WO1982002408A1 - A method of anodically deburring articles of copper or copper alloy - Google Patents

A method of anodically deburring articles of copper or copper alloy Download PDF

Info

Publication number
WO1982002408A1
WO1982002408A1 PCT/SE1982/000010 SE8200010W WO8202408A1 WO 1982002408 A1 WO1982002408 A1 WO 1982002408A1 SE 8200010 W SE8200010 W SE 8200010W WO 8202408 A1 WO8202408 A1 WO 8202408A1
Authority
WO
WIPO (PCT)
Prior art keywords
alkali
bath
copper
solution
sulphamate
Prior art date
Application number
PCT/SE1982/000010
Other languages
French (fr)
Inventor
Karl Ingemar Blomsterberg
Original Assignee
Karl Ingemar Blomsterberg
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 Karl Ingemar Blomsterberg filed Critical Karl Ingemar Blomsterberg
Publication of WO1982002408A1 publication Critical patent/WO1982002408A1/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25FPROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F3/00Electrolytic etching or polishing
    • C25F3/02Etching
    • C25F3/14Etching locally
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25FPROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F3/00Electrolytic etching or polishing
    • C25F3/16Polishing
    • C25F3/22Polishing of heavy metals

Definitions

  • the present invention has for its object to provide an improved method for anodically deburring articles of copper or copper alloys, for instance brass, aluminium bronze or beryllium bronze.
  • the new method according to the invention is characterized thereby that the treatment is carried out in an acid solution having a pH not exceeding 6.5 and containing grams per liter water 100 to 300 alkali sulphamate 50 to 100 polyhydric alcohol 400 to 800 alkali nitrate 50 to 150 at a bath voltage of 5 to 30 volts and a current density (at the anode) of 2 to 50 amperes per square decimeter.
  • the method according to the invention results in a svift and effective removal of burrs and sharp edges from the article treated and imparts a smooth, attractive surface to the same.
  • the alkali salts of the bath consist of ammonium salts. This has proved to result in the advantage that an unimportant volume only of gaseous hydrogen is deve- loped during the treatment.
  • the use of sodium or potassium salts will result in the development of considerable quantities of gaseous hydrogen, which, if the supply of fresh air is inadequate, may cause an explosive mixture of air and hydrogen to form above the surface of the bath.
  • the property of reducing the develop- ment of hydrogen exhibited by the ammonium salts was quite .unexpected and has as yet found no satisfactory explanation.
  • the method according to the invention is preferably carried out at bath voltages in the range of 15 to 20 volts and current densities (at the anode surface) of the order of 10 to 20 amperes per square decimeter.
  • the bath temperature should not exceed 25°C.
  • Preferably the temperature is maintained within the range of 15 to 20°C.
  • the deburring action is known to be due to the fact that the current density and, consequently, the removal of material is considerably more intense at sharp edges and protruding burrs on the article than at the even portions of its surface.
  • This property (usually referred to as "selectivity") depends on several factors, for instance the shape and size of the article treated, the shape of the cathode, the distance between the anode and the cathode, and the conductivity of the bath solution. Too large a conductivity will cause deterioration of the selectivity as well as of the smoothness of the surfaces treated.
  • a substantial improvement of the selectivity can be obtained by supplying the bath current during active intervals separated by idle intervals during which no current flows.
  • the length of the active interval should amount to 1/2 to 2 minutes.
  • the conductivity of the bath can be adjusted in a simple way by adjustment of the content of polyhydric alcohol.
  • the polyhydric alcohol preferably is ethylene glycol.
  • composition specified below is an example of a bath for the method according to the invention.
  • Adjustment of the pH of the bath is carried out by the addition of a small quantity of nitric acid. Fresh additions have to be made from time to time, preferably by means of an automatic dosimeter controlled by a pH meter.
  • the treatment is preferably carried out inter- mittently, the lengths of the active interval and the idle interval being chosen within the ranges specified above.
  • the chemical processes occurring in the bath are complicated and are considered not to be fully clarified.
  • the bath has proved to have a long useful life, provided that its pH is always kept within the stated range of 5 to 6.5 by proper additions of nitric acid, and provided that solid impurities (mostly metal hydroxides) formed during the operation of the bath are successively removed, for instance by filtration.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • ing And Chemical Polishing (AREA)
  • Electroplating And Plating Baths Therefor (AREA)

