KR100612270B1 - External Reference Electrode for a Pressurized, High Temperature Aqueous Environments - Google Patents

External Reference Electrode for a Pressurized, High Temperature Aqueous Environments Download PDF

Info

Publication number
KR100612270B1
KR100612270B1 KR1020040092460A KR20040092460A KR100612270B1 KR 100612270 B1 KR100612270 B1 KR 100612270B1 KR 1020040092460 A KR1020040092460 A KR 1020040092460A KR 20040092460 A KR20040092460 A KR 20040092460A KR 100612270 B1 KR100612270 B1 KR 100612270B1
Authority
KR
South Korea
Prior art keywords
tube
reference electrode
electrode
external reference
metal
Prior art date
Application number
KR1020040092460A
Other languages
Korean (ko)
Other versions
KR20060046932A (en
Inventor
박병기
Original Assignee
주식회사 미래와도전
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 주식회사 미래와도전 filed Critical 주식회사 미래와도전
Priority to KR1020040092460A priority Critical patent/KR100612270B1/en
Publication of KR20060046932A publication Critical patent/KR20060046932A/en
Application granted granted Critical
Publication of KR100612270B1 publication Critical patent/KR100612270B1/en

Links

Images

Classifications

    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28Electrolytic cell components
    • G01N27/30Electrodes, e.g. test electrodes; Half-cells
    • G01N27/301Reference electrodes
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632Organic additives
    • C04B35/634Polymers
    • C04B35/63404Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B35/63436Halogen-containing polymers, e.g. PVC
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N25/00Investigating or analyzing materials by the use of thermal means
    • G01N25/16Investigating or analyzing materials by the use of thermal means by investigating thermal coefficient of expansion
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28Electrolytic cell components
    • G01N27/30Electrodes, e.g. test electrodes; Half-cells
    • G01N27/327Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
    • G01N27/3275Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
    • G01N27/3278Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction involving nanosized elements, e.g. nanogaps or nanoparticles
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52Constituents or additives characterised by their shapes
    • C04B2235/5208Fibers
    • C04B2235/5216Inorganic
    • C04B2235/522Oxidic
    • C04B2235/5236Zirconia

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Molecular Biology (AREA)
  • General Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • Analytical Chemistry (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Ceramic Engineering (AREA)
  • Electrochemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Nanotechnology (AREA)
  • Organic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Testing Resistance To Weather, Investigating Materials By Mechanical Methods (AREA)

Abstract

본 발명은 고온 고압 수화학 환경에서 전기화학적 전위를 측정할 때 기준전위를 제공하는 외부기준전극(External Reference Electrode)에 관한 것으로서, 저온부에 전기화학적 기준전위를 감지하는 전극으로 고체기준전극(Solid-state Reference Electrode)을 사용하고 그 외부에 세라믹 튜브를 형성하고 고온부로 연결하여 기준전위 감지부와 전기적으로 연결되게 하며, 그 외부에 금속튜브를 형성하여 압력경계를 이루도록 하였다. 본 발명은 고온 고압 환경에서 전기화학적 기준전위가 안정하게 유지되는 기준전극을 제공함으로서 전기화학 및 금속/금속합금의 부식연구뿐만 아니라 부식감시에 유용하게 사용될 수 있다.The present invention relates to an external reference electrode that provides a reference potential when measuring an electrochemical potential in a high temperature and high pressure hydrochemical environment. The present invention relates to an electrode for sensing an electrochemical reference potential in a low temperature region. A state reference electrode was used, and a ceramic tube was formed on the outside and connected to a high temperature part to be electrically connected to the reference potential sensing unit. A metal tube was formed on the outside to form a pressure boundary. The present invention can be usefully used for monitoring corrosion as well as corrosion studies of electrochemical and metal / metal alloys by providing a reference electrode in which the electrochemical reference potential is stably maintained in a high temperature and high pressure environment.

Description

고온 고압 수화학 환경을 위한 외부기준전극{External Reference Electrode for a Pressurized, High Temperature Aqueous Environments}External Reference Electrode for a Pressurized, High Temperature Aqueous Environments

도1과 도2는 본 고안에 따르는 외부기준전극의 일실시예의 단면도를 도시하는 도면.1 and 2 are cross-sectional views of one embodiment of an external reference electrode according to the present invention.

