JPH0781972B2 - Hydrogen gas sensor dissolved in oil - Google Patents
Hydrogen gas sensor dissolved in oilInfo
- Publication number
- JPH0781972B2 JPH0781972B2 JP25130987A JP25130987A JPH0781972B2 JP H0781972 B2 JPH0781972 B2 JP H0781972B2 JP 25130987 A JP25130987 A JP 25130987A JP 25130987 A JP25130987 A JP 25130987A JP H0781972 B2 JPH0781972 B2 JP H0781972B2
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen gas
- oil
- thin film
- gas sensor
- dissolved
- 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 - Fee Related
Links
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims description 23
- 239000010409 thin film Substances 0.000 claims description 17
- 229910044991 metal oxide Inorganic materials 0.000 claims description 7
- 150000004706 metal oxides Chemical class 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- 239000007789 gas Substances 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 229920001721 polyimide Polymers 0.000 description 5
- 238000000034 method Methods 0.000 description 3
- -1 reactors Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- 230000005856 abnormality Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
Landscapes
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） この発明は油中に溶存している水素ガスの検知に使用す
るガスセンサに関する。TECHNICAL FIELD The present invention relates to a gas sensor used for detecting hydrogen gas dissolved in oil.
（従来の技術） 周知のように変圧器、コンデンサ、リアクトルその他の
油入電気機器においては、局部的にコロナ放電が発生す
るような異常或いは局部加熱により、絶縁油が分解され
て水素ガスが発生することが知られている。したがって
水素ガスを検出することによって、電気機器の異常を、
事故が発生する以前に検知することができるようにな
る。(Prior Art) As is well known, in transformers, capacitors, reactors, and other oil-filled electrical equipment, insulating oil is decomposed and hydrogen gas is generated due to abnormalities such as local corona discharge or local heating. Is known to do. Therefore, by detecting hydrogen gas, the abnormality of electrical equipment
Be able to detect before an accident occurs.
従来ではこのような水素ガスの検出に、電気機器より絶
縁油を採取し、これより溶存ガスを抽出し、これをガス
クロマトグラフにより分析するようにしている。しかし
このような手段によると、電気機器の設置現場では分析
できないし、またオンライン分析ができないなどの不便
がある。Conventionally, in order to detect such hydrogen gas, insulating oil is sampled from an electric device, dissolved gas is extracted from this, and this is analyzed by a gas chromatograph. However, with such means, there are inconveniences such as the inability to perform analysis at the installation site of electrical equipment and the inability to perform online analysis.
（発明が解決しようとする問題点） この発明は油中に溶存している水素ガスの測定に際し、
これより絶縁油を採取したり、溶存ガスを抽出したりす
ることを必要とせず、その絶縁油中に浸漬するだけの簡
単な作業で、その測定を可能にすることを目的とする。(Problems to be Solved by the Invention) This invention is for measuring hydrogen gas dissolved in oil,
Therefore, it is an object of the present invention to make it possible to perform the measurement by a simple operation of immersing the insulating oil in the insulating oil without collecting the insulating oil or extracting the dissolved gas.
（問題点を解決するための手段） この発明は絶縁性の基板の表面に、金属酸化物の薄膜を
設け、その表面に互いに向かい合う一対の電極を形成す
ることによってセンサ本体を構成し、前記センサ本体の
表面を、フッ素系樹脂からなる薄膜により被覆したこと
を特徴とする。(Means for Solving the Problems) The present invention provides a sensor main body by forming a thin film of a metal oxide on the surface of an insulating substrate and forming a pair of electrodes facing each other on the surface. It is characterized in that the surface of the main body is covered with a thin film made of a fluororesin.
（実施例） この発明の実施例を図によって説明する。１はたとえば
ポリエチレンテレフタレートのような樹脂からなるフイ
ルム状の基板、或いはAl2O3,SiO2などの無機絶縁材料か
らなる基板、２は基板１の表面に設けられた金属酸化物
からなる薄膜である。これはたとえばSnO2、TiO2、W
O3、InO2その他の単体またはこれらのうちの２種以上の
複合体が使用できる。(Embodiment) An embodiment of the present invention will be described with reference to the drawings. Reference numeral 1 is a film-shaped substrate made of a resin such as polyethylene terephthalate, or a substrate made of an inorganic insulating material such as Al 2 O 3 or SiO 2 , and 2 is a thin film made of a metal oxide provided on the surface of the substrate 1. is there. This is for example SnO 2 , TiO 2 , W
O 3 , InO 2 or other simple substance or a composite of two or more of them can be used.
この種の金属酸化物類は、水素ガスによってその表面抵
抗が変化するものとして知られている。なおこれらの金
属酸化物の薄膜は、IVD法、IBS法、真空蒸着法、プラズ
マCVD法などによって適当に設けられる。This type of metal oxide is known to have a surface resistance that changes with hydrogen gas. Note that these metal oxide thin films are appropriately provided by an IVD method, an IBS method, a vacuum evaporation method, a plasma CVD method, or the like.
