JPH0197852A - Minute electrode for electrochemical analysis - Google Patents
Minute electrode for electrochemical analysisInfo
- Publication number
- JPH0197852A JPH0197852A JP63189386A JP18938688A JPH0197852A JP H0197852 A JPH0197852 A JP H0197852A JP 63189386 A JP63189386 A JP 63189386A JP 18938688 A JP18938688 A JP 18938688A JP H0197852 A JPH0197852 A JP H0197852A
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- oxygen
- conductive substance
- length
- micropores
- 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.)
- Pending
Links
- 238000000840 electrochemical analysis Methods 0.000 title claims description 9
- 239000000126 substance Substances 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 abstract description 34
- 239000001301 oxygen Substances 0.000 abstract description 34
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 33
- 229920000049 Carbon (fiber) Polymers 0.000 abstract description 32
- 239000004917 carbon fiber Substances 0.000 abstract description 32
- 238000009792 diffusion process Methods 0.000 abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 238000005259 measurement Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 238000010276 construction Methods 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 29
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 19
- 238000000034 method Methods 0.000 description 15
- 229910052697 platinum Inorganic materials 0.000 description 13
- 229920005989 resin Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 239000003822 epoxy resin Substances 0.000 description 9
- 229920000647 polyepoxide Polymers 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- -1 fluororesin Substances 0.000 description 8
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 8
- 239000004698 Polyethylene Substances 0.000 description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 7
- 229920000573 polyethylene Polymers 0.000 description 7
- 239000010409 thin film Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 239000012811 non-conductive material Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 229910052709 silver Inorganic materials 0.000 description 6
- 239000004332 silver Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 239000008280 blood Substances 0.000 description 3
- 210000004369 blood Anatomy 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 2
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000002785 anti-thrombosis Effects 0.000 description 1
- 230000017531 blood circulation Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000002504 physiological saline solution Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
Landscapes
- Inert Electrodes (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は溶存酸素濃度および流速を同時に測定する微小
加工電極に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a microfabricated electrode for simultaneously measuring dissolved oxygen concentration and flow rate.
［従来の技術］
生物は水の中に溶解した酸素をいろいろなかたちで利用
しており、その濃度を測定することは、しばしば必要で
ある。例えば微生物を発酵させる場合は通常発酵槽内の
溶存酸素量を測定して管理される。また、医療上血液中
の溶存酸素量が測定されることがある。また、環境保全
上、海水中や湖沼中の溶存酸素量が測定されている。現
在、これらの溶存酸素を測定する方法としては電気化学
分析法が広く用いられている。即ち、溶存酸素を電極上
で電気化学的に還元し、その際発生する電流量を測定し
て定量する方法である。しかしながら、この方法は溶液
の流れの影響をうける欠点があり、流速が３０ Ｃｍ／
Ｓｅｃ以上でないと正確な測定結果を与えない。従っ
て例えば海水中の溶存酸素量を測定する場合は酸素計の
先に攪拌器を取付けるなどの面倒な方策がとられている
。また、血中の溶存酸素量をｉｎ ｖｉｖｏで測定する
場合は、そのような攪拌器を取付けることができないの
で従来の技術では正確に測定することができなかった。[Prior Art] Living organisms utilize oxygen dissolved in water in various ways, and it is often necessary to measure its concentration. For example, when fermenting microorganisms, the amount of dissolved oxygen in the fermenter is usually measured and controlled. Further, the amount of dissolved oxygen in blood is sometimes measured for medical purposes. Additionally, for environmental conservation purposes, the amount of dissolved oxygen in seawater and lakes is being measured. Currently, electrochemical analysis is widely used as a method for measuring dissolved oxygen. That is, it is a method in which dissolved oxygen is electrochemically reduced on an electrode, and the amount of current generated at that time is measured and quantified. However, this method has the disadvantage that it is affected by the flow of the solution, and the flow rate is 30 Cm/
Unless it is Sec or more, accurate measurement results will not be given. Therefore, when measuring the amount of dissolved oxygen in seawater, for example, complicated measures are taken such as attaching a stirrer to the end of the oxygen meter. Furthermore, when measuring the amount of dissolved oxygen in blood in vivo, it has not been possible to accurately measure the amount of dissolved oxygen in the blood using conventional techniques because such a stirrer cannot be attached.
また、血流量と溶存酸素量、あるいは、海流の速度と溶
存酸素量など、流速と溶存酸素濃度を同時に測定する要
望があるにも拘らず、このようなセンサーは今までに存
在しなかった。Furthermore, despite the desire to simultaneously measure flow velocity and dissolved oxygen concentration, such as blood flow and dissolved oxygen content, or ocean current speed and dissolved oxygen content, no such sensor has ever existed.
また、電機化学的流速測定法については、既に知られて
いる（明畠高司、佐原−雄、化学工学、第２２巻、第７
＠、４３０−４３５頁： Ｗｉ ｌ ｌ ｉａｍ Ｅ、
Ｒａｎｚ、＾、１．Ｃｈ、Ｅ、ＪＯＬｌｒｎａｌ、Ｖ
Ｏｌ、４．Ｎｏ、３ ｐｐ ３３Ｂ−３４２，Ｓｅｐｔ
ｅｍｂｅｒ、 １９５８ ：アーネスト マイクル リ
ーマ、特開昭５８−４７２６２．５８年３月１８日）。Furthermore, the electrochemical flow rate measurement method is already known (Takashi Akebatake, Yu Sahara, Chemical Engineering, Vol. 22, Vol. 7).
@, pages 430-435: William E.
Ranz, ^, 1. Ch, E., JOLlrnal, V.