<도면 주요 부분에 대한 부호의 설명><Explanation of symbols for the main parts of the drawings>

1. AgCl피막 2. 전극(Ag 와이어)1. AgCl film 2. Electrode (Ag wire)

3. 실런트 4. 제1튜브(세라믹튜브)3. Sealant 4. First tube (ceramic tube)

5. 제1피팅 6. 제2피팅5. First fitting 6. Second fitting

7. 제2튜브 8. 냉각관7. Second tube 8. Cooling tube

9. 제3 피팅 10. 신호연결부9. Third fitting 10. Signal connection

11. 세라믹 가이드 12. 열수축 테프론 튜브11. Ceramic Guide 12. Heat Shrink Teflon Tube

13. 계통수 14. 제4피팅13. System tree 14. Fourth fitting

15. 저온부 16. 고온부15. Low temperature section 16. High temperature section

원자력발전소와 같은 고온, 고압 환경에서 구조물의 손상과 고장의 주요 원 인은 고온 고압의 냉각수에 의해 발생하는 부식현상이다. 이러한 환경에서 금속 및 금속합금의 부식거동을 이해하기 위한 연구는 신뢰성 있고 긴 수명을 보장할 수 있는 전기화학적 기준전극이 필수적이다. 고온, 고압 수화학 환경에서의 전기화학적 전위의 측정을 위하여 개발된 외부기준전극(External Reference Electrode)은 기준전위 감지부인 Ag/AgCl 전극을 저온으로 유지되게 하고 고온부에 위치한 다공성 세라믹 마개와 Ag/AgCl 전극을 열수축 테프론 튜브를 이용하여 연결하고 관내에 일정한 농도의 KCl을 넣고, 외부에 압력경계를 위해 금속튜브를 설치한 구조로 제작되었다. 이러한 구조의 전극은 다니엘슨(Danielson) 및 맥도널드(Macdonald)들에 의해 개발이 되었다. 외부기준전극에서 사용되는 다공성 세라믹 마개는 지르코니아로 만들어지며, 테프론 튜브에 들어 있는 KCl 완충액(Buffer Solution)이 수화학 환경으로 누설되어 발생하는 완충액의 이온 활성도 저하를 예방하고 다공성을 통과하는 미량의 이온으로 기준전극과 수화학 환경 사이를 전기적으로 연결하는 기능을 수행한다. 외부기준전극의 전위는 기준전위 감지부의 기준반응에 의해 발생하는 전위, 저온부와 고온부의 온도차에 의해 발생하는 열간접촉전위(Thermal Liquid junction Potential), 다공성 세라믹 마개를 경계로 두 용액간의 농도차에 의해 발생하는 액간접촉전위(Liquid Junction Potential)의 합으로 구성된다. Ag/AgCl의 기준반응을 이용하는 외부기준전극의 전위차 성분인 열간접촉전위 및 액간접촉전위는 맥도널드를 비롯한 여러 연구자들에 의해 충분하게 해석되어 있어 외부기준전극으로 측정된 전위차는 수소기준전극 (Standard Hydrogen Electrode, SHE)눈금으로 변환된다. 위의 구조를 가지는 외부기준전극은 고온, 고압 수화학 환경의 운전에서 발생하는 압 력변화로 열수축 테프론 튜브의 구조적 안정성이 저해되며, 세라믹 다공성 마개에서 완충액 이온의 누설에 의한 전위의 편향 등과 같은 문제로 수명이 짧은 단점을 가지고 있다. In high temperature and high pressure environments such as nuclear power plants, the main cause of damage and failure of structures is corrosion caused by high temperature and high pressure coolant. To understand the corrosion behavior of metals and metal alloys in this environment, it is necessary to have an electrochemical reference electrode that can guarantee a long and reliable life. The External Reference Electrode, developed for the measurement of electrochemical potential in high temperature and high pressure hydrochemical environments, keeps the Ag / AgCl electrode, which is the reference potential sensor, at low temperature, and the porous ceramic plug and Ag / AgCl located at the high temperature part. The electrodes were connected using heat-shrinkable Teflon tube, put a certain concentration of KCl in the tube, and a metal tube was installed outside for pressure boundary. Electrodes of this structure have been developed by Danielson and Macdonald. The porous ceramic stopper used in the external reference electrode is made of zirconia, and prevents the decrease of ionic activity of the buffer caused by leakage of KCl buffer solution in the Teflon tube into the hydrochemical environment and traces of ions passing through the porosity. It electrically connects between the reference electrode and the hydrochemical environment. The potential of the external reference electrode is determined by the potential generated by the reference reaction of the reference potential sensing unit, the thermal liquid junction potential generated by the temperature difference between the low temperature part and the high temperature part, and the concentration difference between the two solutions at the boundary of the porous ceramic plug. It consists of the sum of the generated liquid junction potentials. The hot contact potential and the liquid contact potential, which are the potential difference components of the external reference electrode using the Ag / AgCl reference reaction, have been sufficiently interpreted by various researchers including McDonald's, so the potential difference measured by the external reference electrode is a hydrogen reference electrode (Standard Hydrogen). Electrode, SHE) to scale. The external reference electrode having the above structure hinders the structural stability of the heat shrinkable Teflon tube due to the pressure change occurring in the operation of high temperature and high pressure hydrochemical environment, and problems such as deflection of potential due to leakage of buffer ions in the ceramic porous plug. It has a short lifespan.

