EP1552042A1 - Retrait des oxydes de surface du cuivre - Google Patents

Retrait des oxydes de surface du cuivre

Info

Publication number
EP1552042A1
EP1552042A1 EP03740525A EP03740525A EP1552042A1 EP 1552042 A1 EP1552042 A1 EP 1552042A1 EP 03740525 A EP03740525 A EP 03740525A EP 03740525 A EP03740525 A EP 03740525A EP 1552042 A1 EP1552042 A1 EP 1552042A1
Authority
EP
European Patent Office
Prior art keywords
copper
anode
cathodic reduction
cathode
oxygen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP03740525A
Other languages
German (de)
English (en)
Inventor
Olli Hyvärinen
Matti Leiponen
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.)
Outokumpu Oyj
Original Assignee
Outokumpu Oyj
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 Outokumpu Oyj filed Critical Outokumpu Oyj
Publication of EP1552042A1 publication Critical patent/EP1552042A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F1/00—Electrolytic cleaning, degreasing, pickling or descaling
    • C25F1/02—Pickling; Descaling
    • C25F1/04—Pickling; Descaling in solution

Definitions

  • the invention relates to a method and arrangement, defined in the independent claims, for improving the quality of an object made of a copper-based metal alloy.
  • Oxide layers are difficult to observe or measure on the copper surface, and they are not necessarily distinguished without specific equipment.
  • the removal of thick oxide layers from the copper surface is relatively simple, but on the other hand, the removal of the last molecular layers has turned out to be more troublesome.
  • Oxide layers on the surface of copper disturb for instance extrusion, so that when removing the oxide layers, there is created harmful extrusion scrap. The treatment and recirculation of extrusion scrap lead to extra expenses.
  • etching In the cleaning of copper metal surfaces, there is generally applied etching, i.e. the metal surface is chemically cleaned of the oxide layer by means of dissolution. It is generally known that all grease and oil should be removed from the product surface before etching. Normally the etching of copper metals is carried out in a sulfuric acid - water solution, and it removes the major part of the oxides created on the surface. In conventional sulfuric acid etching, there is achieved a low oxide layer level immediately after the etching process, but in practice the dissolved oxygen of the acid and the slowness of the final washing may double the oxide layer after drying.
  • One way of preventing the creation of oxides on the surface of a copper object is to insulate the copper object by a protective gas atmosphere in order to prevent oxidation.
  • the object of the present invention is to avoid the drawbacks of the prior art and to introduce a new solution for improving the quality of an object made of a copper- based metal alloy.
  • a particular object of the invention is to improve the quality of an object made of a copper-based metal alloy by removing oxides from the surface thereof by means of cathodic reduction.
  • the method according to the invention has many advantages.
  • the invention relates to a method for improving the quality of an object made of a copper-based metal alloy, according to which method the object is treated at least in an oxide removal unit, so that in the oxide removal unit, oxides are removed from the object surface by means of cathodic reduction.
  • cathodic reduction By applying cathodic reduction, the oxides present on the copper surface are reduced to copper, so that the oxide layer is eliminated from the surface of the copper object.
  • the employed electrolyte in cathodic reduction is sodium carbonate solution.
  • the employed electrolyte in cathodic reduction is sulfuric acid solution.
  • the employed cathode in cathodic reduction is the object made of a copper-based metal alloy, and the employed anode is a non-soluble material, such as a platinum anode or a platinum-coated titanium anode.
  • a non-soluble material such as a platinum anode or a platinum-coated titanium anode.
  • Other suitable anode materials are for example lead or titanium coated with iridium oxide.
