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EP0244626B1 - Electrode et son application - Google Patents

Electrode et son application Download PDF

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Publication number
EP0244626B1
EP0244626B1 EP87104615A EP87104615A EP0244626B1 EP 0244626 B1 EP0244626 B1 EP 0244626B1 EP 87104615 A EP87104615 A EP 87104615A EP 87104615 A EP87104615 A EP 87104615A EP 0244626 B1 EP0244626 B1 EP 0244626B1
Authority
EP
European Patent Office
Prior art keywords
electrodes
brickwork
electrode
drying
desalting
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP87104615A
Other languages
German (de)
English (en)
Other versions
EP0244626A1 (fr
Inventor
Bernard Dr Wessling
Christian Funder
Harald Dr. Volk
Olaf Siemers
Holger Merkle
Manfred Hilleberg
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.)
Wessling Bernhard Dr
Original Assignee
Wessling Bernhard Dr
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 Wessling Bernhard Dr filed Critical Wessling Bernhard Dr
Priority to AT87104615T priority Critical patent/ATE47529T1/de
Publication of EP0244626A1 publication Critical patent/EP0244626A1/fr
Application granted granted Critical
Publication of EP0244626B1 publication Critical patent/EP0244626B1/fr
Expired legal-status Critical Current

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Classifications

    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
    • E04B1/00—Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
    • E04B1/62—Insulation or other protection; Elements or use of specified material therefor
    • E04B1/70—Drying or keeping dry, e.g. by air vents
    • E04B1/7007—Drying or keeping dry, e.g. by air vents by using electricity, e.g. electro-osmosis
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F13/00—Inhibiting corrosion of metals by anodic or cathodic protection
    • C23F13/02—Inhibiting corrosion of metals by anodic or cathodic protection cathodic; Selection of conditions, parameters or procedures for cathodic protection, e.g. of electrical conditions
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F2201/00—Type of materials to be protected by cathodic protection
    • C23F2201/02—Concrete, e.g. reinforced