맥도널드 및 스코트은 전통적인 외부기준전극의 설계를 변경하여 압력균형외부기준전극( Pressure-Balanced External Reference Electrode)을 발명하였다. 이것은 전극의 내부압력과 고온, 고압 수화학 환경의 압력간 균형을 유지하도록 하여 압력변화에 의한 외부기준전극의 수명단축 문제를 해결하였으며, 완충액이 일정한 유량으로 기준전극을 통과하게 함으로서 일정한 열간접촉전위를 유지하는 기준전극을 개발하였지만 복잡한 기준전극의 구조와 압력균형 유지, 일정한 유량 유지를 위한 주변장치의 추가 및 완충액의 용액이 계속 측정하는 영역으로 유입되는 단점이 있다.  McDonald's and Scott invented the Pressure-Balanced External Reference Electrode by changing the design of the traditional external reference electrode. This solves the problem of shortening the lifespan of the external reference electrode due to the pressure change by maintaining the balance between the internal pressure of the electrode and the pressure of the high temperature, high pressure hydrochemical environment, and the constant hot contact potential by allowing the buffer solution to pass through the reference electrode at a constant flow rate. Although the reference electrode was developed to maintain the structure and pressure balance of the complex reference electrode, the addition of a peripheral device for maintaining a constant flow rate and the solution of the buffer solution flows into the area to continuously measure.

상기한 바와 같은 문제점을 해결하기 위하여 본 발명은 구조가 단순하여 제작 및 사용이 용이한 외부기준전극을 제공하는 것을 목적으로 한다. In order to solve the above problems, an object of the present invention is to provide an external reference electrode having a simple structure and easy to manufacture and use.

또한, 외부기준전극과 금속 및 금속합금의 작업전극 사이의 전위를 측정함으로써 고온 고압 수화학 환경에서 금속 및 금속합금의 전기화학 및 부식 연구를 위한 기준전극을 제공하는 것을 목적으로 한다. In addition, it is an object of the present invention to provide a reference electrode for the electrochemical and corrosion studies of metals and metal alloys in a high temperature and high pressure hydrochemical environment by measuring the potential between the external reference electrode and the working electrodes of the metal and metal alloy.

