EP0244626B1 - Electrode and its use - Google Patents

Electrode and its use 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
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Prior art keywords
electrodes
brickwork
electrode
drying
desalting
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German (de)
French (fr)
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EP0244626A1 (en
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Bernard Dr Wessling
Christian Funder
Harald Dr. Volk
Olaf Siemers
Holger Merkle
Manfred Hilleberg
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Wessling Bernhard Dr
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Wessling Bernhard Dr
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    • 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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Abstract

An electrode based on conductive material and macromolecular materials as the binder, which is stable under electrolysis conditions and is particularly suitable for drying masonry, comprising (A) a thermoplastic polar polymer, polycondensate or polyadduct or a mixture thereof, which is wettable by an electrolysis medium and is stable with respect to an electrochemical process taking place on the electrode, and (B) a mixture in a weight ratio of 1:4 to 4:1 of (a) conductive carbon black with a BET-surface of more than 600 m2/g and/or an intrinsically conductive polymer and (b) carbon black with a BET-surface of less than 600 m2/g and/or graphite and/or transition metal oxides and/or an intrinsically conductive polymer.

Description

Die Erfindung betrifft Elektroden auf der Basis von thermoplastischen makromolekularen Werkstoffen und leitfähigen nichtmetallischen Zusätzen sowie deren Verwendung.The invention relates to electrodes based on thermoplastic macromolecular materials and conductive non-metallic additives and the use thereof.

Elektroden werden für verschiedene elektrochemische Zwecke, insbesondere in wässrigen Medien verwendet, z.B. zur elektrochemischen Synthese von Stoffen, zur Elektrolyse, zu Meßzwecken bzw. als Sensoren oder in galvanischen Zellen zur Speicherung elektrischer Energie.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.

Sofern man keine Metalle als Elektrodenmaterial verwendet, werden meist Graphitelektroden eingesetzt. In neuerer Zeit diskutiert man auch die Anwendung von intrinsisch leitfähigen Polymeren in komplexierter (dotierter), reiner Form, z.B. Elektroden aus Polyacetylen, Polypyrrol, Polyanilin, Polyphenylenen, Polyphenylensulfiden, Polyphthalocyaninen, Polythiophenen und auch aus Polymeren mit konjugierten n-Elektronensystemen, die aber bisher nur als Elektroden in wiederaufladbaren Batterien eingesetzt werden konnten (vergl. A.J. Heeger, A.G. McDiarmid u.a., Phys. Rev. Lett. 39, 1089 (1977); P.J. Nigrey u.a., J. Elektrochem. Soc.128, 1651 (1981».If no metals are used as the electrode material, graphite electrodes are mostly used. In recent times, the use of intrinsically conductive polymers in complexed (doped), pure form, e.g. Electrodes made from polyacetylene, polypyrrole, polyaniline, polyphenylenes, polyphenylene sulfides, polyphthalocyanines, polythiophenes and also from polymers with conjugated n-electron systems, which up to now could only be used as electrodes in rechargeable batteries (see AJ Heeger, AG McDiarmid et al., Phys. Rev Lett. 39, 1089 (1977); PJ Nigrey et al., J. Elektrochem. Soc. 128, 1651 (1981 ».

Es sind keine Elektroden bekannt, die mit thermoplastischen Verarbeitungsverfahren (z.B. Extrusion oder Spritzguß) aus Mischungen thermoplastischer makromolekularer Werkstoffe mit leitfähigen nichtmetallischen Zusätzen hergestellt werden können und unter Elektrolysebedingungen stabil sind (vergl. z.B. D. Kyriacon und D. Jannakondakis, "Electrocatalysis for Organic Synthesis", New York 1986). Eine besonders interessante Anwendung für solche Elektroden unter komplexen elektrolytischen Bedingungen stellen elektrische Verfahren zur Entfernung von Kapillarfeuchte in Mauerwerk dar. Die Kapillarfeuchte und Versalzung von Mauerwerk sowie die Korrosion von Stahlbeton stellt ein ernstes volkswirtschaftliches und konservatorisches Problem dar. Die Sanierung von Bauwerken ist hochkompliziert und offenbar - entgegen den Beteuerungen zahlreicher Hersteller und Vertreiber unterschiedlicher mechanischer, chemischer und elektrokinetischer Verfahren - immer noch nicht gelöst (vergl. z.B. C. Ahrendt, "Trockenlegung", Stuttgart, 1983). Gewissen Erfolgen stehen zahlreiche Mißerfolge gegenüber, unabhängig von der Art der Verfahren.No electrodes are known 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). 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. The renovation of structures is highly complicated and evident - contrary to the assertions of numerous manufacturers and distributors of different mechanical, chemical and electrokinetic processes - still not solved (cf., for example, C. Ahrendt, "Trockenlege", Stuttgart, 1983). Certain successes face numerous failures, regardless of the type of procedure.

