EP0244626A1 - Electrode and its use - Google Patents

Electrode and its use Download PDF

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Publication number
EP0244626A1
EP0244626A1 EP87104615A EP87104615A EP0244626A1 EP 0244626 A1 EP0244626 A1 EP 0244626A1 EP 87104615 A EP87104615 A EP 87104615A EP 87104615 A EP87104615 A EP 87104615A EP 0244626 A1 EP0244626 A1 EP 0244626A1
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Prior art keywords
electrodes
electrode
drying
masonry
desalination
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EP87104615A
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German (de)
French (fr)
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EP0244626B1 (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 There are no electrodes 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).
  • 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 is electrical processes for removing capillary moisture in masonry. The capillary moisture and salinization of masonry as well as the corrosion of reinforced concrete is 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 ⁇ 2 V too low working voltage, poor contact with the masonry, very low conductivity).
  • the synthetic macromolecular material A is polar and stable with respect to the electrolysis medium, ie hydrolysis and especially oxidation stable in aqueous media.
  • the material can be processed thermoplastically and can, but need not, be crosslinkable.
  • macromolecular electrode component A polar substances, in particular 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 proven successful. They should be able to be wetted well by the electrolysis medium, but not be swollen, dissolved or (eg hydrolytically) decomposed.
  • the conductive additives B are non-metallic; on the one hand, they can modify the material in a conductive manner, on the other hand, they can build up a potential during use (e.g. measured against a reference electrode before or after a certain period of operation) without significantly affecting the system's operability.
  • Mixtures of a) so-called conductive carbon black (electrically conductive carbon black with a surface area of more than 600 m 2 / g) and / or carbon fibers and / or intrinsically conductive polymers with b) carbon black of lower conductivity with a surface area of less than 600 m 2 come as conductive additives B. / g, graphite, intrinsically conductive polymers (in complexed or compensated form) or transition metal oxides.
  • intrinsically conductive polymers e.g. To name polyacetylene, polypyrrole, polyphenylenes, polyanilines, polythiophenes, polyphthalocyanines and other polymers with conjugated ⁇ -electron systems. These conductive polymers can also form component B alone.
  • metal oxides e.g. Fe (II) / Fe (III) mixed oxides, MnO2, V2O3, Nb2O3 and others into consideration, 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 of component A. If B is a mixture of conductive and potential stabilizing substances, they are used in weight ratios of 1: 4 to 4: 1.
  • the specific resistance preferred for use as electrodes is below 104 ⁇ cm, preferably below 103 ⁇ cm, particularly preferably below 2. 102 ⁇ 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 directly transformed 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 dewatering - 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 display 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.
  • 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 contact problems, while the internal resistance remains at the original level
  • 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 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 separate but electrolytically connected cylinders, the aqueous solution (2g NaCl / 100g H2O) only half covering the electrodes, so that the electrodes can be contacted with welded metal wires outside the electrolysis medium.
  • 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

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 π-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. The use of intrinsically conductive polymers in complex (doped), pure form, e.g. electrodes made of polyacetylene, polypyrrole, polyaniline, polyphenylenes, polyphenylene sulfides, polyphthalocyanines, polythiophenes and also of polymers with conjugated π-electron systems, has also been discussed recently, but so far 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 nicht-metallischen 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.There are no electrodes 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 is electrical processes for removing capillary moisture in masonry. The capillary moisture and salinization of masonry as well as the corrosion of reinforced concrete is a serious economic and conservation problem. The renovation of buildings is highly complicated and apparently - contrary to the assurances of numerous manufacturers and distributors of different mechanical, chemical and electrokinetic processes - still not resolved (see, for example, C. Ahrendt, "dryout", 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.O.) 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, loc. Cit.) And is usually referred to there 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 Cl₂ (nicht, wie oft behauptet wird, O₂) an der Anode entstehen, welches sich sofort zu OCl⁻ (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 resulting electrochemical processes leave H₂ on the cathode and probably primarily Cl₂ (not, as is often claimed, O₂) on the anode, which immediately converts to OCl⁻ (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 ≦ 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 ≦ 2 V too low working voltage, 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 are.

