EP0224851A1 - Electrode pour procédés électrochimiques - Google Patents

Electrode pour procédés électrochimiques Download PDF

Info

Publication number
EP0224851A1
EP0224851A1 EP86116354A EP86116354A EP0224851A1 EP 0224851 A1 EP0224851 A1 EP 0224851A1 EP 86116354 A EP86116354 A EP 86116354A EP 86116354 A EP86116354 A EP 86116354A EP 0224851 A1 EP0224851 A1 EP 0224851A1
Authority
EP
European Patent Office
Prior art keywords
valve metal
current conductor
electrically
conductor
electrode according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP86116354A
Other languages
German (de)
English (en)
Other versions
EP0224851B1 (fr
Inventor
Reinhard Koch
Heinrich Simon
Albrecht Körbitz
Helmut Krebs
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
De Nora Deutschland GmbH
Original Assignee
Heraeus Elektroden GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Heraeus Elektroden GmbH filed Critical Heraeus Elektroden GmbH
Priority to AT86116354T priority Critical patent/ATE47432T1/de
Publication of EP0224851A1 publication Critical patent/EP0224851A1/fr
Application granted granted Critical
Publication of EP0224851B1 publication Critical patent/EP0224851B1/fr
Expired legal-status Critical Current

Links

Images

Classifications

    • 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
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • 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
    • C23F13/06—Constructional parts, or assemblies of cathodic-protection apparatus
    • C23F13/08—Electrodes specially adapted for inhibiting corrosion by cathodic protection; Manufacture thereof; Conducting electric current thereto
    • C23F13/20—Conducting electric current to electrodes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/10—Electrodes, e.g. composition, counter electrode
    • C25D17/12—Shape or form