또한, 구조가 단순하고, 경제적이며, 신뢰성 있는 외부기준 전극, 고온,고압 수화학 환경에서 수소기준전위(Standard Hydrogen Electrode, SHE)눈금으로 작업 전극에 대한 전기 화학적 전위를 측정할 수 있으면서도 기존의 다공성 세라믹 마개 를 사용하지 않아 고온에서 액간접촉전위의 발생을 근원적으로 제거하는 외부기준 전극 구조를 채택하고 저온에서 기준전위를 감지하는 부분에 고체기준전극을 채택함으로서 저온에서 고온으로 연결되는 관에 포함된 용액의 농도변화에 의한 전위편향현상을 억제한 외부기준전극을 제공하는 것을 목적으로 한다. In addition, the structure is simple, economical and reliable external reference electrode, the standard porosity of the standard electrode (SHE) scale in the high temperature, high pressure hydrochemical environment can measure the electrochemical potential on the working electrode while the existing porosity By adopting the external reference electrode structure that eliminates the contact potential between liquid at high temperature without using ceramic plug, and adopting the solid reference electrode at the part that detects the reference potential at low temperature, it is included in the pipe connected from low temperature to high temperature. An object of the present invention is to provide an external reference electrode which suppresses a potential deflection phenomenon due to a change in solution concentration.

상기한 바와 같은 목적을 위해서 본 발명은 고온 고압 수화학 환경에 적합한 외부기준전극을 제공하는데, 상기 외부기준전극은 To this end, the present invention provides an external reference electrode suitable for a high temperature and high pressure hydrochemical environment.

전극으로서, 금속으로 된 와이어 형태이며 그 표면에는 상기 금속의 염화물 피막이 상기 금속의 화학적 및 전기화학적 산화로 형성된, 전극과;An electrode, comprising: an electrode in the form of a wire of metal, the surface of which has a chloride coating of said metal formed by chemical and electrochemical oxidation of said metal;

상기 전극을 둘러싸고, 전기적 연결을 유지하며, 상기 전극에 의해 측정되는 기준전위에 영향을 미칠 수 있는 화학종의 오염을 방지하는, 원통형의 제1 튜브와;A cylindrical first tube surrounding the electrode, maintaining an electrical connection, and preventing contamination of species that may affect the reference potential measured by the electrode;

상기 제1 튜브의 외부에 형성되며, 압력경계를 유지하는, 원통형의 제2 튜브;를 포함할 수 있다 .It may be formed on the outside of the first tube, to maintain a pressure boundary, the second cylindrical tube; may include.

상기 전극은 은(Ag)으로 되어 있으며 , 상기 피막은, 가장 안쪽에 AgCl피막을 화학적 및 전기화학적 산화로 형성한 후 상기 피막의 외부에 PVC(Polyvinyl chloride)+KCl 또는 PVC(Polyvinyl chloride)+NaCl로 고체전해질 피막을 형성한 후 네피온(Nafion)피막을 형성시켜 이루어진 피막인 것일 수 있다. The electrode is made of silver (Ag), and the film is formed on the innermost surface of the AgCl film by chemical and electrochemical oxidation, and then PVC (Polyvinyl chloride) + KCl or PVC (Polyvinyl chloride) + NaCl on the outside of the film. After forming a solid electrolyte film may be a film formed by forming a Nafion (Nafion) film.

상기 제1 튜브는 알루미나, 지르코니아중 어느 하나로 이루어지며 상기 제2튜브는 금속 또는 금속합금 튜브인 것으로 스테인레스, 인코넬등과 같은 재질 일 수 있다. The first tube is made of any one of alumina and zirconia, and the second tube is a metal or metal alloy tube, and may be made of a material such as stainless steel or inconel.

상기 제2튜브의 외부에는 냉각을 위한 냉각장치를 더 포함할 수 있다. 이와 같은 냉각장치는 도1에 도시된 것과 같이 상기 제2튜브를 여러 번 감는 방식으로 형성된 냉각관이 될 수도 있으며, 제2튜브의 외부에 다수개의 핀을 형성하는 방식일수도 있다. The outside of the second tube may further include a cooling device for cooling. Such a cooling device may be a cooling tube formed by winding the second tube several times, as shown in FIG. 1, or may be a method of forming a plurality of fins outside the second tube.