Ol, 4. No, 3 pp 33B-342, Sept.
Ember, 1958: Ernest Michael Riemer, Japanese Patent Publication No. 58-47262. March 18, 1958).
しかしながら、これらの方法は流速測定時に温度や酸素
濃度の変化が生じた場合には、正確な流速を与えない欠
点があった。However, these methods have the disadvantage that they do not provide accurate flow rates when changes in temperature or oxygen concentration occur during flow rate measurements.
［発明が解決しようとする課題］
本発明は、かかる従来技術の欠点を解消しようとするも
のであり、流速の影響を補正した正確な溶存酸素ｍ度が
測定でき、かつ同時に流速も測定できる電気化学分析用
微小電極を提供することを目的とする。[Problems to be Solved by the Invention] The present invention aims to solve the drawbacks of the prior art, and is an electric method that can accurately measure the dissolved oxygen m degree with correction for the influence of flow rate, and can also measure the flow rate at the same time. The purpose is to provide microelectrodes for chemical analysis.
［課題を解決するための手段］ 上記の目的は、以下の本発明により達成される。[Means to solve the problem] The above object is achieved by the present invention as follows.
「（１） 非導電性物質から成り、長さの異なる２以
上の微細孔を備えた成形物の一方の開口端が、電極面に
固着されていることを特徴とする電気化学分析用微小電
極。(1) A microelectrode for electrochemical analysis, characterized in that one open end of a molded product made of a non-conductive substance and provided with two or more micropores of different lengths is fixed to the electrode surface. .
（２） 非導電性物質から成り、１以上の微細孔を供
えた成形物の一方の開口端が、電極面に固着されてなる
電極と、ポーラログラフ電極とからなることを特徴とす
る電気化学分析用微小電極。」より具体的には、まず第
１の発明は、非導性物質に好ましくは直径２０μｍ以下
の貫通微細孔が多数おいている構造を有し、かつ該微細
孔が２種以上の深さの異なった細孔群で構成されている
成形物の、該微細孔の奥に電極が配置されていることを
特徴とする電気化学分析用微小電極である。(2) An electrochemical analysis characterized by comprising an electrode made of a non-conductive substance and having one or more micropores and one open end of which is fixed to the electrode surface, and a polarographic electrode. Microelectrode for use. More specifically, the first invention has a structure in which a non-conductive substance has a large number of penetrating micropores preferably having a diameter of 20 μm or less, and the micropores have two or more depths. This is a microelectrode for electrochemical analysis, characterized in that an electrode is placed deep inside the micropores of a molded article composed of different pore groups.
また、第２の発明は、第１の発明において、該微細孔の
長さがすべて同一である電極と、ポーラログラフ電極と
を組み合わせてなる電気化学分析用微小電極である。こ
のような構成とすることによって、流速の影響を補正し
た溶存酸素濃度、および流速を同時に測定できる微小電
極が得られる。Further, a second invention is a microelectrode for electrochemical analysis, which is a combination of an electrode in which the micropores have the same length and a polarographic electrode in the first invention. With such a configuration, a microelectrode that can simultaneously measure the dissolved oxygen concentration and the flow rate with the influence of the flow rate corrected can be obtained.
本発明の電極としては特に制限はないが、炭素、白金、
イリジウム、金、炭素繊維などの先端を微細加工して用
いることができる。この中でも、炭素繊維を用いること
が好ましいので、以下炭素繊維の例について詳細に説明
する。The electrode of the present invention is not particularly limited, but carbon, platinum,
The tip of iridium, gold, carbon fiber, etc. can be finely processed and used. Among these, it is preferable to use carbon fibers, so examples of carbon fibers will be described in detail below.
第１図は、第１の発明の好ましい微小電極の概念図であ
る。ここで複数本の炭素繊維１が非導電性物質２によっ
て覆われ、炭素繊維束を形成している。同図において、
炭素繊維の上端は、非導電性物質２の上′端から後退し
て外部に解放された貫通した微細孔３，３°を形成し、
微細孔の長さは、３の群と３°の群とで異なった長さに
なっている。FIG. 1 is a conceptual diagram of a preferred microelectrode of the first invention. Here, a plurality of carbon fibers 1 are covered with a non-conductive substance 2 to form a carbon fiber bundle. In the same figure,
The upper end of the carbon fiber recedes from the upper end of the non-conductive material 2 to form a penetrating microhole 3.3° open to the outside;
The length of the micropores is different between the 3° group and the 3° group.
微細孔の底面となる炭素繊維の先端面が電極面となる。The tip surface of the carbon fiber, which becomes the bottom surface of the micropore, becomes the electrode surface.
電極面は必要により電気化学的触媒活性物質４によって
修飾されていてもよい。本電極で溶存酸素濃度を測定す
るときは、拡散層５が水中に生成する。第１図の態様で
は、炭素繊維の電極部分が非導電性物質で覆われている
が、この部分は、非導電性物質がなく電極のみで構成さ
れていても良い。すなわち、非導電性物質から成り長さ
の異なる２以上の微細孔を備えた成形物に固着されてい
る電極部分は、一体成形されていても構わず、その形態
は問わない。The electrode surface may be modified with an electrochemically catalytically active substance 4 if necessary. When measuring dissolved oxygen concentration with this electrode, a diffusion layer 5 is generated in water. In the embodiment shown in FIG. 1, the electrode portion of the carbon fiber is covered with a non-conductive material, but this portion may be composed only of the electrode without the non-conductive material. That is, the electrode portion fixed to a molded product made of a non-conductive material and having two or more micropores of different lengths may be integrally molded, and its form does not matter.
