EP1322221A2 - Cellule electrochimique, utilisation de cette cellule electrochimique et procede de metallisation electrolytique et influence electrochimique d'une surface - Google Patents

Cellule electrochimique, utilisation de cette cellule electrochimique et procede de metallisation electrolytique et influence electrochimique d'une surface

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Publication number
EP1322221A2
EP1322221A2 EP01964794A EP01964794A EP1322221A2 EP 1322221 A2 EP1322221 A2 EP 1322221A2 EP 01964794 A EP01964794 A EP 01964794A EP 01964794 A EP01964794 A EP 01964794A EP 1322221 A2 EP1322221 A2 EP 1322221A2
Authority
EP
European Patent Office
Prior art keywords
electrochemical cell
electrolyte
electrochemical
container
tip
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.)
Withdrawn
Application number
EP01964794A
Other languages
German (de)
English (en)
Inventor
Markus Büchler
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
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 Individual filed Critical Individual
Publication of EP1322221A2 publication Critical patent/EP1322221A2/fr
Withdrawn legal-status Critical Current

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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
    • G01N27/403—Cells and electrode assemblies
    • G01N27/4035—Combination of a single ion-sensing electrode and a single reference electrode
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N17/00—Investigating resistance of materials to the weather, to corrosion, or to light
    • G01N17/02—Electrochemical measuring systems for weathering, corrosion or corrosion-protection measurement
    • 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
    • G01N27/401—Salt-bridge leaks; Liquid junctions

