EP4177376A1 - Metal displacement solution and corresponding method for surface treatment of aluminum or aluminum alloy - Google Patents

Metal displacement solution and corresponding method for surface treatment of aluminum or aluminum alloy Download PDF

Info

Publication number
EP4177376A1
EP4177376A1 EP22204326.7A EP22204326A EP4177376A1 EP 4177376 A1 EP4177376 A1 EP 4177376A1 EP 22204326 A EP22204326 A EP 22204326A EP 4177376 A1 EP4177376 A1 EP 4177376A1
Authority
EP
European Patent Office
Prior art keywords
aluminum
metal
displacement solution
compound
metal displacement
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.)
Pending
Application number
EP22204326.7A
Other languages
German (de)
English (en)
French (fr)
Inventor
Takuma Maekawa
Katsuhisa Tanabe
Sayuri Tanaka
Fuminori Shibayama
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.)
Uemera Kogyo Co Ltd
C Uyemura and Co Ltd
Original Assignee
Uemera Kogyo Co Ltd
C Uyemura and Co Ltd
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 Uemera Kogyo Co Ltd, C Uyemura and Co Ltd filed Critical Uemera Kogyo Co Ltd
Publication of EP4177376A1 publication Critical patent/EP4177376A1/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/48—Coating with alloys
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/54—Contact plating, i.e. electroless electrochemical plating
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
    • C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/08—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of metallic material
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
    • C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
    • C23C18/1827—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment only one step pretreatment
    • C23C18/1831—Use of metal, e.g. activation, sensitisation with noble metals
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
    • C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
    • C23C18/1837—Multistep pretreatment
    • C23C18/1841—Multistep pretreatment with use of metal first
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
    • 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
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/20—Acidic compositions for etching aluminium or alloys thereof
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/12—Light metals
    • C23G1/125—Light metals aluminium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated
    • C25D5/42—Pretreatment of metallic surfaces to be electroplated of light metals
    • C25D5/44—Aluminium