  • oxygen on the anode there is created oxygen, and on the cathode there is created copper.
  • an ion-selective membrane that is impermeable to oxygen.
  • the membrane is advantageously placed between the anode and the cathode in order to prevent the oxygen from being transferred from the anode to the cathode. From the space between the anode and the membrane, oxygen is exhausted along with the solution circulation, or through oxygen exhaustion apertures.
  • the membrane is arranged symmetrically around the cathode, so that it surrounds the whole cathode. In this fashion, the oxidation and reduction reactions are made to proceed smoothly, and the voltage is distributed evenly in the whole cell.
  • an object made of a copper-based metal alloy is subjected to preliminary washing prior to the cathodic reduction.
  • an object made of a copper-based metal alloy is subjected to etching by sulfuric acid before the cathodic reduction.
  • the thickest oxide films are removed rapidly prior to the cathodic reduction.
  • sulfuric acid films are removed by mechanical drying.
  • the object is subjected to a rapid pressurized water washing after the cathodic reduction.
  • the remaining oxide layer after a treatment performed in the oxide removal unit is preferably left at a degree of 0.001 - 0.01 nanometers, i.e. advantageously the oxide film is nearly completely removed.
  • the object is after the oxide removal unit conducted into a working process, such as a continuously operated extrusion treatment.
  • the oxide removal unit and the working process are insulated from the surroundings by protective gas.
  • the invention also relates to an arrangement for realizing the method according to claim 1 for improving the quality of an object made of a copper-based metal alloy, said arrangement comprising at least an oxide removal unit and elements for realizing cathodic reduction, such as an anode, a cathode and an electrolyte, so that the access of the oxygen created on the anode to the cathode is prevented by a membrane that is impermeable to oxygen.
  • FIG. 1 A diagram of the principle of the method according to the invention
  • Figure 1 illustrates the method according to the invention in the form of a block diagram.
  • a round wire-like object 1 made of copper is conducted to an oxide removal unit 3.
  • the oxide removal unit 3 includes a cathodic reduction arrangement.
  • the oxide-free copper wire 2 obtained from the oxide removal unit is conducted to a working process, such as a continuously operated extrusion treatment 4.
  • the oxide removal unit and the working process unit are insulated from the surroundings by protective gas.
  • FIG. 2 shows a cross-section of the cathodic reduction process carried out in an oxide removal unit.
  • copper wire is washed prior to the oxygen removal proper. Thereafter the copper wire is subjected to preliminary etching by sulfuric acid, so that the thickest oxides layers are removed. Sulfuric acid films left after etching are removed for instance by mechanical drying. Then the cathodic reduction is performed.
  • the copper wire 5 is placed in a chamber 9 containing sodium carbonate solution 11 , and electric current is conducted to said chamber.
  • the copper wire 5 serves as a cathode, on which copper oxide is reduced to copper, and thus the oxides are eliminated nearly completely from the copper surface.
  • the employed anode 6 is a non-soluble platinum anode, on which oxygen is created.
  • the solution 11 fills the chamber 9 all over.
  • the access of the oxygen created on the anode is prevented by an ion selective membrane 8 that is impermeable to oxygen, which preferably surrounds the whole cathode.
  • the employed housing for the membrane is an insulated, perforated tube 10 in order to maintain the liquid connection.
  • the membrane is symmetrically arranged around the cathode, which helps the reduction and oxidation reactions to proceed evenly.
  • an oxygen exhaust aperture 7, through which the oxygen created on the anode is removed from the system.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • ing And Chemical Polishing (AREA)