Die Anwendung von elektrischer Spannung zur Mauertrocknung wird in der allgemeinen und Patentliteratur vielfach beschrieben (vergl. z.B. C. Ahrendt, a.a.0.) und dort meist als elektroosmotisches, elektrokinetisches oder elektrophysikalisches Verfahren bezeichnet.The use of electrical voltage for wall drying is described many times in the general and patent literature (see e.g. C. Ahrendt, op. Cit.) And is usually referred to as an electroosmotic, electrokinetic or electrophysical process.

Offenbar wurden bisher die grundlegenden Probleme der elektrischen Mauertrocknung nicht erkannt:

  • 1. Abgesehen von Modellsystemen können aufgrund des Salzgehaltes im Mauerwerk Trocknungseffekte nur oberhalb der Zersetzungsspannung des Wassers beobachtet werden.
  • 2. Die dabei auftretenden elektrochemischen Prozesse lassen H2 an der Kathode und wohl vorrangig CI2 (nicht, wie oft behauptet wird, 02) an der Anode entstehen, welches sich sofort zu OCI-(Hypochlorit) umsetzt. Die Anode ist daher elektrolytischen, oxidativen und durch Ionentransport offenbar auch mechanischen Abbauvorgängen ausgesetzt.
  • 3. Die Elektroden, vor allem rußgefüllte Kunststoffelektroden, bauen ein Gegenpotential von 0,5 bis 2 mV und darüber auf, das dem angelegten Potential entgegenwirkt und den Stromfluß stark reduziert. Außerdem scheinen die Elektroden aufgrund dieses Potentials in ihrer Leistungsfähigkeit stark nachzulassen.
So far, the fundamental problems of electrical wall drying have apparently not been recognized:
  • 1. Apart from model systems, drying effects can only be observed above the decomposition voltage of the water due to the salinity in the masonry.
  • 2. The electrochemical processes that occur give rise to H 2 on the cathode and probably primarily CI 2 (not, as is often claimed, 0 2 ) on the anode, which immediately converts to OCI (hypochlorite). The anode is therefore exposed to electrolytic, oxidative and apparently also mechanical degradation through ion transport.
  • 3. The electrodes, especially soot-filled plastic electrodes, build up a counter potential of 0.5 to 2 mV and above, which counteracts the applied potential and greatly reduces the current flow. In addition, the potential of the electrodes seems to decrease significantly due to this potential.

Sofern man aus naheliegenden Kostengründen keine Edelmetalle verwenden kann, sind die eingesetzten Metall- oder Kunststoffelektroden diesen Prozessen ausgesetzt. Als Gesamtresultat fällt bei allen diesen Elektroden der Strom rasch ab, die Elektroden zerfallen oder bauen einen sehr hohen Widerstand auf. Die in der Patentliteratur beschriebenen Verfahren lassen diese Probleme unberücksichtigt. Beispielhaft seien hier einige Verfahren und ihre jeweiligen Probleme kurz erwähnt: P. Friese u.a. DE-OS 34 30 449 (elektrolytisch abbauende Metallelektrode); C. Meisel-Crone, DE-AS 14 59 998 (gepreßte Graphitelektrode: sehr instabil); H. Oppitz, EP-OS 100 845 und AT-OS 3101/82 (netzwerkartige, leitfähig beschichtete Kohlefaserelektrode: Netz verliert schnell elektrischen Kontakt zur Elektrode, welche ebenfalls kurzfristig abgebaut wird); M.W. Tenge, DE-OS 27 06 172 sowie 27 06 193, 27 05 814, 27 05 813 und 25 03 670 (rußgefüllte PTFE-Elektrode; mit 9 2 V zu niedrige Arbeitsspannung, schlechter Kontakt zum Mauerwerk, sehr niedrige Leitfähigkeit).If it is not possible to use precious metals for obvious cost reasons, the metal or plastic electrodes used are exposed to these processes. As a result, the current drops rapidly for all these electrodes, the electrodes disintegrate or build up a very high resistance. The methods described in the patent literature ignore these problems. Some methods and their respective problems are briefly mentioned here as examples: P. Friese et al. DE-OS 34 30 449 (electrolytically degrading metal electrode); C. Meisel-Crone, DE-AS 14 59 998 (pressed graphite electrode: very unstable); H. Oppitz, 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).

