JPS6156956A - Reference electrode - Google Patents
Reference electrodeInfo
- Publication number
- JPS6156956A JPS6156956A JP17905084A JP17905084A JPS6156956A JP S6156956 A JPS6156956 A JP S6156956A JP 17905084 A JP17905084 A JP 17905084A JP 17905084 A JP17905084 A JP 17905084A JP S6156956 A JPS6156956 A JP S6156956A
- Authority
- JP
- Japan
- Prior art keywords
- reference electrode
- chemically stable
- layer
- crystalline film
- film
- 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
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/301—Reference electrodes
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Measurement Of The Respiration, Hearing Ability, Form, And Blood Characteristics Of Living Organisms (AREA)
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Abstract
Description
【発明の詳細な説明】
〔従来技術および問題点〕
従来の基準電極としては、水素電極、水銀−カロメル電
極、銀／塩化銀電極などが用いられてきた。現在、生体
計測および微量サンプルの計測という点で、基準電極の
微小化が強く望まれているが、これらの基準電極は、い
ずれも内部液を必要とするため、十分な性能を備えつつ
、基準電極を微小化することには、限界があった。この
他、内部液がもれるという点も問題であった。これらの
間鴎を解決するために、醒極上に高分子化合物を被検し
た基準電極が提案されているが、これらはち密な高分子
膜を形成するという点、また、隆期的な安定性と１Ａう
点で問題があつ建、。DETAILED DESCRIPTION OF THE INVENTION [Prior Art and Problems] As conventional reference electrodes, hydrogen electrodes, mercury-calomel electrodes, silver/silver chloride electrodes, etc. have been used. Currently, miniaturization of reference electrodes is strongly desired from the viewpoint of bioinstrumentation and measurement of trace samples.However, since all of these reference electrodes require an internal liquid, they cannot be used as standard electrodes while having sufficient performance. There were limits to miniaturization of electrodes. Another problem was that the internal fluid leaked. In order to solve these problems, reference electrodes have been proposed in which high-molecular compounds are tested. There is a problem with 1A.
このようなことから、本発明の目的は、内部液を有さず
、簡単な構成で、微小化に有利であり、かつ、応答が速
く、長期的に安定な、基準電極を提供することにある。Therefore, an object of the present invention is to provide a reference electrode that does not have an internal liquid, has a simple structure, is advantageous for miniaturization, has a fast response, and is stable over a long period of time. be.
以下、この発明を添付の図に沿って説明する。 The present invention will be described below with reference to the accompanying drawings.
第１図に示すように、この発明の基準電極は、導電性電
極基体１０表面の一層が、化学的に安定な結晶性の皮膜
２で構成されている。導電性電極基体が金属の場合は、
金属酸化物層３を有する。As shown in FIG. 1, in the reference electrode of the present invention, one layer of the surface of a conductive electrode base 10 is composed of a chemically stable crystalline film 2. If the conductive electrode base is metal,
It has a metal oxide layer 3.
さらに、化学的に安定な結晶性皮膜２の上に有機ポリマ
一層４を設けて基準電極としての特性を向上させること
もできる。Furthermore, it is also possible to provide an organic polymer layer 4 on the chemically stable crystalline film 2 to improve the characteristics as a reference electrode.
本発明における、化学的に安定な結晶性皮膜について説
明を加えると、導電性電極基体全チタン、結晶性皮膜を
ＳｉＯ２とした場合、まず、チタン電極上に、５１０２
皮膜を形成させるが、この方法は、金属アルコキシド溶
液を塗布後、加水分解する方法、スパッタによる方法、
蒸着による方法を用いることができる。この後、微量の
酸素の存在下で、１０００℃前後で、熱処理することに
よ＼；
って、チタン電極の表面には酸化チタンが形成し、Ｓｉ
Ｏ！皮膜はＳｉＯ．の微結晶の集合体から成る膜に変化
する。To further explain the chemically stable crystalline film in the present invention, when the conductive electrode substrate is made of all titanium and the crystalline film is SiO2, first, 5102
A film is formed, but this method involves applying a metal alkoxide solution and then hydrolyzing it, a method using sputtering,
A method by vapor deposition can be used. Thereafter, by heat treatment at around 1000°C in the presence of a trace amount of oxygen, titanium oxide is formed on the surface of the titanium electrode, and Si
O! The film is SiO. It changes into a film consisting of an aggregate of microcrystals.
