EP0657564A1 - Process for cleaning and conditioning the surface of an electrolytically oxidizable metal alloy by hyperanodizing said surface - Google Patents

Process for cleaning and conditioning the surface of an electrolytically oxidizable metal alloy by hyperanodizing said surface Download PDF

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Publication number
EP0657564A1
EP0657564A1 EP94203574A EP94203574A EP0657564A1 EP 0657564 A1 EP0657564 A1 EP 0657564A1 EP 94203574 A EP94203574 A EP 94203574A EP 94203574 A EP94203574 A EP 94203574A EP 0657564 A1 EP0657564 A1 EP 0657564A1
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EP
European Patent Office
Prior art keywords
process according
light alloy
hyperanodizing
conditioning
materials treated
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
EP94203574A
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German (de)
French (fr)
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EP0657564B1 (en
Inventor
Dario Felisari
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Individual
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Individual
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Expired - Lifetime legal-status Critical Current

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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

Definitions

  • the washing process commonly used by aluminum alloy manufacturers or fabricators essentially consists in a band degreasing step carried out in order to remove greases or similar organic substances used in the rolling process.
  • Such a removal is carried out by bringing the band to be washed into contact with a liquid phase displaying strong affinity for the impurities, substantially performing the task of transferring the latter from the solid into the liquid phase.
  • Said processes are usually carried out with solvent liquids (e.g., trichloroethylene) or alkaline solutions which are suitably buffered, therefore with reduced reactivity towards aluminum; in order to cause the impurities to diffuse, the processes known from the prior art rely on diffusion (high-temperature processes), or on kinds of fluxing (castings), or on the supply of mechanical energy to the interface (brushing, sonication).
  • solvent liquids e.g., trichloroethylene
  • alkaline solutions which are suitably buffered, therefore with reduced reactivity towards aluminum
  • the processes known from the prior art rely on diffusion (high-temperature processes), or on kinds of fluxing (castings), or on the supply of mechanical energy to the interface (brushing, sonication).
  • a rinsing step follows, often followed, in its turn, by steps of anchoring functional groups for surface protection, or acting as adhesion promoters (oxidation, chromate treatment, phosphating treatment or phospho-chromate treatment).
  • Electrochemical processes are known as well in the practice of metal articles degreasing, which consist in submitting the metal surface to an anodic or cathodic action, while said surface is immersed in suitable electrolytic solutions.
  • the process according to the present patent application consists in an action of ionic type which exclusively occurs at high current density values (superficial electrical intensity comprised within the range of from some tens, up to one hundred A/dm2), in the presence of a polybasic acidic electrolyte, when the electrolytically oxidizable material is submitted to anodizing with a higher voltage than the stopping potential of formed oxide.
  • the voltage gradient concentrated in the immediate nearby of the surface of the metal to be treated, promotes a violent, localized energy development with the results disclosed hereinabove being accomplished.
  • a process results which is governed by easily modulated electrical parameters in which, following a supply of electrical energy (of the order of 1 kW/dm2 of exposed surface) a nearly immediate decontamination of band surface is attained.
  • the essential parameters are constituted by the electrical conductivity of the bath and the local current density on the surface to be treated.
  • the present electrodes necessary for the above events to take place prevailingly perform transport functions, and therefore their composition slowly varies during the process.
  • the energy excess turned into heat must be transferred to a secondary fluid, and can be recovered for the rinsing or drying process.
  • the band to be treated is electrically connected to the positive terminal of power supply unit.
  • the ionic action takes place inside a tank inside which the band can run while being immersed, exposed to the surfaces of opposite polarity electrodes (cathodes).
  • the process consists in submitting the surface layer of an electrolytically oxidizable metal to the action of an electrical field with a higher field intensity than the breakdown intensity during an anodizing step.
  • the process is particularly useful for high-speed treatment of bands of light alloy or other oxidizable materials.

Abstract

The process consists in submitting the surface layer of an electrolytically oxidizable metal to the action of an electrical field with a higher field intensity than the breakdown intensity during an anodizing step.
Under such conditions, extremely intense energy exchanges occur in a region confined on the surface of the immersed article; the resulting physical and chemical processes cause, among others, any impurities to be nearly immediately removed, and a useful surface conditioning layer for subsequent processes to be produced.
The process is particularly useful for high-speed treatment of bands of light alloy or other oxidizable materials.