Abstract

L'invention concerne un procédé permettant d'améliorer la qualité d'un objet constitué d'un alliage métallique à base de cuivre. Ce procédé permet de traiter un objet au moins dans une unité de retrait d'oxydes (3), de sorte que dans cette unité de retrait d'oxydes, les oxydes sont retirés de la surface de l'objet au moyen d'une réduction cathodique. L'invention concerne également un agencement permettant de mettre en oeuvre le procédé, selon la revendication (1), de sorte à améliorer la qualité d'un objet constitué d'un alliage métallique à base de cuivre, ledit arrangement comprenant au moins une unité de retrait d'oxydes. Cet agencement comprend des éléments permettant de mettre en oeuvre une réduction cathodique, notamment une anode (6), une cathode (5) et un électrolyte (11), de sorte que l'accès de l'oxygène créé sur l'anode vers la cathode est obstrué par une membrane (18) qui est imperméable à l'oxygène.
EP03740525A 2002-07-31 2003-07-17 Retrait des oxydes de surface du cuivre Withdrawn EP1552042A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FI20021425 2002-07-31
FI20021425A FI114871B (fi) 2002-07-31 2002-07-31 Kuparin pintaoksidien poistaminen
PCT/FI2003/000572 WO2004011699A1 (fr) 2002-07-31 2003-07-17 Retrait des oxydes de surface du cuivre

Publications (1)

Publication Number Publication Date
EP1552042A1 true EP1552042A1 (fr) 2005-07-13

Family

ID=8564392

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03740525A Withdrawn EP1552042A1 (fr) 2002-07-31 2003-07-17 Retrait des oxydes de surface du cuivre

Country Status (12)

Country Link
US (1) US20060091021A1 (fr)
EP (1) EP1552042A1 (fr)
JP (1) JP2006501362A (fr)
CN (1) CN1671890A (fr)
AU (1) AU2003281678A1 (fr)
BR (1) BR0313009A (fr)
EA (1) EA006828B1 (fr)
FI (1) FI114871B (fr)
MX (1) MXPA05001196A (fr)
PL (1) PL373766A1 (fr)
TW (1) TW200403360A (fr)
WO (1) WO2004011699A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101514477B (zh) * 2009-03-03 2011-02-02 天津力神电池股份有限公司 一种锂离子电池失效后负极铜箔片的清洗电化学方法
EP2570520B1 (fr) * 2011-09-15 2017-11-22 General Electric Company Procédé de régénération d'une structure multicouche
CN103469255B (zh) * 2013-09-09 2015-12-23 重庆潼双机械制造有限公司 铜阳极板泡洗液的循环利用装置及方法

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1773160A (en) * 1927-10-28 1930-08-19 Hanovia Chemical & Mfg Co Process for cupric-oxide removal
GB586250A (en) * 1944-12-11 1947-03-12 Du Pont Electrolytic cleaning of metals
US2749611A (en) * 1951-03-07 1956-06-12 Ver Deutsche Metallwerke Ag Production of wire rod and wire
JPS505988B1 (fr) * 1970-03-23 1975-03-10
GB2133806B (en) * 1983-01-20 1986-06-04 Electricity Council Regenerating solutions for etching copper
JPS59232279A (ja) * 1983-06-13 1984-12-27 Hitachi Ltd 金属表面酸化物の除去方法
CA2109708C (fr) * 1991-05-30 1999-09-28 Hans Joseph May Electrode pour cellule electrolytique, son utilisation et procede l'utilisant
US5795460A (en) * 1996-04-10 1998-08-18 Dynamotive Corporation Method for removal of films from metal surfaces using electrolysis and cavitation action
EP1326721A1 (fr) * 2000-10-19 2003-07-16 Bwe Limited Proc d et dispositif de production d'un produit extrud en continu

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2004011699A1 *

Also Published As

Publication number Publication date
WO2004011699A1 (fr) 2004-02-05
PL373766A1 (en) 2005-09-19
BR0313009A (pt) 2005-06-07
EA006828B1 (ru) 2006-04-28
CN1671890A (zh) 2005-09-21
TW200403360A (en) 2004-03-01
US20060091021A1 (en) 2006-05-04
EA200500075A1 (ru) 2005-08-25
AU2003281678A1 (en) 2004-02-16
JP2006501362A (ja) 2006-01-12
FI20021425A (fi) 2004-02-01
MXPA05001196A (es) 2005-05-16
FI114871B (fi) 2005-01-14
FI20021425A0 (fi) 2002-07-31

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