상기 제1튜브와 상기 전극중 피막이 형성되지 않은 부분은 열수축 테프론으로 전기적으로 절연되며, 상기 제1튜브와 상기 전극사이에는 실런트가 채워지는 데 상기 실런트는 상기 제1튜브의 열팽창 계수보다 큰 것일 수 있다. The uncoated portion of the first tube and the electrode is electrically insulated with heat shrink Teflon, and the sealant is filled between the first tube and the electrode, wherein the sealant may be greater than the coefficient of thermal expansion of the first tube. have.

상기 실런트는 테프론,룰론(Rulon)중 어느 하나인 것일 수 있다. The sealant may be any one of Teflon and Rulon.

상기 외부기준전극의 전위는 저온부에서 발생하는 고체기준전극의 전위와 저온부와 고온부의 온도차에 의해 발생하는 열간접촉전위의 합으로 주어진다. The potential of the external reference electrode is given by the sum of the potential of the solid reference electrode generated in the low temperature portion and the hot contact potential generated by the temperature difference between the low temperature portion and the high temperature portion.

이하, 첨부한 도면을 참고로 하여 본 발명을 상세하게 설명한다. 도1과 도2는 본 발명에 따르는 외부기준전극의 일실시예를 도시하는 도면이다. 도면에서 보듯이 본 발명에서 제공하는 외부기준전극은 고체기준전극이 있는 저온부(15)와 외부와 압력경계를 이루는 금속튜브(7), 고온부(16)와 상기 저온부(15) 및 고온부(16)의 전기적 연결을 유지하는 세라믹튜브(4)로 구성된다. 세라믹 튜브(4)는 고온의 수화학 환경에서 전기화학 전위를 측정하고자 하는 금속 또는 금속합금의 근처에 위치시키게 된다. 외부기준전극의 압력경계는 코낵스 피팅(conax fitting)(제1피팅에 해당), 스에즈록 피팅(Swagelok fitting, 제2피팅에 해당) 및 금속 튜브로 구성되며, 저온부의 온도를 일정하게 유지하기 위하여 고체기준전극이 설치되어 있는 금속튜브(7)의 외부는 냉각관(8)을 사용한다. Hereinafter, the present invention will be described in detail with reference to the accompanying drawings. 1 and 2 illustrate an embodiment of an external reference electrode according to the present invention. As shown in the drawings, the external reference electrode provided in the present invention includes a low temperature unit 15 having a solid reference electrode and a metal tube 7, a high temperature unit 16 and the low temperature unit 15 and the high temperature unit 16 forming a pressure boundary with the outside. It consists of a ceramic tube (4) to maintain the electrical connection of the. The ceramic tube 4 is placed in the vicinity of the metal or metal alloy whose electrochemical potential is to be measured in a high temperature hydrochemical environment. The pressure boundary of the external reference electrode consists of a conax fitting (corresponding to the first fitting), a Swagelok fitting (corresponding to the second fitting), and a metal tube. The cooling tube 8 is used for the outside of the metal tube 7 in which the solid reference electrode is installed.

세라믹관(4)과 상기 전극중 피막이 형성되지 않은 부분은 열수축 테프론(12)으로 전기적으로 절연되며, 상기 세라믹관(4)과 상기 전극(2)사이에는 실런트(3)가 채워지는 데 상기 실런트(3)는 상기세라믹관(4)의 열팽창 계수보다 큰 데 10배정도로 큰것일 수도 있다. 상기 실런트는 테프론을 사용할 수도 있으며 룰론(Rulon)을 사용하는 것도 가능하다. 테프론 실런트(sealant)와 세라믹관(4)의 연결은 테프론의 열팽창계수가 지르코니아 세라믹 관(4)보다 열배정도 크므로 고온 조건에서 결합이 강화되는데 여기에 부가적으로 고온 에폭시로 접착시켜 결합력을 증가시키게 된다. The ceramic tube 4 and the portion of the electrode where no film is formed are electrically insulated by heat shrink Teflon 12, and the sealant 3 is filled between the ceramic tube 4 and the electrode 2. (3) may be about 10 times larger than the thermal expansion coefficient of the ceramic tube 4. The sealant may use Teflon, or Rulon. The connection between Teflon sealant and ceramic tube (4) is ten times greater than that of zirconia ceramic tube (4), so the bond is strengthened under high temperature conditions. Let's go.