Description

  • According to the present state of the art, the washing process commonly used by aluminum alloy manufacturers or fabricators essentially consists in a band degreasing step carried out in order to remove greases or similar organic substances used in the rolling process.
  • Such a removal is carried out by bringing the band to be washed into contact with a liquid phase displaying strong affinity for the impurities, substantially performing the task of transferring the latter from the solid into the liquid phase.
  • Said processes are usually carried out with solvent liquids (e.g., trichloroethylene) or alkaline solutions which are suitably buffered, therefore with reduced reactivity towards aluminum; in order to cause the impurities to diffuse, the processes known from the prior art rely on diffusion (high-temperature processes), or on kinds of fluxing (castings), or on the supply of mechanical energy to the interface (brushing, sonication).
  • A rinsing step follows, often followed, in its turn, by steps of anchoring functional groups for surface protection, or acting as adhesion promoters (oxidation, chromate treatment, phosphating treatment or phospho-chromate treatment).
  • In order to be effective, these processes require a long enough surface-liquid contact time as to make it possible material to diffuse between the metal, the limit layer, and the liquid, which time, when bands are submitted to such a continuous, high-speed treatment, may require that considerably long facilities are used, with consequent large overall dimensions and high costs; furthermore, the use of hydrogenated rolling lubricants, such as, e.g., lauryl alcohol, and the like, having electronic affinity for aluminum, compromises the transfer of impurities to the liquid phase, sometimes rendering necessary a preliminary chemical etching step prior to the subsequent treatments, with problems of disposal of the resulting waste products consequently arising.
  • Electrochemical processes are known as well in the practice of metal articles degreasing, which consist in submitting the metal surface to an anodic or cathodic action, while said surface is immersed in suitable electrolytic solutions.
  • This practice, useful in order to activate the surface as a preliminary step to electrodepositions is, unfortunately, ineffective for degreasing purposes, because the flow of the ionic species, and of the released gases does not interact with the presence of grease or oleol impurities.
  • Due to such a reason, in the practical operations of facilities for continuous band degreasing, this solution is not applied.
  • The process according to the present patent application consists in an action of ionic type which exclusively occurs at high current density values (superficial electrical intensity comprised within the range of from some tens, up to one hundred A/dm²), in the presence of a polybasic acidic electrolyte, when the electrolytically oxidizable material is submitted to anodizing with a higher voltage than the stopping potential of formed oxide.
  • Under such conditions, a sharp potential decrease takes place on that layer which is the nearest to the metal, with unstable ionic species (radicals) being generated, which are capable of destroying the degradable organic substances, or of reducing their affinity for the metal.
  • In other terms, the voltage gradient, concentrated in the immediate nearby of the surface of the metal to be treated, promotes a violent, localized energy development with the results disclosed hereinabove being accomplished.
  • A process results which is governed by easily modulated electrical parameters in which, following a supply of electrical energy (of the order of 1 kW/dm² of exposed surface) a nearly immediate decontamination of band surface is attained.
  • Therefore, the essential parameters are constituted by the electrical conductivity of the bath and the local current density on the surface to be treated.
  • The present electrodes, necessary for the above events to take place prevailingly perform transport functions, and therefore their composition slowly varies during the process.
  • In practical tests, several low-concentration (2 ÷ 5 %) acidic electrolytes were successfully tested under moderately high temperature (80 ÷ 90°C) conditions.
  • In order to maintain the temperature level, the energy excess turned into heat must be transferred to a secondary fluid, and can be recovered for the rinsing or drying process.
  • From a practical viewpoint, the band to be treated is electrically connected to the positive terminal of power supply unit.
  • The ionic action takes place inside a tank inside which the band can run while being immersed, exposed to the surfaces of opposite polarity electrodes (cathodes).
  • Current flow is so controlled as to keep constant energy developed at band surface, correlating it, e.g., to the running speed of said band. In other words the process consists in submitting the surface layer of an electrolytically oxidizable metal to the action of an electrical field with a higher field intensity than the breakdown intensity during an anodizing step.
  • Under such conditions, extremely intense energy exchanges occur in a region confined on the surface of the immersed article; the resulting physical and chemical processes cause, among others, any impurities to be nearly immediately removed, and a useful surface conditioning layer for subsequent processes to be produced.
  • The process is particularly useful for high-speed treatment of bands of light alloy or other oxidizable materials.