さらにニジ学的に安定な結晶性皮膜の別の生成方法とし
て、熱酸化したチタン−酸化チタン電極基体上に、真空
たい積法によって化学的に安定な結晶性皮膜を形成する
こともできる。Furthermore, as another method for producing a chemically stable crystalline film, a chemically stable crystalline film can be formed on a thermally oxidized titanium-titanium oxide electrode substrate by a vacuum deposition method.
（実施例１）
０．５φのチタン線の表面を清浄にした後、テトラエチ
ルシラン・メチルアルコール混合溶液を表面に塗布し、
テトラエチルシランを空気中で加水分解させるか、別の
方法として、上記混合溶液に少量の水を加え、ただちに
チタン線の表面に塗布することに工って表面にＳｉｎ、
薄膜を形成させた。(Example 1) After cleaning the surface of a 0.5φ titanium wire, a mixed solution of tetraethylsilane and methyl alcohol was applied to the surface,
You can hydrolyze tetraethylsilane in the air, or alternatively, add a small amount of water to the above mixed solution and immediately apply it to the surface of the titanium wire to coat the surface with Sin,
A thin film was formed.
次に、微量の酸素の存在下（１０Ｔｏｒｒ程度）にて、
１０００℃で熱処理を行なった。Next, in the presence of a trace amount of oxygen (about 10 Torr),
Heat treatment was performed at 1000°C.
こうして作成しン電極にリード線を取り付け、接続部を
絶縁性用ｉ曲で支援したものについて基準！極としての
特性を調べた。測定用試料溶液とし ゛なった
参照電極として市販の銀／塩化銀電極を用いて起電力の
測定を行なった。起電力と各イオン濃度の関係を第２図
、第３図、第４図に示す。The standard is for the one created in this way, with a lead wire attached to the electrode, and the connection part supported by an insulating i-curve! We investigated its properties as a pole. It became a sample solution for measurement.
Electromotive force was measured using a commercially available silver/silver chloride electrode as a reference electrode. The relationship between the electromotive force and each ion concentration is shown in FIGS. 2, 3, and 4.
本発明のセンサーは、腿／塩化銀電極に対し。The sensor of the present invention is for the thigh/silver chloride electrode.
ＯｍＶ付近で、はぼ一定であり、応答速度も数秒ときわ
めて速く、基準電極として十分動作することがわかった
。さらに、２ケ月間、純水中に浸した後も起電力にほと
んど変化がなく、十分な長期使用に耐えることがわかっ
た。It was found that the voltage was almost constant around OmV, the response speed was extremely fast, several seconds, and it worked well as a reference electrode. Furthermore, even after being immersed in pure water for two months, there was almost no change in electromotive force, and it was found that it could withstand sufficient long-term use.
（実施例２）
実施例１とまったく同じ方法で、基準電極を、作成した
後、テトラヒドロフラン、ジオクチルフタレート、塩化
ビニル混合液を用いて電極表面に塩化、ビニル薄膜を形
成させた。(Example 2) A reference electrode was prepared in exactly the same manner as in Example 1, and then a chlorinated vinyl thin film was formed on the electrode surface using a mixed solution of tetrahydrofuran, dioctyl phthalate, and vinyl chloride.
こうして作成し九基準電極について、実施例１と同様の
方法で、基準電極としての特性を調べたところ、塩化ビ
ニル薄膜を有さない基準電極に較べ、電位の安定性が若
干向上することが認められた。When the characteristics of the nine reference electrodes thus prepared as reference electrodes were investigated in the same manner as in Example 1, it was found that the stability of the potential was slightly improved compared to a reference electrode without a vinyl chloride thin film. It was done.
本発明の基準１！極は、次のような効果および特性を有
する。すなわち、この発明の基準電極は、電極基体表面
の−Ｉ＠Ｋ、化学的に安定な結晶性膜を設けた簡単な構
造であり、内部液を必要とし力の電位が得られる。また
、応答速１度が速く（数秒）、長期的にも安定に使用で
きる。したがって、微小なイオンセンサーと組み合わせ
て、微小溶液におけるイオン濃度の計測や生体計測など
に使用することが可能である。Criterion 1 of the present invention! The pole has the following effects and properties. That is, the reference electrode of the present invention has a simple structure in which -I@K and a chemically stable crystalline film are provided on the surface of the electrode base, and requires an internal liquid to obtain a force potential. In addition, the response speed is fast (several seconds) and can be used stably over a long period of time. Therefore, in combination with a minute ion sensor, it can be used for measuring ion concentration in minute solutions, biological measurements, etc.