저온부(15)에서 기준전위를 감지하는 부분은 Ag/AgCl고체기준전극(2)이 된다. Ag/AgCl고체기준전극은 1M의 HCl 용액에서 전기화학적 산화반응으로 AgCl피막(1)을 형성한 후 PVC(Polyvinyl chloride)+KCl 또는 PVC+NaCl로 고체전해질 피막을 만든다. 고체전해질 막이 형성된 후에 네피온(Nafion)피막을 입혀 제작한다. The portion of the low temperature portion 15 that detects the reference potential becomes the Ag / AgCl solid reference electrode 2. The Ag / AgCl solid reference electrode forms an AgCl film (1) by electrochemical oxidation in 1M HCl solution, and then forms a solid electrolyte film of polyvinyl chloride (PVC) + KCl or PVC + NaCl. After the solid electrolyte membrane is formed, it is prepared by coating a Nafion coating.

기준전위를 감지하는 저온부(15)와 고온부(16)는 세라믹 튜브(알루미나 또는 지르코니아 튜브,4)로 연결되어 있어 기준전위에 영향을 미칠 수 있는 화학종의 누설을 방지하며, 섭씨 300도 이상의 온도에서 기준전위의 측정을 가능하게 한다. The low temperature part 15 and the high temperature part 16 for detecting the reference potential are connected by a ceramic tube (alumina or zirconia tube, 4) to prevent leakage of chemical species that may affect the reference potential, and the temperature is higher than 300 degrees Celsius. This enables the measurement of the reference potential at.

외부기준전극에서 고온, 고압의 수화학 환경과 전기적 연결을 제공하는 다공성 세라믹 마개를 제거함으로서 고온부와 저온부를 연결하는 세라믹 튜브(4)가 측정환경과 같은 용액으로 채워지므로 고온부에서 액간접촉전위가 존재하지 않는다. 따라서 본 발명은 저온부의 고체기준전극 전위와 온도차에 의해 발생하는 열간접촉전위의 합으로 주어지는 기준전위와 다공성 세라믹 마개가 없는 구조가 단순한 외 부기준전극을 제공할 수 있다. By removing the porous ceramic plug which provides electrical connection with high temperature and high pressure hydrochemical environment at the external reference electrode, the ceramic tube (4) connecting the hot and cold parts is filled with the same solution as the measurement environment. I never do that. Accordingly, the present invention can provide an external reference electrode having a simple structure having no reference potential and a porous ceramic plug given by the sum of the hot reference potential generated by the solid reference electrode potential and the temperature difference of the low temperature portion.

본 발명에 따라 기준전극의 완충액과 수화학 환경을 분리하기 위하여 사용되어 왔던 다공성 세라믹 마개를 제거함으로써 외부기준전극은 단순한 구조를 가짐으로서 고온, 고압의 수화학 환경에서 부품의 손실에 의한 고장 가능성을 줄일 수 있었다. By removing the porous ceramic stopper, which has been used to separate the buffer solution and the hydraulic environment of the reference electrode according to the present invention, the external reference electrode has a simple structure, thereby preventing the possibility of failure due to component loss in a high temperature and high pressure hydraulic environment. Could reduce.

또한, 고온, 고압의 수화학 환경에서 금속 및 금속합금의 부식거동을 예측할 수 있는 정밀한 외부기준전극의 개발로 부식전위의 측정 및 고온 염기도 측정을 위한 기준전위를 제공함으로서 금속 및 금속합금의 부식환경을 진단할 수 있는 기본적인 센서를 제공할 수 있었다. In addition, by developing a precise external reference electrode that can predict the corrosion behavior of metals and metal alloys in high-temperature, high-pressure hydrochemical environments, it provides a reference potential for measuring corrosion potential and high-temperature basicity. It could provide a basic sensor to diagnose the problem.