Definitions

  • the invention relates to electrodes based on thermoplastic macromolecular materials and conductive non-metallic additives and the use thereof.
  • Electrodes are used for various electrochemical purposes, especially in aqueous media, e.g. for the electrochemical synthesis of substances, for electrolysis, for measuring purposes or as sensors or in galvanic cells for storing electrical energy.
  • Electrodes which can be produced with thermoplastic processing methods (e.g. extrusion or injection molding) from mixtures of thermoplastic macromolecular materials with conductive non-metallic additives and which are stable under electrolysis conditions (cf. e.g. D. Kyriacon and D. Jannakondakis, "Electrocatalysis for Organic Synthesis ", New York 1986).
  • thermoplastic processing methods e.g. extrusion or injection molding
  • electrolysis conditions cf. e.g. D. Kyriacon and D. Jannakondakis, "Electrocatalysis for Organic Synthesis ", New York 1986.
  • a particularly interesting application for such electrodes under complex electrolytic conditions are electrical processes for removing capillary moisture in masonry.
  • the capillary moisture and salinization of masonry as well as the corrosion of reinforced concrete represent a serious economic and conservation problem.
  • EP-OS 100 845 and AT-OS 3101/82 network-like, conductive coated carbon fiber electrode: network quickly loses electrical contact with the electrode, which is also removed at short notice); M.W. Tenge, DE-OS 27 06 172 and 27 06 193, 27 05 814, 27 05 813 and 25 03 670 (soot-filled PTFE electrode; with 9 2 V working voltage too low, poor contact with the masonry, very low conductivity).
  • the synthetic macromolecular material A is polar and stable with respect to the electrolysis medium, i.e. stable in hydrolysis and above all oxidation in aqueous media.
  • the material can be processed thermoplastically and can, but need not, be crosslinkable.
  • the macromolecular electrode component A has polar substances, including EVA (ethylene vinyl acetate), CPE (chlorinated polyethylene), TPU (thermoplastic polyurethane), in particular polyether polyurethane, hard and soft PVC (polyvinyl chloride), NBR (nitrile rubber), ABS (acrylonitrile butadiene) -Styrene terpolymer), SBR (styrene-butadiene rubber), fluoroelastomers or mixtures of such substances have been proven. They should be able to be well wetted by the electrolysis medium, but not swell or dissolved or (e.g. hydrolytically) decomposed.
  • the conductive additives B are non-metallic; on the one hand, they are capable of modifying the material in a conductive manner, on the other hand, they can build up a potential during use (for example, compared to a reference electrode before or after a certain period of operation), without this significantly affecting the system's operability.
  • the conductive additives B are mixtures of a) so-called conductive carbon black (electrically conductive carbon black with a surface area of more than 600 m 2 / g) and optionally carbon fibers with b) carbon black of lower conductivity with a surface area of less than 600 m 2 / g, graphite , intrinsically conductive polymers (in complexed or compensated form) or transition metal oxides.
  • Examples of intrinsically conductive polymers are polyacetylene, polypyrrole, polyphenylenes, polyanilines, polythiophenes, polyphthalocyanines and other polymers with conjugated ⁇ -electron systems.
  • suitable metal oxides are Fe (II) / Fe (III) mixed oxides, Mn0 2 , V 2 0s, Nb 2 0 3 , that is to say those in which the transition metal can be converted into a higher, likewise stable oxidation state.
  • the conductive additives B are mixed in concentrations of 3 to 75% by weight, preferably 8 to 55% by weight, with 25 to 97, preferably 45 to 92% by weight or component A.
  • Mixture B contains the conductive and the potential stabilizing substances in weight ratios of 1: 4 to 4: 1.
  • the resistivity preferred for use as an electrode is less than 104 fi cm, preferably below 10 3 0 cm, more preferably below the second 102 0 cm.
  • the electrode material is produced on commercially available plastic processing machines such as twin-screw extruders, internal mixers or the like using conventional processing aids such as stabilizers, lubricants, fillers, etc.
  • the mass obtained is granulated or transformed directly into the later electrode shape (foils, plates, profiles, etc.).
  • the electrodes are used in a variety of processes, e.g. as sensors, as electrodes for electrolytic oxidation or reduction, for electrocatalysis, for drainage - e.g. of masonry, sludge, peat and the like - for desalination or corrosion protection.
  • Electrodes were tested with 6 V DC voltage in aqueous NaCl solution. It was found that the current flow drops rapidly with graphite electrodes, and likewise with carbon fiber electrodes. Metal electrodes are consumed. Carbon-filled polymer electrodes made of e.g. cross-linked polyethylene, which contain a metal core, apparently always have contact problems and ultimately break down the metal core through a weak point; wetting by the electrolysis medium is poor.
  • the electrodes according to the invention surprisingly show a completely different behavior: after an initially constant current, the current flow increases by up to 50%, then drops slightly and stabilizes at least at the initial level, but often between the initial and the maximum level.
  • the initial current is essentially determined by the resistance of the electrodes and is therefore higher for the carbon fiber.
  • the electrode according to the invention shows a current which is more than 10 times higher is even higher than the baseline.
  • the electrodes are placed in a flat form, e.g. in the form of foils or plates. Foils that have been punched out (to facilitate plastering) have proven effective for drying walls.
  • the foils are connected by conductors with a large cross section e.g. contacted by welding; these conductors can run inside the masonry, as can the contact point in the masonry (e.g. plaster); the contact between the voltage generator and the conductor must be outside the masonry with protection against moisture.
  • Direct and alternating voltages of the required size can be used to operate the electrodes.
  • use is preferably made between 4 and 48V, and pulsed DC voltage can be used to limit the current flow at voltages of more than 6V.
  • Another anode consisted of PVC and 40% polyaniline hydrochloride (No. 6), the cathode made of PVC, 40% polyaniline and 8% conductive carbon black.
  • a carbon fiber find (No. 7) is used as a further comparison electrode.
  • the electrodes are attached in an electrolysis vessel in spatially separated but electrolytically connected cylinders, the aqueous solution ( 2 g NaCI / 100 g H 2 O) only half covering the electrodes, so that the electrodes are contacted with welded metal wires outside the electrolysis medium can.
  • the cylinders have a valve at the top, so that gases can be periodically released during electrolysis.
  • Example 2 In a long-term test, three electrode compositions composed according to the invention were used as anode and cathode in an aqueous electrolysis according to Example 2. All electrodes contained conductive carbon black (Ketjenblack EC) as component Ba in soft PVC. No. 1 and No. 2 contained as component Bb graphite, No. 3 the mixed oxide of Example 2. The current profile is shown in FIG. 5 (not standardized on the electrode area).
  • conductive carbon black Ketjenblack EC