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, Poly­kondensat oder 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 Verhältnis von 1:4 bis 4:1 aus
    • a) Leitruß mit einer Oberfläche von mehr als 600 m²/g und/oder Kohlefasern und/oder einem intrinsisch leitfähigen Polymer und
    • b) Ruß mit einer Oberfläche von weniger als 600 m²/g und/oder Graphit und/oder Übergangsmetalloxiden und/oder einem intrinsisch leitfähigen Polymer.
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 is particularly suitable for drying masonry and is based on conductive substances and macromolecular materials as a binder, which is characterized in that it consists of
  • A. a thermoplastic polar polymer, polycondensate or 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. from a mixture in a ratio of 1: 4 to 4: 1
    • a) conductive carbon black with a surface area of more than 600 m² / g and / or carbon fibers and / or an intrinsically conductive polymer and
    • b) carbon black with a surface area of less than 600 m² / g and / or graphite 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 (Styrol-Butadien-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, ie hydrolysis and especially oxidation stable in aqueous media. The material can be processed thermoplastically and can, but need not, be crosslinkable. As macromolecular electrode component A, polar substances, in particular 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 proven successful. They should be able to be wetted well by the electrolysis medium, but not be swollen, dissolved or (eg 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. gemessen 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/oder Kohlefasern und/oder intrinsisch leitfähigen Polymeren mit b) Ruß geringerer Leitfähigkeit mit einer Oberfläche von weniger als 600m²/g, Graphit, intrinsisch leitfähigen Polymeren (in komplexierter oder kompensierter Form) oder Übergangsmetalloxiden infrage. Als intrinsisch leitfähige Polymere sind z.B. Polyacetylen, Polypyrrol, Polyphenylene, Polyaniline, Polythiophene, Polyphthalocyanine und andere Polymere mit konjugierten π-Elektronensystemen zu nennen. Diese leitfähigen Polymeren können auch allein die Kompo­nente B bilden. Als Metalloxide kommen z.B. Fe(II)/Fe(III)-­Mischoxide, MnO₂, V₂O₃, Nb₂O₃ u.a. in Betracht, also solche, bei denen das Übergangsmetall in einem höheren, ebenfalls stabilen Oxydationszustand überführt werden kann.The conductive additives B are non-metallic; on the one hand, they can modify the material in a conductive manner, on the other hand, they can build up a potential during use (e.g. measured against a reference electrode before or after a certain period of operation) without significantly affecting the system's operability. Mixtures of a) so-called conductive carbon black (electrically conductive carbon black with a surface area of more than 600 m 2 / g) and / or carbon fibers and / or intrinsically conductive polymers with b) carbon black of lower conductivity with a surface area of less than 600 m 2 come as conductive additives B. / g, graphite, intrinsically conductive polymers (in complexed or compensated form) or transition metal oxides. As intrinsically conductive polymers e.g. To name polyacetylene, polypyrrole, polyphenylenes, polyanilines, polythiophenes, polyphthalocyanines and other polymers with conjugated π-electron systems. These conductive polymers can also form component B alone. As metal oxides e.g. Fe (II) / Fe (III) mixed oxides, MnO₂, V₂O₃, Nb₂O₃ and others into consideration, 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.% der Komponente A vermischt. Falls B eine Mischung aus leitfähigen und potentialstabili­sierenden Stoffen ist, werden diese in Gewichtsverhält­nissen von 1:4 bis 4:1 eingesetzt.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 of component A. If B is a mixture of conductive and potential stabilizing substances, they are used 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 Ωcm, vorzugsweise unter 10³ Ωcm, besonders bevorzugterweise unter 2 . 10² Ωcm.The specific resistance preferred for use as electrodes is below 10⁴ Ωcm, preferably below 10³ Ωcm, particularly preferably below 2. 10² Ωcm.