Nach allem Anschein ist eine Mauertrocknung auf elektrischem Wege aber immer mit Elektrolyse verbunden, die beobachteten Sanierungseffekte werden durch die Elektrolyse in Gang gesetzt.Apparently, wall drying by electrical means is always associated with electrolysis, the observed renovation effects are set in motion by the electrolysis.

Es ist daher Aufgabe der Erfindung, Elektroden für Elektrolyseverfahren bzw. für Anwendungen, bei denen elektrochemische Umwandlungen erwünscht oder unvermeidbar sind, zu schaffen, die unter den jeweiligen Bedingungen stabil sind.It is therefore an object of the invention to provide electrodes for electrolysis processes or for applications in which electrochemical conversions are desired or unavoidable, which are stable under the respective conditions.

Obwohl nach Elektrolyseversuchen mit marktgängigen rußgefüllten Thermoplasten und nach der Literatur keinerlei Hinweise vorlagen, wie die beobachteten Abbauprozesse überwunden werden könnten, wurde nunmehr überraschenderweise gefunden, daß dennoch ganz bestimmte Kombinationen von synthetischen makromolekularen Werkstoffen A und leitfähigen Zusätzen B Elektroden ergeben, die unter den jeweiligen elektrochemischen Bedingungen stabil sind. Gegenstand der Erfindung ist eine unter Elektrolysebedingungen stabile, insbesondere zur Trocknung von Mauerwerk geeignete Elektrode auf Basis von leitfähigen Stoffen und makromolekularen Werkstoffen als Bindemittel, welche dadurch gekennzeichnet ist, daß sie besteht aus

  • A. einem thermoplastischen polaren Polymer, einem thermoplastischen Polykondensat oder einem thermoplastischen Polyaddukt oder deren Gemischen, die durch das Elektrolysemedium gut benetzbar und gegenüber dem an der jeweiligen Elektrode ablaufenden elektrochemischen Vorgang stabil sind, und
  • B. einer Mischung im Gewichtsverhältnis von 1:4 bis 4:1 aus
    • a) Leitruß mit einer Oberfläche von mehr als 600 m2/g und gegebenenfalls Kohlefasern mit
    • b) Ruß mit einer Oberfläche von weniger als 600 m2/g und/oder Übergangsmetalloxiden und/oder einem intrinsisch leitfähigen Polymer besteht.
Although after electrolysis experiments with commercially available soot-filled thermoplastics and according to the literature there were no indications as to how the observed degradation processes could be overcome, it has now surprisingly been found that very specific combinations of synthetic macromolecular materials A and conductive additives B result in electrodes that are among the respective electrochemical ones Conditions are stable. The invention relates to an electrode which is stable under electrolysis conditions and in particular is suitable for drying masonry and is based on conductive substances and macromolecular materials as binders, which are characterized thereby is that it consists of
  • A. a thermoplastic polar polymer, a thermoplastic polycondensate or a thermoplastic polyadduct or mixtures thereof, which are readily wettable by the electrolysis medium and are stable with respect to the electrochemical process taking place at the respective electrode, and
  • B. a mixture in a weight ratio of 1: 4 to 4: 1
    • a) conductive carbon black with a surface area of more than 600 m 2 / g and optionally with carbon fibers
    • b) carbon black with a surface area of less than 600 m2 / g and / or transition metal oxides and / or an intrinsically conductive polymer.