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Architecture (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electromagnetism (AREA)
  • Physics & Mathematics (AREA)
  • Water Supply & Treatment (AREA)
  • Civil Engineering (AREA)
  • Structural Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Conductive Materials (AREA)
  • Primary Cells (AREA)
  • Hybrid Cells (AREA)
  • Electrolytic Production Of Metals (AREA)

Claims (10)

1. Electrode stable dans des conditions d'électrolyse, convenant en particulier au séchage de maçonnerie, réalisée à partir de substances conductrices et de matériaux macromoléculaires faisant fonction de liants, caractérisée en ce qu'elle est constituée de:
A. un polymère thermoplastique polaire, un polycondensat thermoplastique ou un polyadditif thermoplastique, ou leurs mélanges, qui peuvent être correctement mouillés par le milieu électrolytique et sont stables par rapport au processus électrochimique se produisant sur l'électrode concernée, et
B. un mélange d'un rapport en poids de 1:4 à 4:1 composé de:
a) noir de fumée conducteur avec une surface supérieure à 600 m2/g et, le cas échéant, de fibres de carbone et
b) noir de fumée avec une surface inférieure à 600 m2/g et/ou de graphite et/ou d'oxydes métalliques transitoires et/ou d'un polymère intrinsèquement conducteur.
2. Electrode conforme à la revendication 1, caractérisée en ce qu'elle contient, comme composante A, du chlorure de polyvinyle et/ou du polyéthylène chloré.
3. Electrode conforme aux revendications 1 ou 2, caractérisée en ce que les composants A et B sont présents dans un rapport en poids compris entre 97:3 et 25:75.
4. Utilisation de l'électrode conforme à l'une quelconque des revendications 1 à 3, en particulier pour dessaler et sécher la maçonnerie, pour supprimer l'humidité capillaire des tourbes ou des boues, pour protéger contre la corrosion, pour irriguer les sols, dans l'électrosynthèse ou l'électrocatalyse et sous forme de capteurs.
5. Utilisation conforme à la revendication 4 pour dessaler et sécher la maçonnerie, caractérisée en ce qu'une électrode conforme aux revendications 1 à 3 est utilisée comme anode, et en ce que des tensions de 4 à 48 V sont appliquées.
6. Utilisation conforme à l'une quelconque des revendications 4 ou 5, caractérisée en ce que les électrodes possèdent une résistance spécifique inférieure à 104 a cm.
7. Utilisation conforme à l'une quelconque des revendications 4 à 6, caractérisée en ce que les électrodes de grande surface sont mises en contact avec la maçonnerie, les électrodes réalisées sous forme de feuilles ou de pistes étant pourvues de découpages matricés pour en faciliter la pose.
8. Utilisation des électrodes pour dessaler et sécher la maçonnerie conforme à l'une quelconque des revendications 4 à 7, caractérisée en ce que la tension est appliquée aux électrodes par une source de tension, qui est disposée à l'extérieur du mur, par l'intermédiaire de conducteurs de forte section réalisés dans le même matériau que celui des électrodes utilisées.
9. Utilisation des électrodes pour dessaler et sécher la maçonnerie conforme à l'une quelconque des revendications 4 à 9, caractérisée en ce qu'une tension continue pulsée est appliquée.
10. Utilisation des électrodes pour dessaler et sécher la maçonnerie conforme à l'une quelconque des revendications 4 à 9, caractérisée en ce que les électrodes sont appliquées contre la maçonnerie à sécher ou, respectivement, à dessaler au moyen d'un crépi particulièrement riche en hydroxyde et/ou carbonate de calcium.
EP87104615A 1986-03-27 1987-03-27 Electrode et son application Expired EP0244626B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87104615T ATE47529T1 (de) 1986-03-27 1987-03-27 Elektrode sowie deren verwendung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3610388 1986-03-27
DE19863610388 DE3610388A1 (de) 1986-03-27 1986-03-27 Stabile elektroden auf basis makromolekularer werkstoffe und verfahren zu ihrer verwendung

Publications (2)

Publication Number Publication Date
EP0244626A1 EP0244626A1 (fr) 1987-11-11
EP0244626B1 true EP0244626B1 (fr) 1989-10-25

Family

ID=6297415

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87104615A Expired EP0244626B1 (fr) 1986-03-27 1987-03-27 Electrode et son application

Country Status (6)