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 Korrosionschutz.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 directly transformed 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 dewatering - 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 NaCl-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 display 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 contact problems, while the internal resistance remains at the original level) and end potential, however, 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 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.In an internal mixer, 80 parts of ethylene vinyl acetate (20% VA) with 9 parts of conductive carbon black with a surface area of 950 m² / g (Ketjenblack EC) and 11 parts of carbon black (flame black 101 from Degussa AG) with a surface area of 20 m² / 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 NaCl/100g H₂O) 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 separate but electrolytically connected cylinders, the aqueous solution (2g NaCl / 100g H₂O) only half covering the electrodes, so that the electrodes can be contacted with welded metal wires outside the electrolysis medium. 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 erfindunggsgemäße 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% NaCl-Lösung geschaltet. Dabei sind die Vergleichsmaterialien 1 und 2 elektrisch nach 100 bzw. 60 h, mechanisch (Reißfestigkeit) jeweils nach eta 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).In a comparative experiment, two commercially available electrode materials (1: carbon black-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). Comparative materials 1 and 2 are electrical after 100 and 60 hours, respectively, mechanically (tear resistance) destroyed about 60 hours (FIGS. 1 and 2), however, the electrode mass according to the invention still works with significant power even after 800 hours and has not yet been mechanically destroyed (FIGS. 3 and 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 Ionen­einlagerung)
  • - Nr. 3 Anode +1%/Kathode +4% (wesentlich geringere Gewichtsveränderungen bei 8-facher Elektrolysezeit und -leistung)
The weight change is for
  • - 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 (12)