また、第２図は、第２の発明の微小電極の概念図である
。図中１〜５で示される部分は、第１図と同様であり、
微細孔３がすべて同じ長さになっている。ざらに、６は
、電気的触媒活性物質からなるポーラログラフ電極であ
り、通常白金、金および炭素が用いられる。７は、リー
ド線である。 □ポーラログラフ電極は、１〜４に示
される電極となるべく近傍に配置される。Moreover, FIG. 2 is a conceptual diagram of the microelectrode of the second invention. The parts indicated by 1 to 5 in the figure are the same as in FIG.
All of the micropores 3 have the same length. In general, 6 is a polarographic electrode made of electrocatalytically active material, typically platinum, gold and carbon. 7 is a lead wire. □Polarographic electrodes are arranged as close as possible to the electrodes 1 to 4.
非導電性物質としては、特に制限はないが弗素樹脂、ポ
リエステル樹脂、エポキシ樹脂、ポリフェニレンオキシ
ド樹脂、ポリフェニレンスルフィド樹脂、ウレタン樹脂
、シリコン樹脂、塩化ビニル樹脂、フェノール樹脂など
の高分子材料が好ましく用いられる。本発明の微小電極
を生体内に挿入して用いるような場合には、抗血栓性の
すぐれた樹脂・を使用するのが好ましい。The non-conductive substance is not particularly limited, but polymeric materials such as fluororesin, polyester resin, epoxy resin, polyphenylene oxide resin, polyphenylene sulfide resin, urethane resin, silicone resin, vinyl chloride resin, and phenol resin are preferably used. . When using the microelectrode of the present invention by inserting it into a living body, it is preferable to use a resin with excellent antithrombotic properties.
本発明の微小電極は、第１図の様に炭素繊維の各々が非
導電性樹脂によって覆われ、一体として固められ、得ら
れた複合体を繊維軸に対して垂直な面で切った断面を見
たときに非導電性樹脂の海の中に、それぞれの炭素繊維
が島成分として存在するように構成する方が好ましい。In the microelectrode of the present invention, as shown in Fig. 1, each carbon fiber is covered with a non-conductive resin and solidified as a single body, and the cross section of the resulting composite is taken along a plane perpendicular to the fiber axis. It is preferable to configure the structure so that each carbon fiber exists as an island component in a sea of non-conductive resin when viewed.
すなわち、炭素繊維同志は接触しないように構成されて
いる方が好ましい。しかし前記の様に、電極は一体化し
ていてももちろん構わない。炭素繊維の本数は本発明の
微小電極の使用目的に応じて適宜決定されるが一般的に
は５０〜５０，０００本である。この本数が微細孔の数
に相当する。That is, it is preferable that the carbon fibers are configured so that they do not come into contact with each other. However, as mentioned above, the electrodes may of course be integrated. The number of carbon fibers is appropriately determined depending on the purpose of use of the microelectrode of the present invention, but is generally 50 to 50,000. This number corresponds to the number of micropores.
前記の断面の面積中に占める炭素繊維断面積の割合は３
〜６０％が好ましい。炭素繊維の直径は２０μｍ以下で
あることが好ましく、特に１０μｍ以下とするのが好ま
しい。炭素繊維の径は微細孔の径でもあり、その径が２
０μｍ以下になると、いわゆるフィルターの効果を呈す
るようになる。The ratio of the carbon fiber cross-sectional area to the area of the above-mentioned cross-section is 3
~60% is preferred. The diameter of the carbon fiber is preferably 20 μm or less, particularly preferably 10 μm or less. The diameter of carbon fiber is also the diameter of micropores, and the diameter is 2
When the thickness becomes 0 μm or less, a so-called filter effect is exhibited.
微細孔の深さは通常０．５〜５００μｍであり、特に２
０〜４００μｍとするのが好ましい。電極面は平面であ
る必要はなく、例えば鉛筆の芯のように尖っていても逆
に下に凸の形状になっていてもよいが、その場合の微細
孔の深さは最も深い位置で定義するものとする。微細孔
の深さは２群以上に分けられるが、２群に分けるのが好
ましい。The depth of the micropores is usually 0.5 to 500 μm, especially 2
It is preferable to set it as 0-400 micrometers. The electrode surface does not need to be flat; for example, it can be pointed like a pencil lead, or convex downward; however, in that case, the depth of the micropore is defined by the deepest position. It shall be. Although the depth of the micropores can be divided into two or more groups, it is preferable to divide them into two groups.
２群に分けた場合の微細孔の深さは、浅い方の微細孔の
深さに対する深い方の微細孔の深さの割合が、１：１．
２以上の範囲にするのが好ましい。The depth of the micropores when divided into two groups is such that the ratio of the depth of the shallower micropores to the depth of the deeper micropores is 1:1.
It is preferable to set the range to 2 or more.
各詳はなるべく近い距離にあることが好ましい。It is preferable that each detail be as close as possible.
また、それぞれの群は別々にリード線がとりつけられる
。Further, each group is separately attached with a lead wire.
電極面を必要により修飾する電気化学的触媒活性物質は
、白金、銀、金、イリジウム、フタロシアニン類などで
ある。この層を形成させることにより、電極の酸素還元
活性などを高くすることができる。Electrochemically catalytically active substances that modify the electrode surface if necessary include platinum, silver, gold, iridium, phthalocyanines, and the like. By forming this layer, the oxygen reduction activity of the electrode can be increased.