Dabei ist der synthetische makromolekulare Werkstoff A polar und gegenüber dem Elektrolysemedium stabil, d.h. in wässrigen Medien hydrolyse- und vor allem oxidationsstabil. Der Werkstoff ist thermoplastisch verarbeitbar und kann, muß aber nicht vernetzbar sein. Als makromolekulare Elektrodenkomponente A haben sich polare Stoffe, darunter EVA (Ethylenvinylacetat), CPE (Chloriertes Polyethylen), TPU (Thermoplastisches Polyurethan), insbesondere Polyetherpolyurethan, Hart- und Weich-PVC (Polyvinylchlorid), NBR (Nitrilkautschuk), ABS (Acrylnitril-Butadien-Styrol-Terpolymer), SBR (StyrolButadien-Kautschuk), Fluorelastomere oder Mischungen solcher Stoffe bewährt. Sie sollen durch das Elektrolysemedium gut benetzt, aber nicht angequollen oder gelöst bzw. (z.B. hydrolytisch) zersetzt werden können.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.

Die leitfähigen Zusätze B sind nicht-metallisch; sie vermögen einerseits den Werkstoff leitfähig zu modifizieren, andererseits können sie ein Potential während der Anwendung aufbauen (z.B. gegenüber einer Referenzelektrode vor bzw. nach einer gewissen Betriebsdauer), ohne daß dadurch die Betriebsfähigkeit des Systems wesentlich beeinträchtigt wird. Als leitfähige Zusätze B kommen Mischungen aus a) sog. Leitruß (elektrisch leitfähigem Ruß mit einer Oberfläche von mehr als 600 m2/g) und gegebenenfalls Kohlefasern mit b) Ruß geringerer Leitfähigkeit mit einer Oberfläche von weniger als 600 m2/g, Graphit, intrinsisch leitfähigen Polymeren (in komplexierter oder kompensierter Form) oder Übergangsmetalloxiden in Frage. Als intrinsisch leitfähige Polymere sind z.B. Polyacetylen, Polypyrrol, Polyphenylene, Polyaniline, Polythiophene, Polyphthalocyanine und andere Polymere mit konjugierten π-Elektronensystemen zu nennen. Als Metalloxide kommen z.B. Fe(II)/Fe(III)-Mischoxide, Mn02, V20s, Nb203 u.a. in Betracht, also solche, bei denen das Übergangsmetall in einen höheren, ebenfalls stabilen Oxydationszustand überführt werden kann.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 π-electron systems. Examples of 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.

Die leitfähigen Zusätze B werden in Konzentrationen von 3 bis 75 Gew.-%, vorzugsweise 8 bis 55 Gew.-%, mit 25 bis 97, vorzugsweise 45 bis 92 Gew.-% oder Komponente A vermischt.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.

Die Mischung B enthält die leitfähigen und die potentialstabilisierenden Stoffe in Gewichtsverhältnissen von 1:4 bis 4:1.Mixture B contains the conductive and the potential stabilizing substances in weight ratios of 1: 4 to 4: 1.

Als stabil wird eine erfindungsgemäße Elektrode angesehen, wenn

  • a) bei konstanter Gleichspannung ein weitgehend gleichbleibender Strom fließt (dessen Größe natürlich von der Leitfähigkeit der Elektrode und der des Systems abhängig ist), wobei während der notwendigen Betriebsdauer (z.B. in einem Zeitraum von einigen Monaten bis Jahren) die Abnahme der Leistung einen für den jeweiligen Prozeß kritischen Wert nicht unterschreitet;
  • b) die Elektrode (meistens die Anode) mechanisch stabil bleibt (optischer, einfacher Versprödungstest oder Zugprüfung, kein wesentlicher Gewichtsverlust).
An electrode according to the invention is regarded as stable if
  • a) at constant DC voltage, a largely constant current flows (the size of which depends of course on the conductivity of the electrode and that of the system), whereby during the necessary operating time (e.g. in a period of a few months to years) the decrease in power for one the respective process does not fall below the critical value;
  • b) the electrode (usually the anode) remains mechanically stable (optical, simple embrittlement test or tensile test, no significant weight loss).

Der für die Anwendung als Elektroden bevorzugte spezifische Widerstand liegt unter 104 fi cm, vorzugsweise unter 103 0 cm, besonders bevorzugterweise unter 2 . 102 0 cm.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.

Die Herstellung des Elektrodenmaterials erfolgt auf handelsüblichen Kunststoffverarbeitungsmaschinen wie Doppelschneckenextrudern, Innenmischern oder dergleichen unter Verwendung üblicher Verarbeitungshilfsmittel wie Stabilisatoren, Gleitmitteln, Füllstoffen u.a. Die erhaltene Masse wird granuliert oder direkt in die spätere Elektrodenform (Folien, Platten, Profile u.ä.) umgeformt. Die Elektroden finden in vielfältigen Verfahren Anwendung, z.B. als Sensoren, als Elektroden für die elektrolytische Oxidation oder Reduktion, zur Elektrokatalyse, zur Entwässerung - z.B. von Mauerwerk, Schlämmen, Torf und dergl. -zur Entsalzung oder im Korrosionsschutz.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.

Die Prüfung der Elektroden wurde mit 6 V Gleichspannung in wässriger NaCI-Lösung durchgeführt. Dabei zeigte sich, daß der Stromfluß bei Graphitelektroden rasch absinkt, desgleichen bei Kohlefaserelektroden. Metallelektroden werden verbraucht. Rußgefüllte Polymerelektroden aus z.B. vernetztem Polyethylen, die einen Metallkern enthalten, haben offenbar immer Kontaktierungsprobleme und bauen schließlich durch eine Schwachstelle hindurch den Metallkern ab; die Benetzung durch das Elektrolysemedium ist schlecht.The 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.

Die erfindungsgemäßen Elektroden zeigen überraschenderweise ein gänzlich anderes Verhalten: Nach anfänglich konstantem Strom steigt der Stromfluß um bis zu 50% an, fällt dann leicht ab und stabilisiert sich mindestens auf dem Ausgangsniveau, häufig aber zwischen dem Ausgangs- und dem Maximal-Niveau.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.

Eine Erklärung für die beobachteten Phänomene kann noch nicht gegeben werden. Vor allem der Mechanismus der potential- und stromstabilisierenden Funktion ist unklar. Zur Verdeutlichung seien aus den zahlreichen Versuchen, welche z.T. in den Beispielen dokumentiert sind, einige Eckwerte herausgehoben.

Figure imgb0001
An explanation for the observed phenomena cannot yet be given. Above all, the mechanism of the potential and current stabilizing function is unclear. For clarification, a few key values should be highlighted from the numerous tests, some of which are documented in the examples.
Figure imgb0001

Der Anfangsstrom wird im wesentlichen durch den Widerstand der Elektroden bestimmt und ist deshalb bei der Kohlefaser höher. Bei vergleichbarem Endwiderstand (möglicherweise ist bei der erfindungsgemäßen Elektrode nur die äußerste Oberfläche verändert, was durch Kontaktierungsprobleme einen höheren Widerstand vortäuscht, während der innere Widerstand auf ursprünglichem Niveau bleibt) und Endpotential zeigt aber die erfindungsgemäße Elektrode einen mehr als 10-fach höheren Strom, der sogar höher ist als der Ausgangswert. Die nur mit Leitruß gefüllte Elektrode kann ebenfalls den Strom nicht stabilisieren.The initial current is essentially determined by the resistance of the electrodes and is therefore higher for the carbon fiber. With a comparable end resistance (possibly only the outermost surface of the electrode according to the invention is changed, which simulates a higher resistance due to contacting problems, while the internal resistance remains at the original level) and the end potential, the electrode according to the invention shows a current which is more than 10 times higher is even higher than the baseline. The electrode, which is only filled with conductive carbon black, cannot stabilize the current either.

In der Praxis setzt man die Elektroden in flächiger Form, z.B. in Form von Folien oder Platten ein. Für die Trocknung von Mauern haben sich Folien, die ausgestanzt wurden (zur Erleichterung des Anputzens) bewährt. Die Folien werden durch Leiter mit großem Querschnitt z.B. durch Verschweißen kontaktiert; diese Leiter können innerhalb des Mauerwerks verlaufen, ebenso kann die Kontaktstelle im Mauerwerk (z.B. Putz) liegen; der Kontakt zwischen Spannungsgeber und Leiter muß außerhalb des Mauerwerks mit Schutz vor Feuchtigkeitszutritt erfolgen.In practice, 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.

Zum Betrieb der Elektroden können Gleich- und Wechselspannungen in erforderlicher Größe eingesetzt werden. Zur Mauertrocknung wendet man bevorzugterweise zwichen 4 und 48V an, wobei zur Begrenzung des Stromflusses bei Spannungen von mehr als 6 V gepulste Gleichspannung eingesetzt werden kann.Direct and alternating voltages of the required size can be used to operate the electrodes. For wall drying, 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.