1. Unter Elektrolysebedingungen stabile, insbesondere zur Trocknung von Mauerwerk geeignete Elektrode auf Basis von leitfähigen Stoffen und makromolekularen Werkstoffen als Bindemittel, dadurch gekennzeichnet, daß sie aus A. einem thermoplastischen polaren Polymer, Poly­kondensat oder Polyaddukt oder deren Gemischen besteht, 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/oder Kohlefasern und/oder einem intrinsisch leitfähigen Polymer und b) Ruß mit einer Oberfläche von weniger als 600 m²/g und/oder Graphit und/oder Übergangsmetalloxiden und/oder einem intrinsisch leitfähigen Polymer 1. Under electrolysis conditions stable, in particular suitable for drying masonry electrode based on conductive substances and macromolecular materials as binders, characterized in that they are made of A. a thermoplastic polar polymer, polycondensate or 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 m² / g and / or carbon fibers and / or an intrinsically conductive polymer and b) carbon black with a surface area of less than 600 m² / g and / or graphite and / or transition metal oxides and / or an intrinsically conductive polymer besteht.consists. 2. Elektrode, vorzugsweise Anode, nach Anspruch 1, dadurch gekennzeichnet, daß sie als Komponente B nur intrinsisch leitfähige Polymere enthält.2. Electrode, preferably anode, according to claim 1, characterized in that it contains only intrinsically conductive polymers as component B. 3. Elektrode nach Anspruch 1, dadurch gekennzeichnet, daß sie als Komponente A Polyvinylchlorid und/oder chloriertes Polyethylen enthält.3. Electrode according to claim 1, characterized in that it contains as component A polyvinyl chloride and / or chlorinated polyethylene. 4. Elektrode nach den Ansprüchen 1 bis 3, dadurch gekenn­zeichnet, daß die Komponenten A und B in einem Gewichtsverhält­nis zwischen 97:3 und 25:75 vorliegen.4. Electrode according to claims 1 to 3, characterized in that components A and B are present in a weight ratio between 97: 3 and 25:75. 5. Verwendung der Elektrode nach den Ansprüchen 1 bis 4 in Elektrolyseverfahren, insbesondere zur Entsalzung und Trock­nung von Mauerwerk, zur Entfernung von Kapillarfeuchte aus Torfen oder Schlämmen, zum Korrosionsschutz, zur Bodenbe­wässerung, in der Elektrosynthese oder -katalyse und als Sensoren.5. Use of the electrode according to claims 1 to 4 in electrolysis processes, in particular for desalination and drying of masonry, for removing capillary moisture from peat or sludge, for corrosion protection, for soil irrigation, in electrosynthesis or catalysis and as sensors. 6. Verwendung nach Anspruch 5 zur Mauerentsalzung und -trocknung, dadurch gekennzeichnet, daß als Anode eine Elektrode nach den Ansprüchen 1 bis 4 eingesetzt wird und Spannungen von 4 bis 48 V angelegt werden.6. Use according to claim 5 for wall desalination and drying, characterized in that an electrode according to claims 1 to 4 is used as anode and voltages of 4 to 48 V are applied. 7. Verwendung nach einem der Ansprüche 5 oder 6, dadurch gekennzeichnet, daß die Elektroden einen spezifischen Widerstand von weniger als 10⁴ Ω cm aufweisen.7. Use according to one of claims 5 or 6, characterized in that the electrodes have a specific resistance of less than 10⁴ Ω cm. 8. Verwendung nach einem der Ansprüche 5 bis 7, dadurch gekennzeichnet, daß die Elektroden in großflächiger Form mit dem Mauerwerk kontaktiert werden, wobei die in Form von Folien oder Bahnen vorliegenden Elektroden zur Erleichterung der Anbringung mit Ausstanzungen versehen werden.8. Use according to one of claims 5 to 7, characterized in that the electrodes are contacted in a large area with the masonry, wherein the electrodes in the form of foils or sheets are provided with punched-outs to facilitate attachment. 9. Verwendung der Elektroden zur Mauerentsalzung und -trocknung nach den Ansprüchen 5 bis 8, dadurch gekenn­zeichnet, daß die Spannung von einem Spannungsgeber, der außerhalb der Mauer angeordnet ist, über Leiter mit großem Querschnitt aus dem gleichen Material wie die verwendeten Elektroden an die Elektroden angelegt wird.9. Use of the electrodes for wall desalination and drying according to claims 5 to 8, characterized in that the voltage from a voltage generator, which is arranged outside the wall, via conductors with a large cross-section made of the same material as the electrodes used to the electrodes is created. 10. Verwendung der Elektroden zur Mauerentsalzung und -trocknung nach den Ansprüchen 5 bis 9, dadurch gekenn­zeichnet, daß eine gepulste Gleichspannung angelegt wird.10. Use of the electrodes for wall desalination and drying according to claims 5 to 9, characterized in that a pulsed DC voltage is applied. 11. Verwendung der Elektroden zur Mauerentsalzung und -trock­nung nach den Ansprüchen 5 bis 10, dadurch gekennzeichnet, daß die Elektroden mit einem Putz, der besonders reich an Calciumhydroxid und/oder -carbonat ist, an das zu trocknende bzw. zu entsalzende Mauerwerk angebracht werden.11. Use of the electrodes for wall desalination and drying according to claims 5 to 10, characterized in that the electrodes with a plaster, which is particularly rich in calcium hydroxide and / or carbonate, are attached to the masonry to be dried or desalinated .
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EP0333700A1 (en) * 1988-03-15 1989-09-20 Steininger, Karl-Heinz, Dipl.-Ing.Dr.techn. Electrode
EP0421881A1 (en) * 1989-10-05 1991-04-10 Electricite De France Conductive material for electrode, electrical component and their process for manufacturing
FR2652943A1 (en) * 1989-10-05 1991-04-12 Electricite De France CONDUCTIVE MATERIAL FOR ELECTRODE, ELECTRICAL COMPONENT AND METHOD FOR MANUFACTURING SAME.
WO1998020331A1 (en) * 1996-11-07 1998-05-14 Cambridge Sensors Limited Electrodes and their use in assays
US6309535B1 (en) 1996-11-07 2001-10-30 Cambridge Sensors Limited Electrodes and their use in assays
EP2184316A1 (en) 2008-11-06 2010-05-12 Clariant International Ltd. Composition comprising propylene-olefin-copolymer waxes and carbon black
US8741183B2 (en) 2008-11-06 2014-06-03 Clariant Finance (Bvi) Limited Compositions comprising propylene-olefin-copolymer waxes and carbon black

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DE3760843D1 (en) 1989-11-30
DE3610388A1 (en) 1987-10-01
ATE47529T1 (en) 1989-11-15
EP0244626B1 (en) 1989-10-25
US4806212A (en) 1989-02-21
GR3000319T3 (en) 1991-06-07
ES2011275B3 (en) 1990-01-01

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