薄膜２の表面には互いに向かい合う一対の電極３が形成
される。これは図のように櫛型とするのが好ましい。電
極３はたとえばAu,Pdなどよって形成される。なお電極
３にはリードが接続され、後記する袋より外部に導出さ
れる。A pair of electrodes 3 facing each other is formed on the surface of the thin film 2. It is preferably comb-shaped as shown. The electrode 3 is formed of, for example, Au or Pd. A lead is connected to the electrode 3 and is led out from a bag described later.
以上のようにしてセンサ本体４が構成されるが、この発
明ではこのセンサ本体４を、フッ素系樹脂からなる薄膜
５で被覆する。フッ素系樹脂は水素ガスを透過する特性
を具備している。薄膜５で被覆したセンサ本体４を、分
析対象の電気機器の絶縁油中にそのまま浸漬する。The sensor main body 4 is configured as described above, but in the present invention, the sensor main body 4 is covered with the thin film 5 made of a fluororesin. Fluorine-based resin has the property of transmitting hydrogen gas. The sensor body 4 covered with the thin film 5 is immersed as it is in the insulating oil of the electrical device to be analyzed.
ここで薄膜５を透過してきた水素ガスに金属酸化物の薄
膜２が接触して反応すると、その薄膜２の表面抵抗が、
水素ガスの濃度に応じて変化する。したがってこの表面
抵抗を電極３間の抵抗として検知することによって、水
素ガスの濃度を知ることができるようになる。Here, when the metal oxide thin film 2 contacts and reacts with the hydrogen gas that has permeated the thin film 5, the surface resistance of the thin film 2 becomes
It changes according to the concentration of hydrogen gas. Therefore, by detecting this surface resistance as the resistance between the electrodes 3, the concentration of hydrogen gas can be known.
なおここに使用できるフッ素系樹脂としては、４フッ化
エチレン−パーフロロアルキルビニル共重合物、４フッ
化エチレン−６フッ化プロピレン共重合物、４フッ化エ
チレン−エチレン共重合物、４フッ化エチレンなどが使
用できる。The fluororesin that can be used here is a tetrafluoroethylene-perfluoroalkylvinyl copolymer, a tetrafluoroethylene-6-fluoropropylene copolymer, a tetrafluoroethylene-ethylene copolymer, a tetrafluoride. Ethylene etc. can be used.
次のこの発明の実験例について説明する。厚さ15μｍ、
50mm平方のポリエチレンテレフタレートフイルムからな
る基板１の表面に、IVD法により厚さ1.0μｍに金属酸化
物であるSnO2の薄膜２を設け、この薄膜２の表面にAuに
よって櫛状の電極３を形成して、センサ本体４を構成し
た。そしてこれを厚さ1.0μｍの４フッ化エチレン−パ
ーフロロアルキルビニル共重合物からなる薄膜５で被覆
した。Next, an experimental example of the present invention will be described. Thickness 15μm,
A thin film 2 of SnO 2 which is a metal oxide having a thickness of 1.0 μm is provided on the surface of a substrate 1 made of polyethylene terephthalate film of 50 mm square by IVD method, and a comb-shaped electrode 3 is formed on the surface of the thin film 2 by Au. Then, the sensor body 4 was configured. Then, this was coated with a thin film 5 made of a tetrafluoroethylene-perfluoroalkylvinyl copolymer having a thickness of 1.0 μm.
第３図は前記のようにして製作したガスセンサを、水素
ガスが溶存している油中に浸漬して、そのときの水素ガ
ス濃度に対する抵抗変化率（水素ガスと反応した後の抵
抗値／反応前の初期の抵抗値）をグラフにした特性曲線
である。これによれば水素ガス濃度に対して抵抗変化率
は、ほぼ直線的に変化していることが判明する。FIG. 3 shows that the gas sensor manufactured as described above is immersed in oil in which hydrogen gas is dissolved, and the rate of change in resistance with respect to the hydrogen gas concentration at that time (resistance value after reaction with hydrogen gas / reaction It is a characteristic curve that is a graph of the previous initial resistance value). According to this, it is found that the resistance change rate changes almost linearly with respect to the hydrogen gas concentration.
第４図は同じ油内の水素ガス濃度を、ガスクロマトグラ
フによって測定したときの測定値Ａと、この発明による
ガスセンサによって測定したときの測定値（油中濃度換
算値）Ｂとの相関関係を示す特性曲線である。これによ
ると水素ガス濃度が50ppm以上のとき、両測定値A,Bは互
いにほぼ同じ値を呈するようになる。FIG. 4 shows the correlation between the measured value A when the hydrogen gas concentration in the same oil is measured by a gas chromatograph and the measured value (concentration value in oil) B when measured by the gas sensor according to the present invention. It is a characteristic curve. According to this, when the hydrogen gas concentration is 50 ppm or more, both measured values A and B have almost the same value.