Definitions

  • the invention relates to a tubular electrode for electrolytic processes, in particular anode for galvanic processes or cathodic corrosion protection, with a current conductor made of an electrically highly conductive material, which is encased by a tubular valve metal body, which is electrically conductively connected to the current conductor and whose conductor is turned away from the current conductor Surface is provided with a pad made of electrocatalytic material.
  • valve metals In electrolytic processes which require a noble metal from the platinum group as electrochemically active electrode material, it is known to apply this to a carrier made of valve metal for economical use; Such valve metals have an extensive blocking effect in the case of anodic switching, according to which the current transfer in the electrolytes takes place only at the points at which the noble metal coating rests on the carrier. Because valve metals are proportionate have high electrical resistance, it has been proposed several times to remove the function of the current supply of the electrode as much as possible from the material of the carrier and to guide the current supply to the carrier as close as possible to the outlet point in the electrolyte via material with high electrical conductivity.
  • DE-PS 913 768 describes electrodes made from combinations of tantalum as valve metal with metals of high electrical conductivity, in which the tantalum forms only a relatively thin surface layer.
  • Such combinations consist of a base body coated with a closed, thin layer of tantalum or tantalum alloy made of electrically highly conductive metal, such as. B. silver, copper or aluminum.
  • the tantalum layer is coated with a thin layer of platinum or wrapped with a thin platinum wire, possibly in the form of a spiral.
  • AT-PS 212 284 describes the use of titanium as valve metal, which has an electrical resistance value that is about four times higher than that of tantalum.
  • a carrier body made of a core of copper, silver or aluminum should be used, which is covered with a titanium layer or a stronger titanium jacket. The sheathing shields the conductive core against the action of the electrolyte and at the same time achieves the current path through the poorly conductive titanium in the electrolyte over the shortest distance perpendicular to the direction of supply.
  • the electrocatalytically active electrode material made of platinum or a platinum metal is located on the carrier in the form of a closed or interrupted coating or in the form of a spiral of tape or wire.
  • an electrode for di ' chlorine electrolysis is also known, in which on a copper core an envelope made of a valve metal is applied. Valve metal body and core are interconnected by a fusion connection, plating process or spraying process, electrically conductive and mechanically fixed. In addition to an optimal power supply line, the usually existing blocking effect of the valve metal is to be eliminated.
  • valve metals used as carrier material for electrodes with their relatively poor electrical conductivity by current conductors as the core material, the current conductors being shielded from the action of the electrolyte by the valve metal body surrounding them.
  • the valve metals because of their relatively high price, always form only a relatively thin sheathing for a solid core conductor, the dimensions of the solid core conductor being predetermined by the required electrode dimensions. In the case of large-format electrodes in particular, this leads to an oversized conductor cross section for the actual power line and to a relatively high weight due to the solidity of the core conductor.
  • the invention has for its object to build an electrode of high stability in lightweight construction with a current conductor sufficiently dimensioned for practical needs, which is used to supply power to a valve metal body designed as an envelope, the dimensions of which are completely independent of the format of the current conductor. Furthermore, electrodes should be easily assembled as individual elements to form larger electrode units.
  • the object is achieved in that the electrically conductive connection between the current conductor and valve metal body via at least two spaced-apart composite body takes place, each composite body having a region made of valve metal and a region made of electrically highly conductive material and that the valve metal region with the valve metal body and the electrically highly conductive region with the current conductor are electrically conductive and mechanically firmly connected.
  • the composite body is connected to the valve metal body by a welded connection, while it forms a soldered, screwed or pressed connection with the region of the current conductor which it surrounds in a ring.
  • the area of the composite body consisting of the valve metal encloses the ring-shaped area made of the material of good electrical conductivity in the form of a hollow cylinder.
  • valve metal body to the current conductor provided with composite bodies. Due to the lightweight construction, high stability is achieved even when assembled into larger electrode units made up of several electrode elements.
  • Figure la shows an electrode according to the invention in longitudinal section
  • Figure lb the same electrode in a perspective elevation
  • Figure 2 shows an electrode with a double electrical connection.
  • the current conductor 1 which is made of a material with good electrical conductivity, is located in a cylindrically symmetrical valve metal body 2 which is sealed off from the outside and which is arranged coaxially with the current conductor 1.
  • the axis of the conductor is designated 3.
  • the electrical connection between the current conductor 1 and the valve metal body 2 is produced by composite bodies 4, which are arranged at intervals on the current conductor 1 and form a welded joint 7 with the valve metal body.
  • the distances between the composite bodies are chosen so that the Joule heat losses in the valve metal body 2 do not exceed a predetermined value under normal current load; it is therefore a compromise between the smallest possible number of composite bodies and the greatest possible energy yield of the electrode.
  • the composite bodies 4 have an annular structure, the inner region 6 of the rings being made of a material with good electrical conductivity and surrounded by a region 5 of valve metal in the form of a jacket.
  • the area 5 consisting of valve metal is applied to the electrically highly conductive area by extrusion, shrinking, plating or thermal methods; extrusion is preferably used. Electrodes in the form of rods, which are common in practice, are supplied with a current which is in the range from 5 to 100 A / dm 'active anode surface. With an inner diameter of the valve metal body 2 of, for example, 23 mm, an annular width of the composite body 4 of 15 mm results for design reasons.
  • the current conductor 1 is cylindrical and has a diameter of 12 mm, its length being less than the total length of the valve metal body 2. Copper or a copper alloy is used as the material for the current conductor 1, while the material of the valve metal body 2 of the valve metal Region 5 of the composite body 4 consists of titanium; the inner region 6 of the composite body 4 which is in contact with the current conductor 1 can be made of copper or a copper alloy, for example, but it is also possible to use other materials with good specific electrical conductivity.
  • the current conductor 1 is shorter than the valve metal body 2, since the cup-shaped end 10 of the valve metal body 2 is supplied with current by a composite body 4, which is located at a predetermined distance from the end. At its other end, the current conductor 1 is mechanically and electrically conductively connected to the last composite body and a socket 12.
  • the socket 12 has the same basic structure as the other composite body 4, so that the outer surface 13 also consists of the material of the valve metal body.
  • the bushing 12 protruding from the upper end of the valve metal body 2 is welded to the upper edge of the valve metal body 2 in the region of its outer surface 13.
  • the protruding end of the socket 12 is accommodated in a recess 14 in a connecting part 15 and welded to the latter in the edge region of the recess.
  • the distances between the composite bodies are 200 to 1000 mm, the distance between the cup-shaped end 10 and the next composite body 4 being reduced accordingly.
  • a partial electrode can be provided with a connecting element 19, which in turn is screwed in the direction of the axis 3 of the current conductor 1 to a threaded hole for receiving the other partial electrode, which is formed with a threaded bolt in the connecting element 18.
  • the two connecting elements 18, 19 connected to each other on their adjacent surfaces by a circumferential weld seam, in order to shield the connection zone against entry of the electrolyte.
  • an electrode with a double connection from two straight partial electrodes and a U-shaped middle piece, as is explained in more detail with reference to FIG.
  • FIG. 1b shows the electrode according to the invention in a perspective view, the valve metal body being only partially shown for better understanding.
  • the current conductor 1 is provided with four composite bodies 4 which are arranged at regular intervals from one another.
  • Each composite body 4 supplies one jacket area of the valve metal body 2, the length of which corresponds to the respective spacing of the composite body 4.
  • the length of the section to be supplied is correspondingly half as long as the distance between the composite bodies.
  • the soldered socket 12 can be seen, the outer lateral surface 13 of which is welded all around to the upper edge of the valve metal body 2.
  • the Venitlmetallisation 2 is provided at the points provided for the welding between the composite body 4 and the valve metal body 2 each with at least one opening 16 in order to enable an exact positioning of the composite body 4 within the valve metal body 2. After the respective welding process there are hermetically sealed welded connections 7 between the composite bodies 4 and the valve body 2 in the area of these openings, so that the current conductor 1 is shielded against any attack by the electrolyte.
  • the valve metal body 2 serves as a carrier of any more detail here shown elektrokata-Ivtician ll electrode material such as platinum or a metal of the platinum group.
  • FIG. 2 shows a U-shaped electrode with two current connections 20, which results in an increased load capacity.
  • the two partial electrodes each have the same basic structure in the area of their two upper composite bodies 4 as the electrode described in FIGS. 1 a, 1 b.
  • the composite body 4 'arranged in the middle, U-shaped area is connected to the current conductor 1 of the two partial electrodes by means of flexible current conductors 1' following the tube axis with the aid of the connecting elements explained in FIG.
  • a sheathed flexible copper cable is preferably used as the material for the flexible current conductor.
  • the object of the invention is preferably used in hard chromium plating systems, the material to be applied being dissolved in the electrolyte.
  • the subject of the invention as a counter electrode for the cathodic corrosion protection of ships, tanks, pipelines and drilling towers.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Mechanical Engineering (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Prevention Of Electric Corrosion (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Battery Electrode And Active Subsutance (AREA)
EP86116354A 1985-11-27 1986-11-25 Electrode pour procédés électrochimiques Expired EP0224851B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86116354T ATE47432T1 (de) 1985-11-27 1986-11-25 Elektrode fuer elektrochemische verfahren.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3541845 1985-11-27
DE3541845A DE3541845C1 (de) 1985-11-27 1985-11-27 Rohrfoermige Elektrode fuer elektrolytische Verfahren