Country Link
US (1) US4806212A (fr)
EP (1) EP0244626B1 (fr)
AT (1) ATE47529T1 (fr)
DE (2) DE3610388A1 (fr)
ES (1) ES2011275B3 (fr)
GR (1) GR3000319T3 (fr)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT390274B (de) * 1988-03-15 1990-04-10 Steininger Karl Heinz Elektrode
FR2652943B1 (fr) * 1989-10-05 1994-07-01 Electricite De France Materiau conducteur pour electrode, composant electrique et leur procede de fabrication.
US5476612A (en) * 1989-12-30 1995-12-19 Zipperling Kessler & Co., (Gmbh & Co.). Process for making antistatic or electrically conductive polymer compositions
DE3943420A1 (de) * 1989-12-30 1991-07-04 Zipperling Kessler & Co Verfahren zur herstellung von antistatisch bzw. elektrisch leitfaehig ausgeruesteten polymeren zusammensetzungen
DE4024268A1 (de) * 1990-07-31 1992-02-06 Lehmann & Voss & Co Elektrisch leitfaehiges kunststoffelement und seine verwendung
JPH0489561A (ja) * 1990-08-01 1992-03-23 Mitsubishi Petrochem Co Ltd クーロメトリック型電気化学検出器用電極
US5955834A (en) * 1996-08-02 1999-09-21 The Ohio State University Light emitting devices utilizing high work function electrodes
US6623870B1 (en) * 1996-08-02 2003-09-23 The Ohio State University Electroluminescence in light emitting polymers featuring deaggregated polymers
WO1998020331A1 (fr) * 1996-11-07 1998-05-14 Cambridge Sensors Limited Electrodes et leur utilisation dans des dosages
US6323659B1 (en) * 1998-04-29 2001-11-27 General Electric Company Material for improved sensitivity of stray field electrodes
GB2352993B (en) * 1999-08-10 2003-12-24 Clive Alan Francis Blade sharpener
DE10058507A1 (de) * 2000-11-24 2002-06-06 Dutkewitz Wolfgang Vorrichtung zum induzierten, gerichteten Molekül- und Ionentransport in nichtkapillaren sowie insbesondere kapillaren Stoffen mittels dispergierter Elektroden und netzunabhängiger Solarstromversorgung (Sicco-Plan-System)
US20070256932A1 (en) * 2006-05-08 2007-11-08 Siemens Water Technologies Corp. Electrolytic apparatus with polymeric electrode and methods of preparation and use
DE102007062504A1 (de) * 2007-12-20 2009-07-02 Horn GmbH Fabrik für Metall-, Silicon-, und Teflonverarbeitung Körperelektrode
HUE030729T2 (en) * 2008-11-06 2017-05-29 Clariant Int Ltd Composition containing propylene olefin copolymer waxes and carbon black

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US4254727A (en) * 1959-12-30 1981-03-10 Moeller Kurt G F Shock-crush subfoundation
AT238417B (de) * 1962-02-19 1965-02-10 Curt Ing Meisel-Krone Elektrode für die Entfeuchtung bzw. Trockenlegung von Mauerwerk
DE2040510C3 (de) * 1970-08-14 1980-03-06 Dr. Karl Thomae Gmbh, 7950 Biberach Oxazole- und Thiazole eckige Klammer auf 5,4-d] azepin- Derivate
DE2706193A1 (de) * 1975-01-29 1978-08-17 Tenge Hans Werner Anordnung von elektroden bei elektro- physikalischen verfahren
DE2705813A1 (de) * 1975-01-29 1978-08-17 Tenge Hans Werner Anlagen fuer die durchfuehrung elektro- physikalischer verfahren zur beeinflussung von fluessigkeiten in und an feststoffen
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CH656402A5 (de) * 1983-05-06 1986-06-30 Bbc Brown Boveri & Cie Kathodischer stromkollektor.
DD234997A3 (de) * 1983-10-04 1986-04-23 Adw Ddr Elektrodenanordnung zur elektrochemischen entsalzung undtrocknung von mauerwerk
GB2169608B (en) * 1984-12-28 1988-02-24 Hoechst Gosei Kk Process for producting electrically conductive composite polymer article

Also Published As

Publication number Publication date
ATE47529T1 (de) 1989-11-15
ES2011275B3 (es) 1990-01-01
DE3610388C2 (fr) 1987-12-23
DE3610388A1 (de) 1987-10-01
EP0244626A1 (fr) 1987-11-11
DE3760843D1 (en) 1989-11-30
US4806212A (en) 1989-02-21
GR3000319T3 (en) 1991-06-07

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