以上の結果、この発明によるガスセンサによって水素ガ
ス濃度を計測するとき、その濃度に対応して感度よく抵
抗が変化するとともに、これによる測定値は、ガスクロ
マトグラフによる測定値とほぼ匹敵する正確な値となる
ことが理解される。As a result, when measuring the hydrogen gas concentration by the gas sensor according to the present invention, the resistance changes sensitively corresponding to the concentration, and the measured value by this is an accurate value that is almost comparable to the measured value by the gas chromatograph. It is understood that
なお水素ガスを選択的に透過する物質としてポリイミド
樹脂がある。しかしこの種ポリイミド樹脂は水素ガスの
透過係数がフッ素系樹脂に比較して小さく、そのため反
応速度が遅い欠点がある。すなわちポリイミド（膜厚50
μｍ）の透過係数（ml・cm/cm2・Ｓ・cm・Hg）が1.3で
あるのに対し、４フッ化エチレン−パーフロロアルキル
ビニル共重合物（膜厚75μｍ）では16、４フッ化エチレ
ン−６フッ化プロピレン共重合物（膜厚75μｍ）では1
1、４フッ化エチレン−エチレン共重合物（膜厚38μ
ｍ）では3.3、４フッ化エチレン（膜厚50μｍ）では8.9
であって、いずれもポリイミドよりも大きい。したがっ
てこの発明による方が水素ガスに迅速に反応することが
理解されよう。A polyimide resin is a substance that selectively permeates hydrogen gas. However, this kind of polyimide resin has a smaller hydrogen gas permeation coefficient than a fluorine-based resin, and therefore has a drawback that the reaction rate is slow. That is, polyimide (film thickness 50
(μm) permeation coefficient (ml ・ cm / cm 2・ S ・ cm ・ Hg) is 1.3, while tetrafluoroethylene-perfluoroalkylvinyl copolymer (film thickness 75 μm) is 16 tetrafluoride. 1 for ethylene-6 fluorinated propylene copolymer (film thickness 75 μm)
1,4-fluoroethylene-ethylene copolymer (film thickness 38μ
m) 3.3, tetrafluoroethylene (film thickness 50 μm) 8.9
However, both are larger than polyimide. It will therefore be appreciated that the present invention is more responsive to hydrogen gas.
（発明の効果） 以上詳述したようにこの発明によれば、油中に溶存する
水素ガス濃度の測定を、その測定対象の油の中に単に浸
漬するだけの簡単な操作で可能となるし、またポリイミ
ド膜を使用する場合よりも、反応速度が早まるといった
効果を奏する。(Effects of the Invention) As described in detail above, according to the present invention, the concentration of hydrogen gas dissolved in oil can be measured by a simple operation of simply immersing it in the oil to be measured. Further, it has an effect that the reaction speed becomes faster than the case of using a polyimide film.
第１図はこの発明の実施例を示す断面図、第２図は同じ
くセンサ本体の正面図、第３図は抵抗変化率を示す特性
曲線図、第４図は測定値の相関関係を示す特性曲線図で
ある。 １……基板、２……薄膜、３……電極、４……センサ本
体、５……薄膜、FIG. 1 is a sectional view showing an embodiment of the present invention, FIG. 2 is a front view of the sensor body, FIG. 3 is a characteristic curve diagram showing a resistance change rate, and FIG. 4 is a characteristic showing a correlation between measured values. It is a curve figure. 1 ... Substrate, 2 ... Thin film, 3 ... Electrode, 4 ... Sensor body, 5 ... Thin film,
Claims (1)
を設け、その表面に互いに向かい合う一対の電極を形成
することによってセンサ本体を構成し、前記センサ本体
の表面を、フッ素系樹脂からなる薄膜により被覆してな
る油中溶存水素ガスセンサ。1. A sensor body is formed by forming a thin film of a metal oxide on a surface of an insulating substrate and forming a pair of electrodes facing each other on the surface. The surface of the sensor body is made of a fluororesin. Dissolved hydrogen gas sensor in oil covered with a thin film of.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25130987A JPH0781972B2 (en) | 1987-10-05 | 1987-10-05 | Hydrogen gas sensor dissolved in oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25130987A JPH0781972B2 (en) | 1987-10-05 | 1987-10-05 | Hydrogen gas sensor dissolved in oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0194253A JPH0194253A (en) | 1989-04-12 |
| JPH0781972B2 true JPH0781972B2 (en) | 1995-09-06 |
Family
ID=17220890
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25130987A Expired - Fee Related JPH0781972B2 (en) | 1987-10-05 | 1987-10-05 | Hydrogen gas sensor dissolved in oil |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0781972B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4714825B2 (en) * | 2005-03-01 | 2011-06-29 | 国立大学法人東北大学 | Dissolved hydrogen sensor using metal thin film |
| JP5275099B2 (en) * | 2009-03-24 | 2013-08-28 | パナソニック株式会社 | Hydrogen detection element and hydrogen detection sensor |
| CN109459560A (en) * | 2018-12-27 | 2019-03-12 | 日新电机（无锡）有限公司 | A kind of high-voltage parallel capacitor device and power equipment |
-
1987
- 1987-10-05 JP JP25130987A patent/JPH0781972B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0194253A (en) | 1989-04-12 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |