JPH0431060B2 - - Google Patents
Info
- Publication number
- JPH0431060B2 JPH0431060B2 JP59179050A JP17905084A JPH0431060B2 JP H0431060 B2 JPH0431060 B2 JP H0431060B2 JP 59179050 A JP59179050 A JP 59179050A JP 17905084 A JP17905084 A JP 17905084A JP H0431060 B2 JPH0431060 B2 JP H0431060B2
- Authority
- JP
- Japan
- Prior art keywords
- reference electrode
- electrode
- titanium
- chemically stable
- stable crystalline
- 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
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229920000620 organic polymer Polymers 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 1
- 239000013078 crystal Substances 0.000 claims 1
- 229910052814 silicon oxide Inorganic materials 0.000 claims 1
- 239000010408 film Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- VCZQFJFZMMALHB-UHFFFAOYSA-N tetraethylsilane Chemical compound CC[Si](CC)(CC)CC VCZQFJFZMMALHB-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- BAQNULZQXCKSQW-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[Ti+4].[Ti+4] BAQNULZQXCKSQW-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
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
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、限界があつた。この他、内
部液がもれるという点も問題であつた。これらの
問題を解決するために、電極上に高分子化合物を
被覆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、長期
的な安定性という点で問題があつた。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 are limits to miniaturization of electrodes. Another problem was that the internal fluid leaked. To solve these problems, reference electrodes in which the electrode is coated with a polymer compound have been proposed, but these do not form a dense polymer film and have poor long-term stability. There was a problem.
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 have no internal liquid, have a simple structure, and be advantageous for miniaturization.
Another object of the present invention is to provide a reference electrode that has a quick response and is stable over a long period of time.
以下、この発明を添付の図に沿つて説明する。 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１の表面の一層が、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。
さらに、化学的に安定な結晶性被膜２の上に有機
ポリマー層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。 As shown in FIG. 1, the reference electrode of the present invention is
One layer of the surface of the conductive electrode base 1 is composed of a chemically stable crystalline film 2. When the conductive electrode base is metal, it has a metal oxide layer 3.
Furthermore, it is also possible to provide an organic polymer layer 4 on the chemically stable crystalline coating 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被膜に
ついて説明を加えると、導電性電極基体をチタ
ン、結晶性被膜をSiO2とした場合、まず、チタ
ン電極上に、SiO2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、スパツタによる方法、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つ
て、チタン電極の表面には酸化チタンが形成し、
SiO2皮膜は、SiO2の微結晶の集合体から成る膜
に変化する。 To explain the chemically stable crystalline coating in the present invention, when the conductive electrode substrate is titanium and the crystalline coating is SiO 2 , first, a SiO 2 coating is formed on the titanium electrode. As this method, a method in which a metal alkoxide solution is applied and then hydrolyzed, a sputtering method, or a vapor deposition method can be used. After this, titanium oxide is formed on the surface of the titanium electrode by heat treatment at around 1000℃ in the presence of a trace amount of oxygen.
The SiO 2 film changes into a film consisting of an aggregate of SiO 2 microcrystals.
さらに、化学的に安定な結晶性被膜の別の生成
方法として、熱酸化したチタン−酸化チタン電極
基体上に、真空たい積法によつて化学的に安定な
結晶性被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
0.5％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
することによつて表面にSiO2薄膜を形成させた。Example 1 After cleaning the surface of a 0.5% titanium wire, apply a mixed solution of tetraethylsilane and methyl alcohol to the surface and hydrolyze the tetraethylsilane in the air, or as another method, add a small amount to the above mixed solution. of water was added and immediately applied to the surface of the titanium wire to form a SiO 2 thin film on the surface.
次に、微量の酸素の存在下（10-2Torr程度）
にて、1000℃で熱処理を行なつた。 Next, in the presence of a trace amount of oxygen (about 10 -2 Torr)
Heat treatment was performed at 1000℃.