Definitions

  • Electrochemical cell use of the electrochemical cell and method for electrolytic contacting and electrochemical influencing of a surface
  • the invention relates to an electrochemical cell for electrolytic contacting and electrochemical control of surfaces according to the preamble of the first
  • the invention further relates to the use of the electrochemical cell after
  • the invention further relates to a method for electrolytic contacting and electrochemical influencing of a surface according to the preamble of the independent method claim.
  • electrochemical cells for the electrochemical control of surfaces.
  • the surface to be examined is immersed in an electrolyte.
  • the advantage is that uneven surfaces can also be examined electrochemically.
  • the disadvantage is that only the surfaces of small components can be examined, since otherwise a large amount of electrolyte is required.
  • the selective examination of certain areas of the surface is only possible if the rest of the surface is covered with a varnish.
  • the second type of cells as is known for example from DE 19749 111 A1
  • the surface to be examined is attached to a hole in the outer wall of a cell
  • a sealing ring which delimits the surface wetted by the electrolyte.
  • This method can be used to selectively select certain areas of the surface, but the surface must be flat and the size of the component to be examined is usually also limited.
  • a big problem with this type of cell is the gap that forms between the sealing ring and the surface.
  • the electrochemical control is only up to in this gap a certain mass possible. In corrosion investigations, crevice corrosion also preferably occurs in this gap.
  • the sealing ring therefore leads to undesirable heterogeneous behavior.
  • the use of silicone-coated glass capillaries with a diameter in the range of 1 mm and smaller made it possible to examine uneven surfaces, since curved surfaces appear flat on this small scale.
  • the silicone coating also acts as a sealing ring here.
  • a counter electrode is required for the electrochemical control of the surface.
  • a reference electrode is often also used. These reference electrodes consist of a container that contains a saturated solution. In most commercial systems, these are saturated
  • Potassium chloride solutions This container of the reference electrode is usually closed by a porous glass body. This allows the saturated potassium chloride solution to be in contact with the electrolyte and the diffusion between the two bodies is reduced. Over time, however, the potassium chloride will leak from the reference electrode and contaminate the electrolyte. This is particularly undesirable for corrosion tests, since chlorides are extremely aggressive. Therefore, in the previous cells, the electrolyte must be refilled before each measurement. The reference electrode must also be serviced regularly. This requires the handling of sometimes aggressive substances. This preparation of the cell requires a great deal of care, since the smallest air bubbles can prevent the reference electrode from contacting the electrolyte. Incorrect measurements or even the destruction of the surface to be examined are the result.
  • An electrochemical measuring cell is known from DD 263 829 A1.
  • the cell body consists of an electrically non-conductive, chemically resistant material and contains the reference and counter electrodes and takes up a small volume of aqueous electrolyte solution.
  • the test sample is switched as a working electrode and is located completely outside the electrode.
  • the substance and charge carrier exchange takes place via a conditionally permeable sensitive wall.
  • the reference electrode and the test electrolyte must be re-inserted into the cell before each use.
  • the closed cell also leads to problems with atmospheric pressure because of pressure fluctuations the electrolyte is pushed back through the porous wall or is sucked out of the cell.
  • gravity will cause the electrolyte to flow out, which can only be prevented by very fine pores.
  • the fine pores cause an ohmic voltage drop, which influences the measurement.
  • the cells used up to now cannot be used or can only be used with great difficulty on surfaces oriented downwards.
  • the reason for this lies in the force of gravity, which causes air bubbles to rise and thus prevents electrolytic contact with the surface to be checked.
  • the object of the invention is to bring a defined electrolyte into contact locally with a surface without using a sealing ring and thereby to establish an electrolyte connection to a counterelectrode and to control the surface locally electrochemically by applying an electrical current. According to the invention this is achieved by the characterizing features of the first claim.
  • the essence of the invention is that a body with capillary action is placed on a surface.
  • the body with capillary action is referred to below as the tip.
  • the capillary action of the tip can be achieved in different ways.
  • the entire body can be made of a porous material, such as pressed nylon felt.
  • Another variant is the use of a body with one or more capillaries.
  • the cross section of the tip decreases towards the end. A minimal ohmic voltage drop is thereby achieved.
  • the electrolyte flows out of the container through the tip and wets the surface.
  • the container is made of a porous material.
  • the porosity is designed such that the capillary action prevents the electrolyte from flowing out and at the same time can take up a maximum electrolyte volume. This ensures the longest possible service life of the electrochemical cell.
  • the capillary forces prevent the electrolyte from flowing out of the container and from the tip.
  • the container is open during use so that the electrolyte is not prevented from flowing by the build-up of a vacuum. Ideally, the container is sealed off from the environment by a casing to prevent the electrolyte from evaporating.
  • the sheath is designed to be open during use to prevent pressure differences.
  • the electrochemical cell can easily be closed by putting a lid on.
  • an electrolytic connection is established between the surface and a counter electrode, which is immersed in the container.
  • the electrochemical potential of the surface can be influenced by electrical current flow between the surface and the counter electrode.
  • a silver surface is used as the reference electrode, which is ideally coated with silver chloride.
  • a tungsten surface can also be used.
  • the advantage of the invention is that the electrochemical cell is prevented from flowing out without the use of a sealing ring due to the capillary action of the tip and the container, and the surface is wetted with a defined electrolyte by simply removing the lid and fitting the tip. Since both the electrolyte's flow to the surface and from the container to the tip is achieved exclusively by the capillary action, the function of the electrochemical cell is completely independent of gravity. As a result, measurements on surfaces that are oriented downwards are also possible.