本発明の電極は、電極面上を選択透過性の膜で覆うこと
により、電極面の汚染をより受けにくくするようにする
ことができる。この膜は電解酸化重合によって形成され
る電解酸化重合膜であることが望ましい。The electrode of the present invention can be made less susceptible to contamination by covering the electrode surface with a permselective membrane. This membrane is preferably an electrolytic oxidative polymeric membrane formed by electrolytic oxidative polymerization.
本発明の電極は例えば次のようにして製造される。The electrode of the present invention is manufactured, for example, as follows.
まず炭素繊維束を硬化剤を含んだ非導電性樹脂中に通し
、ついで加熱処理等を施すことにより樹脂を硬化させ、
非導電性樹脂によって覆われた針金状の炭素繊維束を得
る。一端には銀ペーストを用いてリード線を接着する。First, the carbon fiber bundle is passed through a non-conductive resin containing a hardening agent, and then the resin is hardened by heat treatment, etc.
A wire-like carbon fiber bundle covered with a non-conductive resin is obtained. A lead wire is glued to one end using silver paste.
この針金状の炭素繊維束を２本以上用い、上記と同様の
操作を繰返し一体化する。これを所望の電極の長さに切
断し、一方の断面を研磨し、研磨した側の炭素繊維は以
下に述べる電解酸化法により、削り込むことによって微
細孔を形成させる。異なる長さの微細孔を形成する場合
には、針金状炭素繊維束毎に、異なる電流量で削り込む
ことによって、炭素繊維束毎に深さの異なる微細孔を形
成させる。Using two or more of these wire-like carbon fiber bundles, the same operation as above is repeated to integrate them. This is cut to the desired length of the electrode, one cross section is polished, and the polished carbon fibers are ground down using the electrolytic oxidation method described below to form micropores. When forming micropores of different lengths, micropores with different depths are formed for each bundle of wire-like carbon fibers by carving with different amounts of current.
電解酸化液としては、酸性あるいはアルカリ性水溶液、
塩類を溶解した水溶液およびメタノールなどのアルコー
ル類が用いられる。炭素繊維束を陽極へ接続し、対極に
金属電極を用いて陽極化する。酸化の際の電圧は１〜１
００ボルトの範囲が好ましい。また酸化と還元を繰返し
行なう方法も好ましい方法の一つである。As the electrolytic oxidizing solution, acidic or alkaline aqueous solution,
Aqueous solutions containing dissolved salts and alcohols such as methanol are used. The carbon fiber bundle is connected to the anode and anodized using a metal electrode as the counter electrode. The voltage during oxidation is 1 to 1
A range of 0.00 volts is preferred. Another preferred method is one in which oxidation and reduction are repeated.
電極面を前記の電気化学的触媒活性物質で修飾する場合
には、メツキ、真空蒸着、スパッタリングなどの方法に
よって行なうことができる。When the electrode surface is modified with the electrochemically catalytically active substance described above, it can be done by methods such as plating, vacuum deposition, and sputtering.
常法により、上記電極を参照電極と組合せて流速兼酸素
計とする。第１図１〜４で示される電極を複数本１つの
プローブに集積せざることも好ましい方法の一つである
。The above electrode is combined with a reference electrode in a conventional manner to form a flow rate/oxygen meter. One preferable method is not to integrate a plurality of electrodes shown in FIGS. 1 to 4 into one probe.
水溶液中の酸素還元反応は拡散支配になっているので、
定常状態での電流値（この値が酸素濃度に比例する）は
次式で表わされる。Since the oxygen reduction reaction in aqueous solution is diffusion-dominated,
The current value in a steady state (this value is proportional to the oxygen concentration) is expressed by the following equation.
ｉ ｏｏ＝ ｎ Ｆ Ｄ Ｃ３／ Ｌ−・・・・（１）
（但し、’ ｏｏ ”定常電流値、ｎ：反応電子数（こ
の場合は４）、 Ｆ：ファラデ一定数（９６５００＾
・Ｓ／ｍｏｌｅ） 、 Ｄ ： Ｆ１ａ素の拡散常数＞
、ｃ：ｍ水濃度。i oo = n FD C3/ L-...(1)
(However, 'oo'' steady current value, n: number of reaction electrons (4 in this case), F: Faraday constant number (96500^
・S/mole), D: Diffusion constant of F1a element>
, c: m water concentration.
Ｓ：電極面積、 Ｌ：全拡散層の長さ）本発明の電極で
は全拡散層の長さは、微細孔３の長さ、および非導電物
質２の上端に生成する拡散層５の厚さの和となる。拡散
層５の厚さは流速が決れば決るものであり、酸素濃度と
は無関係であり、また、拡散常数りによる影響もない。S: electrode area, L: length of the total diffusion layer) In the electrode of the present invention, the length of the total diffusion layer is the length of the micropore 3 and the thickness of the diffusion layer 5 formed at the upper end of the non-conductive material 2. is the sum of The thickness of the diffusion layer 5 is determined by the flow rate and is unrelated to the oxygen concentration, and is not affected by the diffusion constant.
まず、第１図においてＡ群の微細孔の深さをＱａとし、
Ｂ群の深さをαｂとし、拡散層５の厚さをり、ｃとする
と、Ａ群およびＢ群に流れる定常電流１ａｉ１およ（ｊ
ｉ２は次式で表される。First, in Fig. 1, the depth of the micropores in group A is Qa,
When the depth of group B is αb and the thickness of the diffusion layer 5 is c, the steady currents 1ai1 and (j
i2 is expressed by the following formula.