Claims (16)

  1. Surface washing and conditioning process accomplished by means of a hyperanodizing process of electrolytically oxidizable alloys.
  2. Process according to claim 1, characterized in that the anodizing voltage exceeds the breakdown potential of generated oxide.
  3. Process according to claim 2, characterized in that as process liquid an acidic electrolyte is used.
  4. Process according to claim 3, characterized in that as process liquid a phosphoric acid acidic electrolyte is used.
  5. Process according to claim 4, characterized in that concentrations of from 1 to 6 %, by weight, are used.
  6. Process according to claim 5, characterized in that temperatures are used which are comprised within the range of from 50 to 100°C.
  7. Process according to claim 2, applied to light alloy bands.
  8. Process according to claim 3, applied to light alloy bands.
  9. Process according to claim 4, applied to light alloy bands.
  10. Process according to claim 5, applied to light alloy bands.
  11. Process according to claim 6, applied to light alloy bands.
  12. Materials treated by means of process according to claim 7.
  13. Materials treated by means of process according to claim 8.
  14. Materials treated by means of process according to claim 9.
  15. Materials treated by means of process according to claim 10.
  16. Materials treated by means of process according to claim 11.
EP94203574A 1993-12-09 1994-12-07 Process for cleaning and conditioning the surface of an electrolytically oxidizable metal alloy by hyperanodizing said surface Expired - Lifetime EP0657564B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT93MI002585A IT1265263B1 (en) 1993-12-09 1993-12-09 WASHING AND SURFACE CONDITIONING PROCESS OBTAINED THROUGH A HYPER-ANODIZATION PROCESS OF OXIDABLE ALLOYS
ITMI932585 1993-12-09

Publications (2)

Publication Number Publication Date
EP0657564A1 true EP0657564A1 (en) 1995-06-14
EP0657564B1 EP0657564B1 (en) 1999-04-21

Family

ID=11367311

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94203574A Expired - Lifetime EP0657564B1 (en) 1993-12-09 1994-12-07 Process for cleaning and conditioning the surface of an electrolytically oxidizable metal alloy by hyperanodizing said surface

Country Status (5)

Country Link
EP (1) EP0657564B1 (en)
AT (1) ATE179228T1 (en)
DE (1) DE69418004T2 (en)
ES (1) ES2131632T3 (en)
IT (1) IT1265263B1 (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5700366A (en) * 1996-03-20 1997-12-23 Metal Technology, Inc. Electrolytic process for cleaning and coating electrically conducting surfaces
WO1997048839A1 (en) * 1996-06-17 1997-12-24 Alcan International Limited Treating aluminium workpieces
US5958604A (en) * 1996-03-20 1999-09-28 Metal Technology, Inc. Electrolytic process for cleaning and coating electrically conducting surfaces and product thereof
US5981084A (en) * 1996-03-20 1999-11-09 Metal Technology, Inc. Electrolytic process for cleaning electrically conducting surfaces and product thereof
CN102787346A (en) * 2012-07-31 2012-11-21 北京天艺创新科技有限公司 Coating film cleaning process for clean environment-friendly plasma

Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB517415A (en) * 1938-04-22 1940-01-30 Samuel Joseph Blaut Improvements in electrochemical treatment of metal
DE1021229B (en) * 1953-05-19 1957-12-19 Magnesium Elektron Ltd Application of the anodic treatment of alloys based on magnesium for the removal of molding sand contamination on castings made from such alloys
GB1071249A (en) * 1964-12-22 1967-06-07 Ruthner Ind Planungs Ag Scale removal
LU53840A1 (en) * 1966-06-10 1968-03-07
FR1544974A (en) * 1966-11-18 1968-11-08 Revere Copper & Brass Inc Process for treating sheet copper surfaces
US3756931A (en) * 1971-09-13 1973-09-04 Boer C De Electrolytic cleaning and corrosi on removal process
JPS5188435A (en) * 1975-02-03 1976-08-03 DENKAISENJOHO
EP0059527A1 (en) * 1981-02-27 1982-09-08 Allegheny Ludlum Steel Corporation High current density, acid-free electrolytic descaling process
JPS5855597A (en) * 1981-09-28 1983-04-01 Agency Of Ind Science & Technol Method for removing scale of sus304 stainless steel
US4397721A (en) * 1981-02-12 1983-08-09 Fokker B.V. Pickling of aluminum
JPS60140199A (en) * 1983-12-28 1985-07-25 日立プラント建設株式会社 Method of electrolytically decontaminating radioactive metallic waste
SU1244216A1 (en) * 1983-01-11 1986-07-15 Всесоюзный Ордена Трудового Красного Знамени Научно-Исследовательский Институт Сельскохозяйственного Машиностроения Им.В.П.Горячкина Method of cleaning metal parts
US4640752A (en) * 1985-10-28 1987-02-03 Engelhard Corporation Method for producing silver colored brazing alloy
JPH02182900A (en) * 1989-01-09 1990-07-17 Sky Alum Co Ltd Production of base material for printed circuit board
RU1798393C (en) * 1990-01-09 1993-02-28 Всесоюзный научно-исследовательский институт метизной промышленности Method for electrochemical cleaning of long-length steal products
DE4310749A1 (en) * 1993-04-01 1993-09-09 Siemens Ag Electrochemical decontamination of metal component using strongly alkaline electrolyte liq. - used to remove radioactive oxide layers from PWR and BWR components