Abstract

Articles of copper or copper alloy are anodically deburred in an acid solution (pH not above 6.5) containing: water 100 to 300 g/l; alkali sulphamate 50 to 150 g/l; polyhydric alcohol 400 to 800; alkali nitrate 50 to 150 g/l. The bath voltage is to be within the range of 5 to 30 volts, and the current density (at the anode) is to be within the range of 2 to 50 amperes per square decimeter.

Description

A Method of Anodical ly Deburring Articles of Copper or Copper Al loy
The present invention has for its object to provide an improved method for anodically deburring articles of copper or copper alloys, for instance brass, aluminium bronze or beryllium bronze. The new method according to the invention is characterized thereby that the treatment is carried out in an acid solution having a pH not exceeding 6.5 and containing grams per liter water 100 to 300 alkali sulphamate 50 to 100 polyhydric alcohol 400 to 800 alkali nitrate 50 to 150 at a bath voltage of 5 to 30 volts and a current density (at the anode) of 2 to 50 amperes per square decimeter.
The method according to the invention results in a svift and effective removal of burrs and sharp edges from the article treated and imparts a smooth, attractive surface to the same. In a preferred form of the method according to the invention, the alkali salts of the bath consist of ammonium salts. This has proved to result in the advantage that an unimportant volume only of gaseous hydrogen is deve- loped during the treatment. In contradistinction thereto, the use of sodium or potassium salts will result in the development of considerable quantities of gaseous hydrogen, which, if the supply of fresh air is inadequate, may cause an explosive mixture of air and hydrogen to form above the surface of the bath. The property of reducing the develop- ment of hydrogen exhibited by the ammonium salts was quite .unexpected and has as yet found no satisfactory explanation. The method according to the invention is preferably carried out at bath voltages in the range of 15 to 20 volts and current densities (at the anode surface) of the order of 10 to 20 amperes per square decimeter. The bath temperature should not exceed 25°C. Preferably the temperature is maintained within the range of 15 to 20°C.
The deburring action is known to be due to the fact that the current density and, consequently, the removal of material is considerably more intense at sharp edges and protruding burrs on the article than at the even portions of its surface. This property (usually referred to as "selectivity") depends on several factors, for instance the shape and size of the article treated, the shape of the cathode, the distance between the anode and the cathode, and the conductivity of the bath solution. Too large a conductivity will cause deterioration of the selectivity as well as of the smoothness of the surfaces treated. Moreover, it has been found that in the method according to the invention a substantial improvement of the selectivity can be obtained by supplying the bath current during active intervals separated by idle intervals during which no current flows. Preferably the length of the active interval should amount to 1/2 to 2 minutes. For the idle interval, a length of a few seconds only, for instance 5 to 10 seconds, is sufficient and suitable.
In the method according to the invention, the conductivity of the bath can be adjusted in a simple way by adjustment of the content of polyhydric alcohol. In the preferred form of the invention in which the alkali salts are ammonium salts, the polyhydric alcohol preferably is ethylene glycol.
The composition specified below is an example of a bath for the method according to the invention. Ethylene glycol 650 parts by weight Ammonium sulphamate 100 " " "
Ammonium nitrate 100 " " " Water 150 " " " The following conditions are suitable for the anodic deburring of articles of steel or aluminium alloy in the bath above specified:
Bath temperature 15 to 20ºC
Bath voltage 15 to 25 volts Anodic current density 10-20 amperes per square decimeter pH 5.0 to 6.5
Adjustment of the pH of the bath is carried out by the addition of a small quantity of nitric acid. Fresh additions have to be made from time to time, preferably by means of an automatic dosimeter controlled by a pH meter.
The treatment is preferably carried out inter- mittently, the lengths of the active interval and the idle interval being chosen within the ranges specified above.
The chemical processes occurring in the bath are complicated and are considered not to be fully clarified. The bath has proved to have a long useful life, provided that its pH is always kept within the stated range of 5 to 6.5 by proper additions of nitric acid, and provided that solid impurities (mostly metal hydroxides) formed during the operation of the bath are successively removed, for instance by filtration.