ｉ １＝ｎＦＣ３１／ （Ｑｃ／Ｄ１−ｔ４ａ／Ｄ２）
・・・・・・ （２）
ｉ ２＝ｎＦＣ３２／ （Ｑｃ／Ｄｔ ＋Ｄ、ｂ／Ｄ２
＞・・・・・・ （３）
（但し、Ｓｌ：へ群の電極面積、Ｓ２：Ｂ群の電極面積
、Ｄｌ：ＱＣでの酸素拡散常数、Ｄ２：Ｑａおよびり、
ｂでの酸素拡散常数）。i 1=nFC31/ (Qc/D1-t4a/D2)
...... (2) i2=nFC32/ (Qc/Dt +D, b/D2
>... (3) (However, Sl: electrode area of group B, S2: electrode area of group B, Dl: oxygen diffusion constant at QC, D2: Qa and
(oxygen diffusion constant at b).
ここで、ｉ １ ／ ｉ ２ ＝ ｒ、（＄１・Ｄｌ）
／（３２・、Ｄ２＞＝にと置くと、
ｒ−ｋ ・・・・・・ （４）となり、二つ
の電極を流れる電流の比（ｒを測定することにより、拡
散層の厚さ（１）を求めることができる。次で公知の方
法により境膜の厚さから流速および補正された溶存酸素
濃度を計算により求めることができる。Here, i 1 / i 2 = r, ($1・Dl)
/(32・, D2>=, r−k ...... (4), and by measuring the ratio (r) of the current flowing through the two electrodes, the thickness of the diffusion layer (1 ) can be determined.Next, the flow velocity and corrected dissolved oxygen concentration can be calculated from the thickness of the boundary film using a known method.
［実施例］ 本発明を実施例によりさらに具体的に説明する。[Example] The present invention will be explained in more detail with reference to Examples.
実施例１〜４
炭素繊維１０００本の束（“トレカＴ−１３００ＩＫ”
、直径約７μｍ）を硬化剤を含んだエポキシ樹脂中を走
らせ樹脂を含浸させたまま加熱して硬化させ、直径約Ｑ
、３ｍｍの針金状の複合材料を得た。これらの側面をエ
ポキシ樹脂で完全に絶縁したのち切断し、一方の端に銀
ペーストを用いてリード線を接着した。該複合材の２本
を、内径１ｍｍのポリエチレンのチューブに挿入し、エ
ポキシ樹脂を注入し、加熱硬化させた。リード線のつい
ている反対側の断面を常法で研磨した。Examples 1 to 4 Bundle of 1000 carbon fibers (“Trading Card T-1300IK”)
, diameter of approximately 7 μm) is run through an epoxy resin containing a hardening agent, heated and cured while impregnated with the resin, and the diameter is approximately Q.
, a 3 mm wire-like composite material was obtained. After completely insulating these sides with epoxy resin, they were cut, and a lead wire was glued to one end using silver paste. Two pieces of the composite material were inserted into a polyethylene tube with an inner diameter of 1 mm, an epoxy resin was injected, and the tube was heated and cured. The cross section on the opposite side where the lead wire was attached was polished using a conventional method.
研磨した部分を０．２モルの＠酸ナトリウムを溶解した
２ミリモルの硫酸水溶液につけ対極に白金線を用い、次
の条件で陽極酸化を行なった。即ち、２本のうち、１本
は０．３ミリアンペアの電流を１２．５分流した。微細
孔の深さは２００μｍであった。２本のうちの他の１本
は、実施例１では、０．３ミリアンペアの電流を６．３
分流した。微細孔の深さは１００μｍであった。実施例
２では、０．１ミリアンペアの電流を１１．４分流した
。微細孔の深さは６０μｍであった。実施例３では、０
．１ミリアンペアの電流を７．６分流した。微細孔の深
さは４０μｍであった。実施例４では、０．１ミリアン
ペアの電流を３．８分流した。微細孔の深さは２０μｍ
であった。The polished portion was immersed in a 2 mmol sulfuric acid aqueous solution containing 0.2 mol of sodium oxide dissolved therein, and anodic oxidation was performed under the following conditions using a platinum wire as a counter electrode. That is, one of the two wires passed a current of 0.3 milliampere for 12.5 minutes. The depth of the micropores was 200 μm. In Example 1, the other one of the two wires carries a current of 0.3 milliampere to 6.3 milliamps.
Divided. The depth of the micropores was 100 μm. In Example 2, a current of 0.1 milliampere was passed for 11.4 minutes. The depth of the micropores was 60 μm. In Example 3, 0
．． A current of 1 milliampere was applied for 7.6 minutes. The depth of the micropores was 40 μm. In Example 4, a current of 0.1 milliampere was passed for 3.8 minutes. The depth of micropores is 20μm
Met.
上記に得られた微細孔電極上に、次に説明する方法で、
白金の薄膜を生成せしめた。即ち、塩化白金１１０．０
３７モル／Ｌリシリンンモニウム０．１３４１Ｅ−ル／
ｆｆ、リン酸ナトリウム０．７０４モル／Ｄ、を含む水
溶液に上記微細孔電極を浸漬し、白金を対極として炭素
繊維１０００本当り８ミリクーロンの電流を流した。得
られた電極を水でよく洗浄した。電子顕微鏡の観察では
、約０゜６μｍの白金薄膜が電極上に均一に付着してい
た。On the microporous electrode obtained above, by the method described below,
A thin film of platinum was produced. That is, platinum chloride 110.0
37 mol/L ricylinmonium 0.1341E-L/
The microporous electrode was immersed in an aqueous solution containing 0.704 mol/D of sodium phosphate, and a current of 8 millicoulombs per 1000 carbon fibers was applied using platinum as a counter electrode. The obtained electrode was thoroughly washed with water. Observation using an electron microscope revealed that a thin platinum film of approximately 0.6 μm was uniformly adhered to the electrode.