Claims (6)

외부기준전극으로서, As an external reference electrode, 전극으로서 금속으로 된 와이어 형태이며 그 표면에는 상기 금속의 염화물 피막이 상기 금속의 화학적 및 전기화학적 산화로 형성된 전극과;An electrode in the form of a wire made of metal, the surface of which has a chloride coating of the metal formed by chemical and electrochemical oxidation of the metal; 상기 전극을 둘러싸고, 전기적 연결을 유지하며, 상기 전극에 의해 측정되는 기준전위에 영향을 미칠 수 있는 화학종의 오염을 방지하는, 원통형의 제1 튜브와;A cylindrical first tube surrounding the electrode, maintaining an electrical connection, and preventing contamination of species that may affect the reference potential measured by the electrode; 상기 제1 튜브의 외부에 형성되며, 압력경계를 유지하는, 원통형의 제2 튜브;A second cylindrical tube formed outside the first tube and maintaining a pressure boundary; 를 포함하는, 외부기준전극.Including, the external reference electrode. 제1항에 있어서, 상기 전극은 은(Ag)으로 되어 있으며 , 상기 피막은, 가장 안쪽에 AgCl피막을 화학적 및 전기화학적 산화로 형성한 후 상기 피막의 외부에 PVC(Polyvinyl chloride)+KCl과 PVC(Polyvinyl chloride)+NaCl로 고체전해질 피막을 형성한후 네피온(Nafion)피막을 형성시켜 이루어진 피막인 것을 특징으로 하는, 외부기준전극. The method of claim 1, wherein the electrode is made of silver (Ag), and the coating is formed on the innermost AgCl coating by chemical and electrochemical oxidation and then PVC (Polyvinyl chloride) + KCl and PVC on the outside of the coating (Polyvinyl chloride) + NaCl after forming a solid electrolyte film, a film formed by forming a Nafion (Nafion) film, the external reference electrode. 제1항에 있어서, 상기 제1 튜브는 알루미늄, 지르코니아중 어느 하나로 이루어지며 상기 제2튜브는 금속 또는 금속합금 튜브인 것을 특징으로 하는, 외부기준전극. The external reference electrode of claim 1, wherein the first tube is made of any one of aluminum and zirconia, and the second tube is a metal or metal alloy tube. 제1항에 있어서 상기 제2튜브의 외부에는 냉각을 위한 냉각장치를 더 포함하는 것을 특징으로 하는, 외부기준전극.The external reference electrode of claim 1, further comprising a cooling device for cooling the outside of the second tube. 제1항에 있어서, 상기 제1튜브와 상기 전극중 피막이 형성되지 않은 부분은 열수축 테프론으로 전기적으로 절연되며, 상기 제1튜브와 상기 전극사이에는 실런트가 채워지는 데 상기 실런트는 상기 제1튜브의 열팽창 계수보다 큰 것을 특징으로 하는, 외부기준 전극.According to claim 1, wherein the portion of the first tube and the electrode is not formed of the film is electrically insulated by heat shrink Teflon, the sealant is filled between the first tube and the electrode is the sealant of the first tube An external reference electrode, characterized in that greater than the coefficient of thermal expansion. 제5항에 있어서, 상기 실런트는 테프론, 룰론(Rulon)중 어느 하나인 것을 특징으로 하는, 외부기준전극.The external reference electrode of claim 5, wherein the sealant is one of Teflon and Rulon.
KR1020040092460A 2004-11-12 2004-11-12 External Reference Electrode for a Pressurized, High Temperature Aqueous Environments KR100612270B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1020040092460A KR100612270B1 (en) 2004-11-12 2004-11-12 External Reference Electrode for a Pressurized, High Temperature Aqueous Environments

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
KR1020040092460A KR100612270B1 (en) 2004-11-12 2004-11-12 External Reference Electrode for a Pressurized, High Temperature Aqueous Environments

Publications (2)

Publication Number Publication Date
KR20060046932A KR20060046932A (en) 2006-05-18
KR100612270B1 true KR100612270B1 (en) 2006-08-25

Family

ID=37149566

Family Applications (1)

Application Number Title Priority Date Filing Date
KR1020040092460A KR100612270B1 (en) 2004-11-12 2004-11-12 External Reference Electrode for a Pressurized, High Temperature Aqueous Environments

Country Status (1)

Country Link
KR (1) KR100612270B1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20150125456A (en) * 2014-04-30 2015-11-09 주식회사 미래와도전 Elctrode for test section