Publications (2)

Publication Number Publication Date
EP0224851A1 true EP0224851A1 (fr) 1987-06-10
EP0224851B1 EP0224851B1 (fr) 1989-10-18

Family

ID=6286930

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86116354A Expired EP0224851B1 (fr) 1985-11-27 1986-11-25 Electrode pour procédés électrochimiques

Country Status (3)

Country Link
EP (1) EP0224851B1 (fr)
AT (1) ATE47432T1 (fr)
DE (2) DE3541845C1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2351739A (en) * 1999-07-01 2001-01-10 Atraverda Ltd Electrode containing an electrical conductor connected inside
WO2001002626A1 (fr) * 1999-07-01 2001-01-11 Atraverda Limited Electrode
US6884092B2 (en) 2000-03-06 2005-04-26 Atraverda Limited Electrode for use in an electrochemical treatment process

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1468670A (en) * 1973-08-02 1977-03-30 Ici Ltd Anodes
US4256810A (en) * 1978-12-04 1981-03-17 Gould Inc. High conductivity titanium electrode
GB2114158A (en) * 1981-08-05 1983-08-17 Toyota Motor Co Ltd Electrode for use in cationic electrodeposition coating and coating method using the same
US4486288A (en) * 1982-03-11 1984-12-04 Linder Bjoern H Oxide anode for use in impressed current cathodic corrosion protection
EP0132029A2 (fr) * 1983-06-13 1985-01-23 Kiyosumi Takayasu Electrode insoluble en plomb ou alliage de plomb
US4526666A (en) * 1983-06-23 1985-07-02 Oronzio De Nora Method for electrically connecting non corrodible anodes to the corrodible core of a power supply cable
US4544464A (en) * 1983-12-23 1985-10-01 Oronzio De Nora S.A. Ground anode prepacked with backfill in a flexible structure for cathode protection with impressed currents

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1970804A (en) * 1932-12-24 1934-08-21 Paul C Kerk Electrode for electrolytic baths

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1468670A (en) * 1973-08-02 1977-03-30 Ici Ltd Anodes
US4256810A (en) * 1978-12-04 1981-03-17 Gould Inc. High conductivity titanium electrode
GB2114158A (en) * 1981-08-05 1983-08-17 Toyota Motor Co Ltd Electrode for use in cationic electrodeposition coating and coating method using the same
US4486288A (en) * 1982-03-11 1984-12-04 Linder Bjoern H Oxide anode for use in impressed current cathodic corrosion protection
EP0132029A2 (fr) * 1983-06-13 1985-01-23 Kiyosumi Takayasu Electrode insoluble en plomb ou alliage de plomb
US4526666A (en) * 1983-06-23 1985-07-02 Oronzio De Nora Method for electrically connecting non corrodible anodes to the corrodible core of a power supply cable
US4544464A (en) * 1983-12-23 1985-10-01 Oronzio De Nora S.A. Ground anode prepacked with backfill in a flexible structure for cathode protection with impressed currents