上記の白金メツキを行なった電極上に、下記に詳述する
方法で電解酸化重合法を用いてポリアニリンの薄膜を形
成せしめた。A thin film of polyaniline was formed on the platinum-plated electrode using an electrolytic oxidation polymerization method as detailed below.
即ち、白金メツキした微細孔電極を、アニリン０．０１
モル／Ｄ、、過塩素酸ソーダ０．１モル／ａ、ピリジン
０．０２モル／ａを含むアセトニトリル溶液に浸漬し、
１．２ボルトの正電位を与えて電流が流れなくなるまで
重合を行なった。電子顕微鏡による観察で白金上に重合
体薄膜の生成が認められた。That is, a platinum-plated microporous electrode was coated with 0.01 aniline.
mol/D, immersed in an acetonitrile solution containing 0.1 mol/a of sodium perchlorate and 0.02 mol/a of pyridine,
Polymerization was carried out by applying a positive potential of 1.2 volts until no current flowed. Observation using an electron microscope revealed the formation of a thin polymer film on the platinum.
ｊｑられた電極の先端を、３７℃に保った生理食塩水に
つけ作動極とし、対極に銀／塩化銀電極を装着した。作
動極に０．６ボルトの負電圧をかけ、流れる電流を測定
した。The tip of the jqed electrode was immersed in physiological saline kept at 37°C to serve as a working electrode, and a silver/silver chloride electrode was attached to the counter electrode. A negative voltage of 0.6 volts was applied to the working electrode, and the flowing current was measured.
実施例１〜４の、それぞれの電極の２００μｍエツチン
グした方の電極に流れる電流と流速の関係を第２図に示
した。即ち、酸素飽和状態で、流速毎秒５０ｃｍのとき
に流れる電流値を１とし、流速を徐々に落し、流速□が
Ｏになるまで変化させそのとぎに流れる電流値の毎秒５
Ｑｃｍのときに対する比（相対電流値）の変化を第２図
にプロットした。FIG. 2 shows the relationship between the current flowing through the 200 μm etched electrode of Examples 1 to 4 and the flow rate. That is, in an oxygen-saturated state, the current value flowing when the flow rate is 50 cm per second is set to 1, the flow rate is gradually decreased until the flow rate □ becomes O, and then the current value flowing is 5 cm per second.
Changes in the ratio (relative current value) with respect to Qcm are plotted in FIG.
また、それぞれの電極の、他の１本に流れる電流につい
ても、同様に流速毎秒５Ｑｃｍのときに流れる電流値を
それぞれ１とし、流速を変更し、毎秒５ＱＣｍのときの
電流値に対する比（相対電流値）を求めた。Regarding the current flowing through the other electrode of each electrode, similarly, the current value flowing when the flow rate is 5 Qcm per second is set to 1, and the flow rate is changed, and the ratio (relative current) to the current value when the flow rate is 5 Qcm per second. value) was calculated.
実施例１については、２００１１ｍ電極と１００μｍ電
極の相対電流値の比を求め第３図の１００μｍと示した
曲線で示した。実施例２〜４については、それぞれ、６
０μｍ、４０μｍ、２０μｍと示した曲線で示した。以
上で補正を終了した。Regarding Example 1, the ratio of the relative current values of the 20011m electrode and the 100 μm electrode was determined and shown in the curve shown as 100 μm in FIG. For Examples 2 to 4, 6
The curves are shown as 0 μm, 40 μm, and 20 μm. This completes the correction.
任意の水溶液に、実施例１〜４のセンサをつけ、相対電
流値の比を測定し、第３図から流速を求めた。これは実
測値とよく一致した。また、第２図を用い流速が遅いと
きの測定値から、流速毎秒５Ｑｃｍ以上のときの溶存酸
素量を求めた。これも実測値とよく一致した。The sensors of Examples 1 to 4 were attached to any aqueous solution, the ratio of relative current values was measured, and the flow velocity was determined from FIG. This was in good agreement with the measured value. Further, using FIG. 2, the amount of dissolved oxygen when the flow rate was 5 Qcm per second or more was determined from the measured value when the flow rate was slow. This also agreed well with the measured value.
実施例５
実施例４において、炭素繊維の複合材の２本を、内径１
＃のポリエチレンのチューブに挿入し、エポキシ樹脂を
注入し、加熱硬化させ、ざらに、ポリエチレンのチュー
ブを除去し、内径４＃のポリエチレンチューブに挿入し
、同様にエポキシ樹脂を注入し加熱硬化させたのちポリ
エチレンチューブを取除き外径４ｍのセンサーを作製し
、リード線のついている反対側の断面を研磨し半球状と
した以外は、実施例４と同様にして、微細孔電極を得、
さらに同様にして、該電極上に白金薄膜、重合体薄膜を
生成した。Example 5 In Example 4, two pieces of carbon fiber composite material with an inner diameter of 1
Insert it into a ## polyethylene tube, inject epoxy resin, heat and harden it, roughly remove the polyethylene tube, insert it into a #4 polyethylene tube, and inject epoxy resin in the same way and heat harden it. Afterwards, the polyethylene tube was removed to prepare a sensor with an outer diameter of 4 m, and a microporous electrode was obtained in the same manner as in Example 4, except that the cross section on the opposite side to which the lead wire was attached was polished and made into a hemispherical shape.
Furthermore, a platinum thin film and a polymer thin film were formed on the electrode in the same manner.
上記により得られたセンサーの先端部に直径１ミリの銀
線を巻付け、その表面に塩化銀被膜を生成させた。かく
して、流速兼酸素計を作成した。A silver wire with a diameter of 1 mm was wrapped around the tip of the sensor obtained above, and a silver chloride film was formed on the surface of the wire. In this way, a flow velocity and oxygen meter was created.