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100974565B1 (en) 2008-05-26 2010-08-06 한국원자력연구원 Reference Electrode Containing Light Absorbed Chemicals In The Electrolyte And Automatic Electrochemical Potential Correction Apparatus Using The Same
KR102066275B1 (en) * 2013-02-28 2020-01-14 주식회사 미래와도전 Electrode structure
CN106706744B (en) * 2015-11-12 2019-03-15 中国科学院过程工程研究所 A kind of electrochemical detection device and its processing method and purposes
KR102609730B1 (en) 2021-04-29 2023-12-05 주식회사 아이센스 Apparatus and method for correcting reference potential of electrochemical sensor

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20150125456A (en) * 2014-04-30 2015-11-09 주식회사 미래와도전 Elctrode for test section
KR101616125B1 (en) * 2014-04-30 2016-04-27 주식회사 미래와도전 Elctrode for test section

Also Published As

Publication number Publication date
KR20060046932A (en) 2006-05-18

Similar Documents

Publication Publication Date Title
JP5898595B2 (en) Corrosion potential sensor
JP2581833B2 (en) Plant operation status monitoring system
BRPI0910551B1 (en) DEVICE FOR THE MEASUREMENT AND MONITORING OF OXYREDUCTION POTENTIAL UNDER HIGH TEMPERATURE AND PRESSURE FOR HOT WATER SYSTEMS
JP4991683B2 (en) Electrochemical potential automatic correction device
US5516413A (en) Rugged electrode for electrochemical measurements at high temperatures and pressures
KR100612270B1 (en) External Reference Electrode for a Pressurized, High Temperature Aqueous Environments
CN102735737B (en) Liquid state alloy oxygen concentration sensor
Bosch et al. Simple and robust external reference electrodes for high-temperature electrochemical measurements
CN113984864A (en) Integrated sealed type liquid lead bismuth alloy oxygen concentration sensor
US5596134A (en) Continuous oxygen content monitor
JPH0560721A (en) Ag/ag ion electrode type reference electrode for high-temperature high-pressure water and plant control system using the same
RU66056U1 (en) DEVICE FOR MEASURING HYDROGEN CONTENT IN LIQUIDS AND GASES
US20130221971A1 (en) Electrode for Application in Electrochemical Measuring Systems
EP3236250A1 (en) Sensor for sensing hydrogen in gaseous media
RU2334979C1 (en) Device for measurement of hydrogen content in liquids and gases
JPS5838746B2 (en) Measuring device and reference electrode for measuring the amount of dissolved oxygen in liquid
JP5956368B2 (en) Corrosion potential sensor
US4290872A (en) High temperature reference electrode
RU2785081C1 (en) Potentiometric oxygen sensor for measuring oxygen concentration in liquid metal, its use for measurement of oxygen content in liquid sodium of sodium-fast nuclear reactor
Oh et al. Evaluation of thermal liquid junction potential of water-filled external Ag/AgCl reference electrodes
CN216792099U (en) Integrated sealed oxygen concentration sensor for liquid lead-bismuth alloy
JP5790923B2 (en) Na + concentration measurement system using pH meter
JP5358554B2 (en) Corrosion potential sensor and corrosion potential sensor installation structure
JP4476207B2 (en) Hydrogen detector
US10962502B2 (en) Hydrogen detector for gas and fluid media

Legal Events

Date Code Title Description
A201 Request for examination
E701 Decision to grant or registration of patent right
N231 Notification of change of applicant
GRNT Written decision to grant
FPAY Annual fee payment

Payment date: 20120807

Year of fee payment: 7

FPAY Annual fee payment

Payment date: 20130807

Year of fee payment: 8

FPAY Annual fee payment

Payment date: 20150807

Year of fee payment: 10

FPAY Annual fee payment

Payment date: 20160808

Year of fee payment: 11

FPAY Annual fee payment

Payment date: 20170807

Year of fee payment: 12

FPAY Annual fee payment

Payment date: 20180730

Year of fee payment: 13

FPAY Annual fee payment

Payment date: 20190807

Year of fee payment: 14