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN, unexamined applications, C Field, Vol. 7, Nr. 268, 30. November 1983 THE PATENT OFFICE JAPANESE GOVERNMENT Seite 31 C 197 & JP-A-58-147 595 (mishima kousan k.k.) *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2351739A (en) * 1999-07-01 2001-01-10 Atraverda Ltd Electrode containing an electrical conductor connected inside
WO2001002626A1 (fr) * 1999-07-01 2001-01-11 Atraverda Limited Electrode
GB2351739B (en) * 1999-07-01 2004-01-21 Atraverda Ltd Electrode
US6998031B1 (en) 1999-07-01 2006-02-14 Atraverda Limited Electrode
US6884092B2 (en) 2000-03-06 2005-04-26 Atraverda Limited Electrode for use in an electrochemical treatment process

Also Published As

Publication number Publication date
DE3541845C1 (de) 1987-01-08
EP0224851B1 (fr) 1989-10-18
ATE47432T1 (de) 1989-11-15
DE3666465D1 (en) 1989-11-23

Similar Documents

Publication Publication Date Title
DE2731976A1 (de) Kathodisches schutzsystem fuer metallische oberflaechen
CH632014A5 (de) Bipolare elektrode.
EP0089475B1 (fr) Anode revêtue à base de métal soupape pour l'obtention électrolytique de métaux ou oxydes de métaux
EP0036677B1 (fr) Cellule d'électrolyse
DE2812055C2 (de) Bipolare Elektrode
DE1191136B (de) Hygrometerzelle
DE2046479B2 (de) Anodenanordnung in einer elektrolysezelle
EP0224851B1 (fr) Electrode pour procédés électrochimiques
DE3406797C2 (de) Beschichtete Ventilmetallanode zur elektrolytischen Gewinnung von Metallen oder Metalloxiden
EP0141353A2 (fr) Elément de stockage d'énergie électrochimique
EP0436078B1 (fr) Dispositif anodique pour cellule d'électrolyse
DE2506285C3 (de) Verfahren zur Herstellung einer Elektrodenplatte für die elektrolytische Gewinnung von Nichteisenmetallen
DE3528587C2 (fr)
DE2627732B2 (de) Walze zur kontinuierlichen elektrolytischen Behandlung von bandförmigen metallischen Materialien
DD144174A1 (de) Elektrolysezelle und methode zur herstellung derselben
DE3406777C2 (de) Beschichtete Ventilmetallanode zur elektrolytischen Gewinnung von Metallen oder Metalloxiden
EP1045419B1 (fr) Ensemble d'électrodes pour dispositifs électriques avec métal liquide
DE2832003C2 (fr)
DE2721958A1 (de) Metallelektrode fuer elektrolyseapparate zum elektrolytischen herstellen von chlor
DE2820033A1 (de) Korrosionsschutzanode
DE4419864A1 (de) Elektrode zur elektrolytischen Innenbeschichtung und/oder zum Elektropolieren von Waffenrohren
DE4025253C2 (de) Stromzuleiter für eine Elektrode
AT399166B (de) Anode für galvanische bäder, sowie verfahren zur herstellung und verwendung dieser anode
AT249086B (de) Elektrischer Leiter und Verfahren zu seiner Herstellung
DE3406823C2 (de) Beschichtete Ventilmetallanode zur elektrolytischen Gewinnung von Metallen oder Metalloxiden

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19861205

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE FR GB IT LI LU NL SE

17Q First examination report despatched

Effective date: 19880707

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE FR GB IT LI LU NL SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19891018

Ref country code: NL

Effective date: 19891018

Ref country code: BE

Effective date: 19891018

REF Corresponds to:

Ref document number: 47432

Country of ref document: AT

Date of ref document: 19891115

Kind code of ref document: T

ET Fr: translation filed
REF Corresponds to:

Ref document number: 3666465

Country of ref document: DE

Date of ref document: 19891123

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19891130

Ref country code: LI

Effective date: 19891130

Ref country code: CH

Effective date: 19891130

ITF It: translation for a ep patent filed

Owner name: SOCIETA' ITALIANA BREVETTI S.P.A.

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)
NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19901018

Year of fee payment: 5

ITTA It: last paid annual fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19921001

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 19921019

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19921124

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19921127

Year of fee payment: 7

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19931125

Ref country code: AT

Effective date: 19931125

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19931125

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19940729

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20051125