Zur weiteren Erläuterung der Erfindung sollen nachfolgende Beispiele dienen, auf welche die Erfindung aber nicht beschränkt ist. Alle Mengenangaben beziehen sich auf das Gewicht.The following examples serve to explain the invention further, but the invention is not restricted to these. All quantities refer to the weight.

Beispiel 1example 1

In einem Innenmischer werden 80 Teile Ethylen-Vinylacetat (20% VA) mit 9 Teilen Leitruß mit einer Oberfläche von 950 m2/g (Ketjenblack EC) und 11 Teilen Flammruß (Flammruß 101 der Degussa AG) mit einer Oberfläche von 20 m2/g und 3 Teilen Stabilisatoren und Gleitmitteln gemischt, plastifiziert und granuliert (Rezept Nr. 1). Analog wird verfahren mit TPU (Polyethertyp) (Rezept Nr. 2) und Weich-PVC (Nr. 3). Weiterhin wird die Mischung 1 in gleicher Zusammensetzung, aber anstelle des Furnaceruß mit Graphit (Nr. 4), sowie zum Vergleich ohne Furnaceruß (Nr. 5) ausgeführt. Die Granulate werden zu Platten von 2 mm Dicke gepreßt und zu Elektroden von 12,5 mm Länge und 20 mm Breite geschnitten.80 parts of ethylene-vinyl acetate (20% VA) with 9 parts of conductive carbon black with a surface area of 950 m 2 / g (Ketjenblack EC) and 11 parts of carbon black (flame black 101 from Degussa AG) with a surface area of 20 m 2 / g and 3 parts of stabilizers and lubricants mixed, plasticized and granulated (Recipe No. 1). The same procedure is followed with TPU (polyether type) (recipe No. 2) and soft PVC (No. 3). Mixture 1 is also carried out in the same composition, but instead of furnace black with graphite (No. 4), and for comparison without furnace black (No. 5). The granules are pressed into sheets 2 mm thick and cut into electrodes 12.5 mm long and 20 mm wide.

Eine weitere Anode bestand aus PVC und 40% Polyanilinhydrochlorid (Nr. 6), die Kathode aus PVC, 40% Polyanilin und 8% Leitruß. Als weitere Vergleichselektrode wird ein Kohlefaserfand (Nr. 7) eingesetzt. Die Elektroden werden in einem Elektrolysegefäß in räumlich getrennten, aber elektrolytisch verbundenen Zylindern angebracht, wobei die wässrige Lösung (2g NaCI/100g H20) die Elektroden nur halb bedeckt, so daß die Kontaktierung der Elektroden mit eingeschweißten Metalldrähten außerhalb des Elektrolyse-Mediums erfolgen kann. Die Zylinder haben ein oben angebrachtes Ventil, so daß entstehende Gase während der Elektrolyse periodisch abgelassen werden können.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.

Bei Betrieb mit 6 V Gleichspannung wurden die in der nachfolgenden Tabelle enthaltenen Ergebnisse erhalten. Die nicht erfindungsgemäßen Elektroden sind deutlich unterlegen.

Figure imgb0002
When operating with 6 V DC, the results shown in the table below were obtained. The electrodes not according to the invention are clearly inferior.
Figure imgb0002

Beispiel 2Example 2

In einem Vergleichsversuch wurden zwei handelsübliche Elektrodenmaterialien (1: rußgefülltes PE, 2: Kohlefaserband) und eine erfindungsgemäße Elektrodenmasse (Zusammensetzung des Beispiels 1, Nr. 3, welche jedoch als Komponente Bb statt Flammruß ein Fe(II)/Fe(III)-Mischoxid (Eisenoxid-Pigment 130 M der Bayer AG) enthielt, als Anoden in wässriger Elektrolyse (6 V) (2% NaCI-Lösung geschaltet. Dabei sind die Vergleichsmaterialien 1 und 2 elektrisch nach 100 bzw. 60 h, mechanisch (Reißfestigkeit) jeweils nach etwa 60 h zerstört (Fig. 1 und 2). Die erfindungsgemäße Elektrodenmasse arbeitet jedoch auch nach 800 h noch mit nennenswerter Leistung und ist mechanisch noch nicht zerstört (Fig. 3 und 4). Die Gewichtsänderung beträgt für

