WO2004011699A1 - Removing surface oxides from copper - Google Patents

Removing surface oxides from copper Download PDF

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Publication number
WO2004011699A1
WO2004011699A1 PCT/FI2003/000572 FI0300572W WO2004011699A1 WO 2004011699 A1 WO2004011699 A1 WO 2004011699A1 FI 0300572 W FI0300572 W FI 0300572W WO 2004011699 A1 WO2004011699 A1 WO 2004011699A1
Authority
WO
WIPO (PCT)
Prior art keywords
copper
anode
cathodic reduction
cathode
oxygen
Prior art date
Application number
PCT/FI2003/000572
Other languages
English (en)
French (fr)
Inventor
Olli Hyvärinen
Matti Leiponen
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
Priority to US10/523,552 priority Critical patent/US20060091021A1/en
Priority to MXPA05001196A priority patent/MXPA05001196A/es
Priority to AU2003281678A priority patent/AU2003281678A1/en
Priority to BR0313009-6A priority patent/BR0313009A/pt
Priority to JP2004523829A priority patent/JP2006501362A/ja
Priority to EA200500075A priority patent/EA006828B1/ru
Priority to EP03740525A priority patent/EP1552042A1/en
Publication of WO2004011699A1 publication Critical patent/WO2004011699A1/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25FPROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F1/00Electrolytic cleaning, degreasing, pickling or descaling
    • C25F1/02Pickling; Descaling
    • C25F1/04Pickling; 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)
PCT/FI2003/000572 2002-07-31 2003-07-17 Removing surface oxides from copper WO2004011699A1 (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
US10/523,552 US20060091021A1 (en) 2002-07-31 2003-07-17 Removing surface oxides from copper
MXPA05001196A MXPA05001196A (es) 2002-07-31 2003-07-17 Remocion de oxidos de superficies de cobre.
AU2003281678A AU2003281678A1 (en) 2002-07-31 2003-07-17 Removing surface oxides from copper
BR0313009-6A BR0313009A (pt) 2002-07-31 2003-07-17 Método para a remoção de óxidos de superfìcie a partir de cobre
JP2004523829A JP2006501362A (ja) 2002-07-31 2003-07-17 銅の表面酸化物の除去
EA200500075A EA006828B1 (ru) 2002-07-31 2003-07-17 Удаление оксидов с поверхности меди
EP03740525A EP1552042A1 (en) 2002-07-31 2003-07-17 Removing surface oxides from copper

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FI20021425 2002-07-31
FI20021425A FI114871B (fi) 2002-07-31 2002-07-31 Kuparin pintaoksidien poistaminen

Publications (1)

Publication Number Publication Date
WO2004011699A1 true WO2004011699A1 (en) 2004-02-05

Family

ID=8564392

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/FI2003/000572 WO2004011699A1 (en) 2002-07-31 2003-07-17 Removing surface oxides from copper

Country Status (12)

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

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 (en) * 2011-09-15 2017-11-22 General Electric Company Method of rejuvenating a multilayer structure
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

Citations (8)

* 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
JPS505988B1 (ru) * 1970-03-23 1975-03-10
US4544462A (en) * 1983-06-13 1985-10-01 Hitachi, Ltd. Process for removing metal surface oxide
US4545877A (en) * 1983-01-20 1985-10-08 Hillis Maurice R Method and apparatus for etching copper
US5639360A (en) * 1991-05-30 1997-06-17 Sikel N.V. Electrode for an electrolytic cell, use thereof and method using same
US5795460A (en) * 1996-04-10 1998-08-18 Dynamotive Corporation Method for removal of films from metal surfaces using electrolysis and cavitation action
WO2002032595A1 (en) * 2000-10-19 2002-04-25 Bwe Limited Method and apparatus for production of a continuously extruded product

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2749611A (en) * 1951-03-07 1956-06-12 Ver Deutsche Metallwerke Ag Production of wire rod and wire

Patent Citations (8)

* 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
JPS505988B1 (ru) * 1970-03-23 1975-03-10
US4545877A (en) * 1983-01-20 1985-10-08 Hillis Maurice R Method and apparatus for etching copper
US4544462A (en) * 1983-06-13 1985-10-01 Hitachi, Ltd. Process for removing metal surface oxide
US5639360A (en) * 1991-05-30 1997-06-17 Sikel N.V. Electrode for an electrolytic cell, use thereof and method using same
US5795460A (en) * 1996-04-10 1998-08-18 Dynamotive Corporation Method for removal of films from metal surfaces using electrolysis and cavitation action
WO2002032595A1 (en) * 2000-10-19 2002-04-25 Bwe Limited Method and apparatus for production of a continuously extruded product

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 197514, Derwent World Patents Index; Class M11, AN 1975-23404W, XP002986688 *

Also Published As

Publication number Publication date
EP1552042A1 (en) 2005-07-13
FI114871B (fi) 2005-01-14
EA006828B1 (ru) 2006-04-28
PL373766A1 (en) 2005-09-19
TW200403360A (en) 2004-03-01
FI20021425A (fi) 2004-02-01
MXPA05001196A (es) 2005-05-16
CN1671890A (zh) 2005-09-21
US20060091021A1 (en) 2006-05-04
BR0313009A (pt) 2005-06-07
FI20021425A0 (fi) 2002-07-31
JP2006501362A (ja) 2006-01-12
EA200500075A1 (ru) 2005-08-25
AU2003281678A1 (en) 2004-02-16

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