第１図は本発明の基準電極の一実施例を示す断面図、第
２図〜第４図は起電力と各イオン濃度との関係を示すグ
ラフである。
１・・・・・・導電性電極基体
２・・・・・・化学的に安定な結晶性膜３・・＝・・・
金量酸化物
４・・・・・・有機ポリマ一層
５・・・・・・絶縁性樹脂
６・・・・・・リード線
以 上
出願人 セイコー電子工業株式会社
代理人 弁理士 最 上 務
；！
第］−図FIG. 1 is a sectional view showing one embodiment of the reference electrode of the present invention, and FIGS. 2 to 4 are graphs showing the relationship between electromotive force and each ion concentration. 1... Conductive electrode base 2... Chemically stable crystalline film 3... =...
Gold oxide 4...Organic polymer layer 5...Insulating resin 6...Lead wire or more Applicant Seiko Electronics Co., Ltd. Agent Patent attorney Mogami; ! ]-Fig.
Claims (5)
学的に安定な結晶性の皮膜で構成された基準電極。(1) A reference electrode in which the surface or one layer of the surface of a conductive electrode base is composed of a chemically stable crystalline film.
物、第二層が、化学的に安定な結晶性皮膜から成る、特
許請求の範囲第一項記載の基準電極。(2) The reference electrode according to claim 1, wherein the conductive electrode substrate is a metal, the first layer is a metal oxide, and the second layer is a chemically stable crystalline film.
化チタンから成る、特許請求の範囲第一項または第二項
記載の基準電極。(3) The reference electrode according to claim 1 or 2, wherein the conductive electrode substrate is made of titanium and the first layer is made of titanium oxide.
る、特許請求の範囲第一項または第二項記載の基準電極
。(4) The reference electrode according to claim 1 or 2, wherein the crystalline film is composed of an aggregate of SiO_2 microcrystals.
被着することによつて得られる、特許請求の範囲第一項
または第二項記載の基準電極。(5) The reference electrode according to claim 1 or 2, which is obtained by depositing an organic polymer on a chemically stable crystalline film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17905084A JPS6156956A (en) | 1984-08-28 | 1984-08-28 | Reference electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17905084A JPS6156956A (en) | 1984-08-28 | 1984-08-28 | Reference electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6156956A true JPS6156956A (en) | 1986-03-22 |
| JPH0431060B2 JPH0431060B2 (en) | 1992-05-25 |
Family
ID=16059245
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17905084A Granted JPS6156956A (en) | 1984-08-28 | 1984-08-28 | Reference electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6156956A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL1003458C2 (en) * | 1996-06-28 | 1998-01-07 | Sentron Europ B V | Reference electrode for measuring, e.g., pH value of liquid |
| JP2009089811A (en) * | 2007-10-05 | 2009-04-30 | Hitachi Appliances Inc | Vacuum cleaner |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57186163A (en) * | 1981-05-13 | 1982-11-16 | Fuji Photo Film Co Ltd | Silver/silver halide electrode and its preparation |
| JPS5825221A (en) * | 1982-05-26 | 1983-02-15 | Toshiba Corp | Manufacture of semiconductor device |
| JPS5942445A (en) * | 1982-05-12 | 1984-03-09 | カジヤ−ニ・オ−ワイ | Electrode device for coulometric measuring device |
| JPS59170262U (en) * | 1983-04-28 | 1984-11-14 | 日本防蝕工業株式会社 | Silver/silver chloride reference electrode |
-
1984
- 1984-08-28 JP JP17905084A patent/JPS6156956A/en active Granted
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57186163A (en) * | 1981-05-13 | 1982-11-16 | Fuji Photo Film Co Ltd | Silver/silver halide electrode and its preparation |
| JPS5942445A (en) * | 1982-05-12 | 1984-03-09 | カジヤ−ニ・オ−ワイ | Electrode device for coulometric measuring device |
| JPS5825221A (en) * | 1982-05-26 | 1983-02-15 | Toshiba Corp | Manufacture of semiconductor device |
| JPS59170262U (en) * | 1983-04-28 | 1984-11-14 | 日本防蝕工業株式会社 | Silver/silver chloride reference electrode |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL1003458C2 (en) * | 1996-06-28 | 1998-01-07 | Sentron Europ B V | Reference electrode for measuring, e.g., pH value of liquid |
| JP2009089811A (en) * | 2007-10-05 | 2009-04-30 | Hitachi Appliances Inc | Vacuum cleaner |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0431060B2 (en) | 1992-05-25 |
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