram of the gas detection element of the present invention. 1, 2... wire, 3... gas adsorption section, 4-7...
Lead part.
Claims (1)
記線が白金属元素と錫、銅又は亜鉛等から成る合
金を加熱酸化して表面に錫、銅又は亜鉛の酸化物
を形成していることを特徴とするガス検知素子。1 Consisting of two wires twisted together, the wires are formed by heating and oxidizing an alloy consisting of a platinum metal element and tin, copper or zinc to form tin, copper or zinc oxides on the surface. Characteristic gas detection element.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8341579A JPS568539A (en) | 1979-07-03 | 1979-07-03 | Gas detecting element and its manufacture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8341579A JPS568539A (en) | 1979-07-03 | 1979-07-03 | Gas detecting element and its manufacture |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS568539A JPS568539A (en) | 1981-01-28 |
| JPS6125306B2 true JPS6125306B2 (en) | 1986-06-14 |
Family
ID=13801797
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8341579A Granted JPS568539A (en) | 1979-07-03 | 1979-07-03 | Gas detecting element and its manufacture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS568539A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58191762U (en) * | 1982-06-16 | 1983-12-20 | 沖電気工業株式会社 | ring trip circuit |
| JP2010043905A (en) * | 2008-08-11 | 2010-02-25 | Sumitomo Electric Ind Ltd | Gas sensor |
-
1979
- 1979-07-03 JP JP8341579A patent/JPS568539A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS568539A (en) | 1981-01-28 |
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