  • measurements can also be carried out without problems in weightlessness. Since the container is open, the atmospheric pressure has no significant influence on the measurement. Since the cross-section of the tip decreases towards the end and the container has a maximum porosity, a large volume is available for conducting the electrolytic current in the container and in the tip. The ohmic voltage drop therefore only occurs at the very end of the tip. The falsification of the measurement by the ohmic voltage drop can thereby be reduced to a minimum. Placing the cell on the surface to be examined is problem-free, since when the tip is lifted off, the capillary action of the tip prevents the electrolyte from flowing out. If the tip when placing on the surface is not significantly deformed, the contact surface with the surface is only selective.
  • the gap area is thus smaller than when using a sealing ring, where the entire circumference of the wetted surface consists of a gap. If, on the other hand, the tip deforms due to the contact pressure, it adapts to the surface geometry and the entire wetted surface then consists of a gap.
  • the heterogeneous behavior that is observed when using a sealing ring therefore does not occur or only occurs to a small extent.
  • the electrochemical cell Since the electrochemical cell is prevented from flowing out even without the tip contacting the surface due to the capillary action of the tip, the electrochemical cell is very easy to handle. It can be held in the hand, for example, and placed on the strongly curved surface of a component of any size (computer chip, automobile, pipeline, etc.). Since the tip's support is only selective or the tip adapts to the surface elastically, any curved surface geometry can be examined. When using a sealing ring, the surface must allow a circular support of the sealing ring, which places demands on the planarity or the surface radius. The surface of the component is wetted locally with the electrolyte, which enables electrochemical investigations with local resolution.
  • the electrochemical cell When the cell is lifted off, the capillary action prevents the cell from flowing out again.
  • the electrochemical cell When closed, the electrochemical cell can be stored ready for use for longer periods of time and can be used at any time without preparation. This saves a lot of time when performing electrochemical measurements. Furthermore, the electrochemical cell can be economically prefabricated completely ready for use, making it possible to use it in series production.
  • the electrolyte at the tip evaporates, which leads to a concentration. This can be avoided if the tip is surrounded by a coat. A high level of air humidity will quickly set up inside the jacket, preventing further evaporation. In this way, long-term measurements can also be carried out with the electrochemical cell.
  • the jacket can also take on additional functions. It can be made of a conductive material and thus provide the electromagnetic shielding of the cell or make conductive contact with the surface. With the additional use of a spring, the jacket can also be used to ensure a constant contact pressure. This increases the reproducibility of the measurements and the service life of the tip. Thanks to its porous structure, the tip prevents any convection of the electrolyte.
  • the capillary action of the porous film transports the electrolyte away to the side. Evaporation on the large surface of the film creates a continuous flow of electrolyte, which transports the reaction products away to the side. In this way, an easy-to-use flow cell is achieved.
  • the composition of the electrolyte can be characterized electrochemically. This requires the use of a further potentiostat or, ideally, a bipotentiostat.
  • the tip is ideally mounted in the sleeve by means of a clamp. The tip is pushed into a tube, which is threaded and the walls of which can be elastically deformed in the radial direction. This elastic deformability is ideally achieved through slits in
  • the opening in the sleeve is conical, so that the diameter of the tube is reduced when the tube is screwed in. Clamping is achieved by screwing the tube with the tip into the sleeve. This means that the tip can be easily replaced at any time.
  • FIG. 2 shows electrochemical measurements at various points on a component made of stainless steel (DIN 1.4529) with a weld seam.
  • DIN 1.4529 stainless steel
  • SCE saturated Calomel electrode
  • FIG. 6 shows an electrochemical measurement of a heterogeneous surface by automatic scanning with the electrochemical cell.
  • the measuring area is 18x18 mm.
  • the current density is shown at a constant electrochemical potential of 0.16 V SCE.
  • the maximum current density is 5 ⁇ A.
  • a tip 2 is in contact with an open container consisting of a porous material 3, which contains an electrolyte.
  • the container 3 is surrounded by an open shell 4 with an opening 18 in order to evaporate the
  • the tip consists of a body with capillary action, the cross-sectional area of which decreases towards the end, whereby the ohmic voltage drop is reduced to a minimum.
  • the capillary action can be achieved, for example, by a body made of a porous material or by a body with one or more capillaries with any cross-sectional area.
  • the tip can be made of pressed nylon felt, a fiber bundle or two concentric plastic cylinders with a cylindrical gap. It is also possible to manufacture the container and the tip from the same body. For example, a nylon felt used as a container may be hot pressed on one side thereof, thereby forming the tapered tip.
  • the capillary action is such that the electrolyte is prevented from flowing out when the tip is lifted off.
  • the electrolyte flows out of the container through the tip and locally wets the surface.
  • the capillary force between surface 7 and tip 2 prevents the electrolyte 15 from flowing out of the container, as is shown by the enlargement of the tip in FIG. 1.
  • the enlargement shows the case of a tip that is not deformed when it is put on. There is therefore only a small gap.
  • the tip preferably has a smaller diameter at the end than at the junction with the container 3.
  • the container is made of a porous material or another material with a capillary effect, such as felt.
  • a counter electrode 5 is mounted in this container and is in contact with the electrolyte.
  • This counter electrode consists of an electrically conductive, preferably inert material such as platinum, graphite, gold, silver, titanium or stainless steel.