こうして作成した電極にリード線を取り付け、
接続部を絶縁性樹脂で皮覆したものについて基準
電極としての特性を調べた。測定用試料溶液とし
ては、PHの場合は、市販の標準緩衝溶液を用
い、Na+、K+濃度の場合は、各標準溶液の調整
を行なつた。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つた。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。本発明のセンサーは、銀／塩化銀電極に対
し、omV付近で、ほぼ一定であり、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
ることがわかつた。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つた。 Attach lead wires to the electrodes created in this way,
The characteristics of a reference electrode whose connection part was covered with an insulating resin were investigated. As sample solutions for measurement, commercially available standard buffer solutions were used in the case of pH, and each standard solution was adjusted in the case of Na + and K + concentrations. 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. It was found that the sensor of the present invention has a substantially constant value in the vicinity of omV with respect to the silver/silver chloride electrode, has an extremely fast response speed of several seconds, and can function satisfactorily as a reference electrode. Furthermore, even after being immersed in pure water for two months, there was almost no change in electromotive force, indicating that it could withstand sufficient long-term use.
実施例 ２
実施例１とまつたく同じ方法で、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 vinyl chloride thin film was formed on the electrode surface using a mixed solution of tetrahydrofuran, dioctyl phthalate, and vinyl chloride.
こうして作成した基準電極について、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。 Regarding the reference electrode created in this way, Example 1
When the characteristics as a reference electrode were investigated using the same method as above, it was found that the potential stability was slightly improved compared to a reference electrode without a vinyl chloride thin film.
本発明の基準電極は、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、
電極基体表面の一層に、化学的に安定な結晶性膜
を設けた簡単な構造であり、内部液を必要としな
いことから、微小化に有利である。さらに、
PH、Na+、K+など広い濃度範囲にわたり、ほぼ
一定の電位が得られる。また、応答速度が速く
（数秒）、長期的にも安定に使用できる。したがつ
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。
The reference electrode of the present invention has the following effects and characteristics. That is, the reference electrode of this invention is
It has a simple structure in which a chemically stable crystalline film is provided in one layer on the surface of the electrode base, and because it does not require an internal liquid, it is advantageous for miniaturization. moreover,
A nearly constant potential can be obtained over a wide range of concentrations such as PH, Na + , and K + . It also has a fast response time (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 a minute solution, biological measurement, 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……金属酸化物、４……有機ポリマ
ー層、５……絶縁性樹脂、６……リード線。
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. DESCRIPTION OF SYMBOLS 1... Conductive electrode base, 2... Chemically stable crystalline film, 3... Metal oxide, 4... Organic polymer layer, 5... Insulating resin, 6... Lead wire.
Claims (1)
に熱処理により形成された金属酸化物層と、該金
属酸化物層の表面に熱処理により形成された、酸
化シリコンの微結晶の集合体から成る化学的に安
定な結晶性被膜を有することを特徴とする基準電
極。 ２ 前記導電性電極基体がチタンであり、前記金
属酸化物層が酸化チタンからなる特許請求の範囲
第１項記載の基準電極。 ３ 前記化学的に安定な結晶性被膜上に被着され
た有機ポリマー層を、有する特許請求の範囲第１
項記載の基準電極。[Claims] 1. A conductive electrode base, a metal oxide layer formed on the surface of the conductive electrode base by heat treatment, and a silicon oxide microstructure formed on the surface of the metal oxide layer by heat treatment. A reference electrode characterized by having a chemically stable crystalline coating consisting of an aggregate of crystals. 2. The reference electrode according to claim 1, wherein the conductive electrode base is made of titanium, and the metal oxide layer is made of titanium oxide. 3. Claim 1 comprising an organic polymer layer deposited on said chemically stable crystalline coating.
Reference electrode as described in section.
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 JPS6156956A (en) | 1986-03-22 |
| JPH0431060B2 true 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) |
Families Citing this family (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 |
| JP4909865B2 (en) * | 2007-10-05 | 2012-04-04 | 日立アプライアンス株式会社 | Vacuum cleaner |
Citations (3)
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 (3)
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6156956A (en) | 1986-03-22 |
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