下記に本センサを用いた実施例を説明する。２電極力式
で動作電極に−０，６ボルトを印加した。An example using this sensor will be described below. -0.6 volts was applied to the working electrode using a two-electrode force method.
攪拌機をそなえ３７°Ｃに保ったビーカ中にセンサを入
れ攪拌機の回転数を変え流速を変化させ、２つの電極に
流れる電流を測定した。流速はレーザ・ドツプラー流速
計を用いて設定した。拡散層の厚さ（０）は
（ｋｈ２−ｒｈｔ ）／ （ｒ−ｋ＞
但しｈ２＝２０．ｈ１＝２００．に＝１、ｒ＝ｉ１／ｉ
２で計算した。溶存酸素濃度補正値は測定値に補正係数
（２００十Ｑｍｉｎ ＞／ （２００十α）を乗じて求
めた。流速（Ｖ）はＶ−νＬ／１（（Ｅしνは動粘度、
Ｌはセンサーの直径）の式を用いて求めた。結果を表１
に示した。A sensor was placed in a beaker equipped with a stirrer and kept at 37°C, and the rotation speed of the stirrer was changed to change the flow rate, and the current flowing through the two electrodes was measured. Flow velocity was set using a laser Doppler velocimeter. The thickness (0) of the diffusion layer is (kh2-rht)/(r-k> where h2=20.h1=200.=1, r=i1/i
Calculated using 2. The dissolved oxygen concentration correction value was obtained by multiplying the measured value by the correction coefficient (200 Qmin ＞/ (200 α).
L is the diameter of the sensor). Table 1 shows the results.
It was shown to.
測定流速値と設定流速値とは、よく一致した。The measured flow velocity value and the set flow velocity value were in good agreement.
流れの影響を受けない溶存酸素を測定することができた
。We were able to measure dissolved oxygen unaffected by flow.
実施例６
炭素繊維１０００本の束（“トレカ” Ｔ−３００Ｉ
に、直径約７μＴｒｔ）を硬化剤を含んだエポキシ樹脂
中を走らぜ樹脂を含浸させた。次に、この含浸した繊維
束を引張ったまま加熱して硬化させ、直径約０．３８の
針金状の複合材料を得た。これらの側面をエポキシ樹脂
で完全に絶縁したのち切断し、一方の端に銀ペーストを
用いてリード線を接着した。該複合材と直径０．３ミリ
の白金線とを、内径１ｍのポリエチレンのチューブに挿
入し、エポキシ樹脂を注入し、加熱硬化させた。ポリエ
チレンチューブに除去し、外径６ｍのステンレスチュー
ブに鎖管とともに挿入し、同様にボキシ樹脂を注入し加
熱硬化させたのちコネクターを取付はコネクタのついて
いる反対側の断面を研磨した。Example 6 Bundle of 1000 carbon fibers (“Trading Card” T-300I
A diameter of approximately 7 μTrt) was run through an epoxy resin containing a curing agent to impregnate the resin. Next, this impregnated fiber bundle was heated and cured while being stretched, to obtain a wire-like composite material with a diameter of about 0.38 mm. After completely insulating these sides with epoxy resin, they were cut, and a lead wire was glued to one end using silver paste. The composite material and a platinum wire with a diameter of 0.3 mm were inserted into a polyethylene tube with an inner diameter of 1 m, and an epoxy resin was injected and hardened by heating. It was removed into a polyethylene tube, inserted into a stainless steel tube with an outer diameter of 6 m together with a chain tube, and the boxy resin was similarly injected and heated to harden. Then, the connector was attached by polishing the cross section on the opposite side where the connector was attached.
研磨面には中心に炭素繊維電極および白金電極、その周
りに銀電極が位置している。On the polishing surface, a carbon fiber electrode and a platinum electrode are located in the center, and a silver electrode is located around them.
研磨した部分を０．２モルの硫酸ナトリウムを溶解した
２ミリモルの硫酸水溶液につけ対極に白金線を用い、炭
素繊維電極の陽極酸化を行なった。The polished portion was immersed in a 2 mmol sulfuric acid aqueous solution containing 0.2 mol of sodium sulfate, and a platinum wire was used as a counter electrode to anodize the carbon fiber electrode.
即ち、０．３ミリアンペアの電流を１２．５分流した。That is, a current of 0.3 milliampere was passed for 12.5 minutes.
微細孔の深さは２００μｍｃ必った。The depth of the micropores was required to be 200 μmc.
上記に得られた微細孔電極上に、次に説明する方法で、
白金の薄膜を生成せしめた。即ち、塩化白金１０．０３
７モル／Ｄ、、リン酸アンモニウム０．１３４モル／ρ
、リン酸ナトリウム０．７０４モル／Ｑを含む水溶液に
上記微細孔電極を浸漬し、白金を対極として炭素繊維１
０００本当り８ミリクーロンの電流を流した。得られた
電極を水でよく洗浄した。電子顕微鏡の１２察では、約
０゜６μｍの白金薄膜が電極上に均一に付着していた。On the microporous electrode obtained above, by the method described below,
A thin film of platinum was produced. That is, platinum chloride 10.03
7 mol/D, ammonium phosphate 0.134 mol/ρ
, the above microporous electrode was immersed in an aqueous solution containing 0.704 mol/Q of sodium phosphate, and the carbon fiber 1 was immersed with platinum as a counter electrode.