Claims

C l a i m s
1. A method of anodically deburring articles of copper or copper alloy, c h a r a c t e r i z e d i n that the treatment is carried out in an acid solution having a pH not exceeding 6.5 and containing grams per liter water 100 to 300 alkali sulphamate 50 to 150 polyhydric alcohol 400 to 800 alkali nitrate 50 to 150 at a bath voltage of 5 to 30 volts and a current density of 2 to 50 amperes per square decimeter.
2. A method as claimed in Claim 1, c h a r a c t e r i z e d i n that the treatment is carried out in a solution the alkali salts of which consist exclusively or predominantly of ammonium salts.
3. A method as claimed in Claim 1 or 2, c h a r a c t e r i z e d i n that the treatment is carried out in a solution having a total content of alkali sulphamate and alkali nitrate not exceeding 250 grams per litre.
4. A method as claimed in any of Claims 1 to 3, c h a r a c t e r i z e d i n that the treatment is carried out in a solution having a pH not lower than 5.
5. A method as claimed in any preceding claim, c h a r a c t e r i z e d i n that the acidity of the solution is adjusted by the additon of nitric acid to the solution.
6. A bath for the anodic deburring of articles of copper or copper alloy by the method claimed in Claim 1, c h a r a c t e r i z e d b y the following constituents: grams per liter water 100 to 300 alkali sulphamate 50 to 150 polyhydric alcohol 400 to 800 alkali nitrate 50 to 150 and free acid in the quantity required to adjust the pH of the bath to not more than 6.5.
7. A bath as claimed in Claim 6, c h a r a c t e r i z e d i n that the alkali salts contained therein consist exclusively or predominantly of ammonium salts.
8. A bath as claimed in Claim 6 or 7, c h a r a c t e r i z e d i n that its total content of alkali sulphamate and alkali nitrate does not exceed 250 grams per liter.
9. A bath as claimed in any of Claims 6 to 8 , c h a r a c t e r i z e d b y a pH not lower than 5.
10. A bath as claimed in any of Claims 6 to 9, c h a r a c t e r i z e d b y a content of free nitric acid.
PCT/SE1982/000010 1981-01-15 1982-01-15 A method of anodically deburring articles of copper or copper alloy WO1982002408A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SE8100202A SE425103B (en) 1981-01-15 1981-01-15 PROCEDURE KIT AND BATH FOR ANODIC DEGRADATION OF COPPER OR COPPER ALLOY
SE8100202810115 1981-01-15

Publications (1)

Publication Number Publication Date
WO1982002408A1 true WO1982002408A1 (en) 1982-07-22

Family

ID=20342884

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/SE1982/000010 WO1982002408A1 (en) 1981-01-15 1982-01-15 A method of anodically deburring articles of copper or copper alloy

Country Status (4)

Country Link
EP (1) EP0070288A1 (en)
CH (1) CH652421A5 (en)
SE (1) SE425103B (en)
WO (1) WO1982002408A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0511557A1 (en) * 1991-04-29 1992-11-04 Siemens Aktiengesellschaft Procedure and equipment for deburring of contact pins
WO2001051683A1 (en) * 2000-01-07 2001-07-19 Huntsman Petrochemical Corporation Galvanic methods of accelerating copper dissolution into solutions containing nitrogen compounds