Patent Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB517415A (en) * 1938-04-22 1940-01-30 Samuel Joseph Blaut Improvements in electrochemical treatment of metal
DE1021229B (en) * 1953-05-19 1957-12-19 Magnesium Elektron Ltd Application of the anodic treatment of alloys based on magnesium for the removal of molding sand contamination on castings made from such alloys
GB1071249A (en) * 1964-12-22 1967-06-07 Ruthner Ind Planungs Ag Scale removal
LU53840A1 (en) * 1966-06-10 1968-03-07
FR1544974A (en) * 1966-11-18 1968-11-08 Revere Copper & Brass Inc Process for treating sheet copper surfaces
US3756931A (en) * 1971-09-13 1973-09-04 Boer C De Electrolytic cleaning and corrosi on removal process
JPS5188435A (en) * 1975-02-03 1976-08-03 DENKAISENJOHO
US4397721A (en) * 1981-02-12 1983-08-09 Fokker B.V. Pickling of aluminum
EP0059527A1 (en) * 1981-02-27 1982-09-08 Allegheny Ludlum Steel Corporation High current density, acid-free electrolytic descaling process
JPS5855597A (en) * 1981-09-28 1983-04-01 Agency Of Ind Science & Technol Method for removing scale of sus304 stainless steel
SU1244216A1 (en) * 1983-01-11 1986-07-15 Всесоюзный Ордена Трудового Красного Знамени Научно-Исследовательский Институт Сельскохозяйственного Машиностроения Им.В.П.Горячкина Method of cleaning metal parts
JPS60140199A (en) * 1983-12-28 1985-07-25 日立プラント建設株式会社 Method of electrolytically decontaminating radioactive metallic waste
US4640752A (en) * 1985-10-28 1987-02-03 Engelhard Corporation Method for producing silver colored brazing alloy
JPH02182900A (en) * 1989-01-09 1990-07-17 Sky Alum Co Ltd Production of base material for printed circuit board
RU1798393C (en) * 1990-01-09 1993-02-28 Всесоюзный научно-исследовательский институт метизной промышленности Method for electrochemical cleaning of long-length steal products
DE4310749A1 (en) * 1993-04-01 1993-09-09 Siemens Ag Electrochemical decontamination of metal component using strongly alkaline electrolyte liq. - used to remove radioactive oxide layers from PWR and BWR components

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Derwent World Patents Index; AN 76-71063X *
DATABASE WPI Derwent World Patents Index; AN 85-219648 *
DATABASE WPI Derwent World Patents Index; AN 87-077758 *
DATABASE WPI Derwent World Patents Index; AN 94-149436 *
PATENT ABSTRACTS OF JAPAN vol. 14, no. 458 (C - 0766) *
PATENT ABSTRACTS OF JAPAN vol. 7, no. 143 (C - 172) *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5700366A (en) * 1996-03-20 1997-12-23 Metal Technology, Inc. Electrolytic process for cleaning and coating electrically conducting surfaces
US5958604A (en) * 1996-03-20 1999-09-28 Metal Technology, Inc. Electrolytic process for cleaning and coating electrically conducting surfaces and product thereof
US5981084A (en) * 1996-03-20 1999-11-09 Metal Technology, Inc. Electrolytic process for cleaning electrically conducting surfaces and product thereof
WO1997048839A1 (en) * 1996-06-17 1997-12-24 Alcan International Limited Treating aluminium workpieces
US6267870B1 (en) 1996-06-17 2001-07-31 Alcan International Limited Treating aluminum workpieces
CN102787346A (en) * 2012-07-31 2012-11-21 北京天艺创新科技有限公司 Coating film cleaning process for clean environment-friendly plasma
CN102787346B (en) * 2012-07-31 2015-12-02 沙福国 Plasma cleaning process before clean and environment-friendly plated film

Also Published As

Publication number Publication date
EP0657564B1 (en) 1999-04-21
ATE179228T1 (en) 1999-05-15
DE69418004T2 (en) 1999-10-21
IT1265263B1 (en) 1996-10-31
ES2131632T3 (en) 1999-08-01
ITMI932585A0 (en) 1993-12-09
DE69418004D1 (en) 1999-05-27
ITMI932585A1 (en) 1995-06-09

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