  • - Nr. 1 Anode - 11 %/Kathode -8% (Zerstörung durch Oxidation bzw. Reduktion, Materialabtrag)
  • - Nr. 2 Anode +9%/Kathode +14% (Zerstörung durch loneneinlagerung)
  • - Nr. 3 Anode +1%/Kathode +4% (wesentlich geringere Gewichtsveränderungen bei 8-facher Elektrolysezeit und -leistung)
In a comparative experiment, two commercially available electrode materials (1: soot-filled PE, 2: carbon fiber tape) and an electrode composition according to the invention (composition of Example 1, No. 3, which, however, as component Bb instead of flame black, an Fe (II) / Fe (III) mixed oxide (Iron oxide pigment 130 M from Bayer AG) contained, as anode in aqueous electrolysis (6 V) (2% NaCl solution). The comparison materials 1 and 2 are electrical after 100 and 60 hours, respectively, mechanically (tear resistance) destroyed about 60 h (Fig. 1 and 2.) However, the electrode mass according to the invention still works with significant power even after 800 h and has not yet been mechanically destroyed (Fig. 3 and 4)
  • - No. 1 anode - 11% / cathode -8% (destruction by oxidation or reduction, material removal)
  • - No. 2 anode + 9% / cathode + 14% (destruction by ion storage)
  • - No. 3 anode + 1% / cathode + 4% (significantly smaller weight changes with 8 times the electrolysis time and performance)

Beispiel 3Example 3

In einem Langzeittest wurden drei erfindungsgemäß zusammengesetzte Elektrodenmassen als Anode und Kathode in einer wässrigen Elektrolyse gemäß Beispiel 2 eingesetzt. Alle Elektroden enthielten Leitruß (Ketjenblack EC) als Komponente Ba in Weich-PVC. Nr. 1 und Nr. 2 enthielten als Komponente Bb Graphit, Nr. 3 das Mischoxid des Beispiels 2. Der Stromverlauf ist in Fig. 5 dargestellt (nicht auf Elektrodenfläche normiert).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).

Claims (10)

1. Electrode which is stable under electrolysis conditions and suitable in particular for drying brickwork, based on conductive substances and macromolecular materials as the binder, characterized in that it consists of
A. a thermoplastic polar polymer, a thermoplastic polycondensate or a thermoplastic addition polymer or mixtures of these, which are easily wettable by electrolysis medium and are stable with regard to the electrochemical process proceeding at the respective electrode, and
B. a mixture in a weight ratio of 1:4 to 4:1 of
a) conductive carbon black with a surface of more than 600 m2/g, and optionally carbon fibres, with
b) carbon black with a surface of less than 600 m2/g and/or graphite and/or transition-metal oxides and/or an intrinsically conductive polymer.
2. Electrode according to claim 1, characterized in that it contains polyvinyl chloride and/or chlorinated polyethylene as component A.
3. Electrode according to claim 1 or 2, characterized in that the components A and B are present in a weight ratio between 97:3 and 25:75.
4. Use of the electrode according to claims 1 to 3 in electrolysis processes, in particular for desalting and drying brickwork, for removing capillary moisture from peats or slurries, for protection from corrosion, for soil irrigation, in electrosynthesis or electrocatalysis and as sensors.
5. Use according to claim 4 for desalting and drying brickwork, characterized in that an electrode according to claim 1 to 3 is used as the anode, and that voltages of 4 to 48 V are applied.
6. Use according to claim 4 or 5, characterized in that the electrodes have a specific resistance of less than 104 Q cm.
7. Use according to one of claims 4 to 6, characterized in that the electrodes are contacted with the brickwork in large-area form, and the electrodes in the form of films or webs are provided with punched - out regions to facilitate application.
8. Use of the electrodes for the desalting and drying of brickwork according to claims 4 to 7, characterized in that the voltage is applied to the electrodes by a voltage source, which is arranged outside the wall, via conductors with a large cross-section and of the same material as the electrodes used.
9. Use of the electrodes for desalting and drying brickwork according to claims 4 to 9, characterized in that a pulsed d.c. voltage is applied.
10. Use of the electrodes for desalting and drying brickwork according to claims 4 to 9, characterized in that the electrodes are applied to the brickwork to be dried or desalted with a plaster which is particularly rich in calcium hydroxide and/or calcium carbonate.
EP87104615A 1986-03-27 1987-03-27 Electrode and its use Expired EP0244626B1 (en)

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