A current of 8 millicoulombs was applied per 000 wires. The obtained electrode was thoroughly washed with water. Twelve observations using an electron microscope revealed that a platinum thin film of approximately 0.6 μm was uniformly adhered to the electrode.
上記に白金メツキを行なった電極上に、下記に詳述する
方法で電解酸化重合法を用いてポリアニリンの薄膜を形
成せしめた。A thin film of polyaniline was formed on the platinum-plated electrode using an electrolytic oxidation polymerization method as detailed below.
即ち、白金メツキした微細孔電極を、アニリン０．０１
モル／Ｉ２、過塩素酸ソーダ０．１モル／ａ１ピリジン
０．０２モル／ａを含むアセトニトリル溶液に浸漬し、
１．２ボルトの正電位を与えて電流が流れなくなるまで
重合を行なった。電子顕微鏡による観察で白金上に重合
体薄膜の生成が認められた。かくしてセンサが完成した
。That is, a platinum-plated microporous electrode was coated with 0.01 aniline.
mol/I2, sodium perchlorate 0.1 mol/a1 pyridine 0.02 mol/a immersed in an acetonitrile solution,
Polymerization was carried out by applying a positive potential of 1.2 volts until no current flowed. Observation using an electron microscope revealed the formation of a thin polymer film on the platinum. The sensor was thus completed.
本センサを用いて、流れる電流を測定した。充分攪拌し
たときの電流値を１とした。拡散層の厚ざａは次式で計
算した。Using this sensor, we measured the flowing current. The current value when sufficiently stirred was set to 1. The thickness a of the diffusion layer was calculated using the following formula.
α＝ｈ１ ｘ、Ｑｍｉｎ ／ｒｘ （ｈＩ 十〇、ｍｉ
ｎ ）但しｈｌ ＝２００．ｆｆｍ１ｎ ＝７．５、ｒ
＝ ｉ １ ／ ｉ ２
結果を表２に示す。α=h1 x, Qmin/rx (hI 10, mi
n) However, hl = 200. ffm1n =7.5, r
= i 1 / i 2 The results are shown in Table 2.
［発明の効果コ
本発明の電気化学分析用微小電極は、流速の影響を補正
した正確な溶存酸素濃度が測定できる。[Effects of the Invention] The microelectrode for electrochemical analysis of the present invention can accurately measure dissolved oxygen concentration with the influence of flow rate corrected.
また同時に流速も測定できる微小電極であるため−非常
に有用である。It is also very useful because it is a microelectrode that can also measure flow velocity at the same time.
第１図は本発明の実施例１の微小電極を、第２図は流速
と相対電流値の関係を、第３図は流速と相対電流値の比
の関係を示す。
第４図は、本発明の実施例６の微小電極を示す。
１・・・・・・炭素繊維
２・・・・・・非導電性物質
３．３”・・・・・・微細孔
４・・・・・・電気化学的触媒活性物質５・・・・・・
拡散層
６・・・・・・ポーラログラフ電極
７・・・・・・リード線
特許出願人 東 し 株 式 会 社
第１図
第２図
第３図FIG. 1 shows the microelectrode of Example 1 of the present invention, FIG. 2 shows the relationship between flow velocity and relative current value, and FIG. 3 shows the relationship between flow velocity and the ratio of relative current value. FIG. 4 shows a microelectrode of Example 6 of the present invention. 1... Carbon fiber 2... Non-conductive material 3.3"... Micropores 4... Electrochemically catalytically active material 5...・・・
Diffusion layer 6... Polarographic electrode 7... Lead wire Patent applicant Toshi Co., Ltd. Figure 1 Figure 2 Figure 3
Claims (2)
細孔を備えた成形物の一方の開口端が、電極面に固着さ
れていることを特徴とする電気化学分析用微小電極。(1) A microelectrode for electrochemical analysis, characterized in that one open end of a molded product made of a non-conductive substance and provided with two or more micropores of different lengths is fixed to an electrode surface.
成形物の一方の開口端が、電極面に固着されてなる電極
と、ポーラログラフ電極とからなることを特徴とする電
気化学分析用微小電極。(2) Electrochemical analysis characterized by comprising an electrode made of a non-conductive substance and having one or more open ends of a molded article fixed to the electrode surface, and a polarographic electrode. Microelectrode for use.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63189386A JPH0197852A (en) | 1987-07-28 | 1988-07-28 | Minute electrode for electrochemical analysis |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18950987 | 1987-07-28 | ||
| JP62-189509 | 1987-07-28 | ||
| JP63189386A JPH0197852A (en) | 1987-07-28 | 1988-07-28 | Minute electrode for electrochemical analysis |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0197852A true JPH0197852A (en) | 1989-04-17 |
Family
ID=26505445
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63189386A Pending JPH0197852A (en) | 1987-07-28 | 1988-07-28 | Minute electrode for electrochemical analysis |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0197852A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000512743A (en) * | 1996-05-16 | 2000-09-26 | センデックス メディカル，インク． | Sensor having microminiature through-holes and method of manufacturing such a sensor |
| JP2019536982A (en) * | 2016-09-08 | 2019-12-19 | ザ フランシス クリック インスティチュート リミティッド | Electrochemical wire electrode array and corresponding manufacturing method |
-
1988
- 1988-07-28 JP JP63189386A patent/JPH0197852A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000512743A (en) * | 1996-05-16 | 2000-09-26 | センデックス メディカル，インク． | Sensor having microminiature through-holes and method of manufacturing such a sensor |
| JP2019536982A (en) * | 2016-09-08 | 2019-12-19 | ザ フランシス クリック インスティチュート リミティッド | Electrochemical wire electrode array and corresponding manufacturing method |
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