  • the counter electrode is electrically conductively connected to a current source 8, such as a battery, a potentiostat or a galvanostat.
  • This current source is also electrically conductively connected to the surface to be examined.
  • the surface in the wetted area is influenced electrochemically by current flow between the surface 7 and counter electrode 5.
  • the tip can slide or step over the surface, electrochemically affecting different areas of the surface. Both the wetting of the surface and the reflow of the electrolyte 15 are brought about by the capillary action of the tip and the container.
  • the use of the electrochemical cell is independent of gravity. Use on downward-facing surfaces and in zero gravity is possible without any problems.
  • a reference electrode 6 the detection of the electrochemical potential of the surface 7 is also possible.
  • this reference electrode can consist of a silver surface, which is ideally coated with silver chloride.
  • This jacket 9 can consist, for example, of a solid plastic cylinder or a soft rubber sleeve. It is essential that it rests on the surface and prevents or at least strongly prevents the exchange of air with the environment. By additionally using a spring 10, a constant contact pressure of the tip 2 against the surface 7 can be achieved. If the sheath consists of an electrically conductive material, it can also be used for shielding electromagnetic fields and / or for electrically contacting the surface 7. According to FIG. 4, by using a porous film 11, such as a nylon fabric, an electrolyte flow and thus a continuous renewal of the electrolyte on the examined surface can be achieved.
  • a porous film 11 such as a nylon fabric
  • the rate of corrosion can be determined with minimal influence on the surface.
  • Semiconductor properties such as the flat band potential and the
  • Coating resistance and capacitance can be examined.
  • Local coatings can be applied by electrodeposition.
  • the local application of copper, polypyrrole or other substances is possible without any masking of the surface with photolithography.
  • a local etching process can be carried out by electrical dissolution. Since the tip can be slid over the surface gradually, material sizes (such as capacity or penetration resistance etc.) can be determined with lateral resolution. Structures, such as conductor tracks, can also be painted on surfaces by electrodeposition.
  • the electrochemical cell can be prefabricated completely or partially industrially at low cost. Since the cell can be used immediately without preparation, considerable time is saved. After the measurement, the electrochemical cell can be closed until the next measurement.
  • FIG. 1 an application example of the invention is shown.
  • the tip 2 is connected to a container 3 which contains a 1 M NaCl solution. Their evaporation is prevented by the casing 4.
  • a platinum wire is immersed in the electrolyte as counter electrode 5 and a silver wire coated with silver chloride as reference electrode 6.
  • These electrodes are connected via electrical connections to a potentiostat 8, which is additionally connected to the surface 7 of a welded component, which in this example consists of stainless steel (DIN 1.4529).
  • a welded component which in this example consists of stainless steel (DIN 1.4529).
  • the tip was placed on different parts of the component.
  • the resistance of the material at these points was examined by measuring current density-potential curves with the potentiostat. The results are shown in Figure 2.
  • pitting does not occur in the base material (a) or on the weld seam (c).
  • a strong current rise was found in the heat affected zone (b) even at low potential values, which shows the poor resistance of this area to local corrosion attacks. It is therefore clear that the welding parameters must be improved in order to achieve high corrosion resistance in all areas.
  • the electrochemical cell can be closed until the next measurement. Storage is possible over longer periods of time and no preparation is required for later measurements.
  • a jacket 9 In long-term investigations, it is essential that the evaporation of the electrolyte is prevented by a jacket 9. This is possible by using a jacket 9, as shown in FIG. 3.
  • the jacket 9 greatly reduces the exchange of air with the surroundings, so that the air around the tip saturates very quickly through evaporation of the electrolyte. The further evaporation comes to a standstill.
  • the jacket 9 is selected from a conductive material, it can be used simultaneously for the shielding and the contacting of the surface 7. By using a spring 10, the jacket 9 can also be used for setting a reproducible contact pressure.
  • FIG. 1 An example of an application for measurements under electrolyte flow is shown in FIG.
  • a porous film 11 such as a nylon fabric
  • the electrolyte is removed by the capillary action of the film
  • a continuous electrolyte flow is achieved by continuous evaporation on the comparatively large surface of the porous body. In this way, reaction products are simply removed. If the film is in contact with an electrically conductive, preferably inert, material, the composition of the removed electrolyte can also be analyzed electrochemically.
  • the jacket 9 can take over the function of the electrode, for example. In the case of this configuration, a bipotentiostat 12 is used.
  • a design sketch of the electrochemical cell is shown in FIG. The tip 2 is screwed into the open shell 4 with a tube 13. As a result, the tip 2 is clamped, which enables the tip 2 to be replaced easily. By opening the cover 14, the opening 18 and the tip 2 are closed.
  • FIG. 6 shows a measurement on a thermally sprayed coating.
  • the electrochemical cell was slid over the surface to be examined.
  • the examined area is 18x18 mm.
  • the current density is shown in the vertical axis with a constant electrochemical potential of 0.16 V converted to a calomel electrode.
  • the maximum value of the current density is 5 ⁇ A with a measuring area of 0.25 mm 2 .
  • there are two types of defects in the layer The one are isolated pinholes 16 and the other are surface defects 17, which may be due to cracks and poor adhesion of the layer. Based on the measurement, it is clear that the manufacturing parameters must be optimized.
  • the electrochemical cell can also be used to carry out potentiostatic and galvanostatic holding tests and jumping tests.
  • impedance measurements can be carried out, for example, and electrodeposition and dissolution on the surface are also possible.
  • the potentiostat can, for example, also be replaced by a simpler voltage source, such as a battery.
  • the surface is wetted locally by the tip of a defined electrolyte flowing from an open porous container, and that the surface is electrochemically influenced by an electrical current between the surface and the counter electrode.