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3556957A (en) * 1966-01-03 1971-01-19 Honeywell Inc Metal treatment
SE413681B (en) * 1977-11-22 1980-06-16 Blomsterberg Karl Ingemar SET AND BATH FOR CATODIC CLEANING OF METAL SURFACES IN A NEUTRAL WATER SOLUTION OF AN ALKALISAL
SE415891B (en) * 1979-02-19 1980-11-10 Blomsterberg Karl Ingemar SET TO ANODICALLY DEGREE AND / OR POLISH A STALL FORM IN AN ELECTROLYTICAL BATH AND BATH FOR EXECUTION OF THE SET

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3556957A (en) * 1966-01-03 1971-01-19 Honeywell Inc Metal treatment
SE413681B (en) * 1977-11-22 1980-06-16 Blomsterberg Karl Ingemar SET AND BATH FOR CATODIC CLEANING OF METAL SURFACES IN A NEUTRAL WATER SOLUTION OF AN ALKALISAL
SE415891B (en) * 1979-02-19 1980-11-10 Blomsterberg Karl Ingemar SET TO ANODICALLY DEGREE AND / OR POLISH A STALL FORM IN AN ELECTROLYTICAL BATH AND BATH FOR EXECUTION OF THE SET

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0511557A1 (en) * 1991-04-29 1992-11-04 Siemens Aktiengesellschaft Procedure and equipment for deburring of contact pins
WO2001051683A1 (en) * 2000-01-07 2001-07-19 Huntsman Petrochemical Corporation Galvanic methods of accelerating copper dissolution into solutions containing nitrogen compounds
US6294071B1 (en) 2000-01-07 2001-09-25 Huntsman Petrochemical Corporation Methods of forming copper solutions

Also Published As

Publication number Publication date
SE425103B (en) 1982-08-30
CH652421A5 (en) 1985-11-15
EP0070288A1 (en) 1983-01-26
SE8100202L (en) 1982-07-16

Similar Documents

Publication Publication Date Title
US3619390A (en) Aqueous electrolytic stripping bath to remove metal coatings from bases of steel
US4242417A (en) Lithographic substrates
US4324841A (en) Lithographic substrates
US4405422A (en) Method of anodically deburring articles of copper or copper alloy
US2542779A (en) Electropolishing composition and process
US4411751A (en) Method of anodically deburring articles of steel or aluminium alloys in an electrolytic bath, and a bath for carrying out the method
GB1309497A (en) Method of electro-plating copper onto aluminium metal or alloy
WO1982002408A1 (en) A method of anodically deburring articles of copper or copper alloy
US3775264A (en) Plating copper on aluminum
US2753301A (en) Electropolishing of copper and its alloys
US2581490A (en) Electrolytic process of stripping metallic coatings from a ferrous metal base
US2464168A (en) Electrolytic iron for powder metallurgy purposes
US4521282A (en) Cyanide-free copper electrolyte and process
US4297179A (en) Palladium electroplating bath and process
US3729396A (en) Rhodium plating composition and method for plating rhodium
WO1982002407A1 (en) A method of anodically deburring articles of steel or aluminium alloys in an electrolytic bath,and a bath for carrying out the method
EP0088192B1 (en) Control of anode gas evolution in trivalent chromium plating bath
US3242062A (en) Fluorine-cuntaining electrolyte for electrolytic cutting of metals
US2694041A (en) Electrodeposition of nickel
US2820750A (en) Electrolytic treatment of metals and alloys
US4197172A (en) Gold plating composition and method
US2796394A (en) Separating and recovering nonferrous alloys from ferrous materials coated therewith
US3274079A (en) Bath and process for the electrodeposition of nickel and nickel-cobalt alloys
RU2133305C1 (en) Electrolyte for brilliant nickel plating
US2712525A (en) Electropolishing of gold alloys

Legal Events

Date Code Title Description
AK Designated states

Designated state(s): CH DE GB JP US

AL Designated countries for regional patents

Designated state(s): FR