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Pathology (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Physics & Mathematics (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Molecular Biology (AREA)
  • Biodiversity & Conservation Biology (AREA)
  • Ecology (AREA)
  • Environmental & Geological Engineering (AREA)
  • Environmental Sciences (AREA)
  • Testing Resistance To Weather, Investigating Materials By Mechanical Methods (AREA)

Abstract

L'invention concerne une cellule électrochimique pour la métallisation électrolytique et le contrôle électrochimique de surfaces, qui effectue un contact électrolytique avec la surface par l'intermédiaire d'un corps à effet capillaire. La force capillaire entre la surface et le corps à effet capillaire empêche l'électrolyte de s'écouler hors de la cellule sans faire appel à une bague d'étanchéité. Le corps à force capillaire permet à l'électrolyte de continuer à s'écouler d'un récipient poreux ouvert, ainsi que l'imprégnation de la surface au contact de la cellule électrochimique avec ladite surface. L'écoulement de la cellule ouverte est évité par l'effet capillaire du récipient et de la pointe lorsque la cellule électrochimique est soulevée de la surface. Ladite cellule électrochimique est indépendante de la force de gravité et permet de ce fait d'effectuer des mesures sur des surfaces, quelle que soit leur orientation. La cellule électrochimique permet d'effectuer une pluralité d'examens et de processus électrochimiques. Cette cellule électrochimique peut être guidée par glissement au-dessus de la surface, ce qui permet d'effectuer des examens ou des processus électrochimiques à résolution latérale. L'utilisation d'une électrode de référence sans entretien permet de préfabriquer la cellule électrochimique de manière entièrement industrielle et de la conserver longtemps par scellement hermétique.
EP01964794A 2000-09-22 2001-09-18 Cellule electrochimique, utilisation de cette cellule electrochimique et procede de metallisation electrolytique et influence electrochimique d'une surface Withdrawn EP1322221A2 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
CH184300 2000-09-22
CH18432000 2000-09-22
CH365012001 2001-02-28
CH00365/01A CH697205A5 (de) 2000-09-22 2001-02-28 Elektrochemische Zelle und Verwendung der elektrochemischen Zelle.
PCT/CH2001/000562 WO2002025249A2 (fr) 2000-09-22 2001-09-18 Cellule electrochimique, utilisation de cette cellule electrochimique et procede de metallisation electrolytique et influence electrochimique d'une surface

Publications (1)

Publication Number Publication Date
EP1322221A2 true EP1322221A2 (fr) 2003-07-02

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EP01964794A Withdrawn EP1322221A2 (fr) 2000-09-22 2001-09-18 Cellule electrochimique, utilisation de cette cellule electrochimique et procede de metallisation electrolytique et influence electrochimique d'une surface

Country Status (5)

Country Link
US (1) US20030178321A1 (fr)
EP (1) EP1322221A2 (fr)
AU (1) AU2001285637A1 (fr)
CH (1) CH697205A5 (fr)
WO (1) WO2002025249A2 (fr)

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CN101002103A (zh) * 2004-08-05 2007-07-18 Sv探针私人有限公司 探针尖部镀
DE102005020734B8 (de) * 2005-05-04 2007-02-15 Gesellschaft für Schwerionenforschung mbH Elektrolytische Zellenanordnung
CN103149192B (zh) * 2013-02-22 2015-05-13 厦门大学 一种用于非水体系的原位电化学-拉曼联用测试装置
NO20160373A1 (en) 2016-03-03 2017-09-04 Vetco Gray Scandinavia As Rapid non-destructive evaluation of the degree of sensitization in stainless steels and nickel based alloys
CN106802274A (zh) * 2016-12-30 2017-06-06 中国石油集团工程设计有限责任公司 缓蚀剂对油气管焊缝腐蚀控制效果的测定方法
JP7142856B2 (ja) * 2018-03-08 2022-09-28 マツダ株式会社 金属材の耐食性試験方法及び耐食性試験装置
PL446474A1 (pl) * 2023-10-24 2025-04-28 Uniwersytet Jagielloński Urządzenie do prowadzenia reakcji elektrochemicznej w przesuwanym menisku i sposób prowadzenia reakcji elektrochemicznej w przesuwanym menisku

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Also Published As

Publication number Publication date
AU2001285637A1 (en) 2002-04-02
CH697205A5 (de) 2008-06-25
US20030178321A1 (en) 2003-09-25
WO2002025249A3 (fr) 2002-10-31
WO2002025249A2 (fr) 2002-03-28

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