Definitions

  • the present invention relates to a metal displacement solution and a method for surface treatment of aluminum or an aluminum alloy.
  • Aluminum readily forms an oxide film in the air or water. It is known that when aluminum or an aluminum alloy is subjected to plating, the plating film has low adhesion due to such an oxide film. Hence, zinc displacement (zincate treatment) has been performed prior to plating in order to remove the oxide film on the aluminum or aluminum alloy surface and thereby ensure adhesion to a plating film to be formed on the aluminum (e.g., Patent Literatures 1 to 3 and Non-Patent Literatures 1 to 3).
  • the present invention aims to solve the problem newly found by the present inventors and provide a metal displacement solution that can provide good adhesion to a plating film (metal film), and a method for surface treatment of aluminum or an aluminum alloy using the metal displacement solution.
  • the present invention relates to a metal displacement solution, containing:
  • the metal displacement solution contains the zinc compound in an amount corresponding to a zinc concentration of 0.2 to 5.0 g/L.
  • the metal displacement solution contains the nickel compound in an amount corresponding to a nickel concentration of 0.2 to 10 g/L.
  • the metal displacement solution contains the germanium compound in an amount corresponding to a germanium concentration of 0.2 to 5.0 g/L.
  • the metal displacement solution contains the fluorine compound in an amount corresponding to a fluorine concentration of 5.0 to 50 g/L.
  • the metal displacement solution has a ratio of zinc concentration to germanium concentration of 1:5 to 5:1.
  • the metal displacement solution has a pH of 4.0 to 6.5.
  • the metal displacement solution is for treating aluminum or an aluminum alloy.
  • the present invention also relates to a method for surface treatment of aluminum or an aluminum alloy, the method including: bringing a workpiece having aluminum or an aluminum alloy on its surface into contact with the metal displacement solution to remove an oxide film on the aluminum or aluminum alloy and displace the aluminum with the metals in the metal displacement solution to form a displacement metal film containing the metals on the surface of the workpiece.
  • the method includes, after forming the displacement metal film, forming a plating film on a surface of the displacement metal film.
  • the metal displacement solution according to the present invention contains a zinc compound, a nickel compound, a germanium compound, and a fluorine compound and thus can provide good adhesion to a plating film (metal film).
  • the metal displacement solution of the present invention contains a zinc compound, a nickel compound, a germanium compound, and a fluorine compound. This can provide good adhesion to a plating film (metal film).
  • zinc (Zn) may co-deposit with nickel (Ni) and germanium (Ge) to form a displacement metal film containing Zn, Ni, and Ge on a surface of the aluminum or aluminum alloy.
  • the Zn, Ni, and Ge present in the displacement metal film may act synergistically between the aluminum or aluminum alloy and the plating film (metal film, e.g., nickel film), thereby providing good adhesion to the plating film (metal film) to the aluminum or aluminum alloy.
  • the metal displacement solution of the present invention contains a zinc compound, a nickel compound, a germanium compound, and a fluorine compound.
  • the zinc compound is not limited as long as it is a water-soluble zinc compound. Specific examples include zinc sulfate, zinc nitrate, zinc chloride, zinc acetate, zinc oxide, and zinc gluconate. These may be used alone or in combinations of two or more. Preferred among these is zinc sulfate.
  • the metal displacement solution preferably contains at least one zinc compound in an amount corresponding to a zinc (metallic zinc (Zn)) concentration of 0.1 to 7.0 g/L, more preferably 0.2 to 5.0 g/L, still more preferably 0.2 to 4.0 g/L.
  • Zn metal zinc
  • the nickel compound is not limited as long as it is a water-soluble nickel compound. Specific examples include nickel sulfate, nickel nitrate, nickel chloride, nickel acetate, and nickel gluconate. These may be used alone or in combinations of two or more. Preferred among these is nickel sulfate.
  • the metal displacement solution preferably contains at least one nickel compound in an amount corresponding to a nickel (metallic nickel (Ni)) concentration of 0.1 to 12 g/L, more preferably 0.2 to 10 g/L.
  • Ni nickel
  • concentration of lower than 0.1 g/L the co-deposition with Zn tends to be reduced, failing to ensure sufficient adhesion.
  • concentration of higher than 12 g/L the co-deposition with Zn tends to be excessive, failing to ensure sufficient adhesion.
  • the germanium compound is not limited as long as it is a water-soluble germanium compound. Specific examples include germanium dioxide, germanium sulfate, germanium sulfide, germanium fluoride, germanium chloride, and germanium iodide. These may be used alone or in combinations of two or more. Preferred among these is germanium dioxide.
  • a compound that corresponds to both a germanium compound and a fluorine compound, such as germanium fluoride is regarded as a germanium compound.
  • a zinc compound and a nickel compound are also regarded as a zinc compound and a nickel compound, respectively.
  • the metal displacement solution preferably contains at least one germanium compound in an amount corresponding to a germanium (metallic germanium (Ge)) concentration of 0.1 to 7.0 g/L, more preferably 0.2 to 5.0 g/L.
  • a germanium (metallic germanium (Ge)) concentration of 0.1 to 7.0 g/L, more preferably 0.2 to 5.0 g/L.
  • the ratio of the zinc concentration to the germanium concentration is preferably 1:5 to 5:1.
  • the fluorine compound dissolves aluminum from the oxide film on the aluminum or aluminum alloy surface to allow it to be smoothly displaced with the metals such as zinc.
  • fluorine compound examples include hydrofluoboric acid, sodium fluoride, potassium fluoride, ammonium hydrogen fluoride, ammonium fluoride, hydrogen fluoride, and lithium fluoride. These may be used alone or in combinations of two or more. Preferred among these are hydrofluoboric acid, sodium fluoride, potassium fluoride, ammonium hydrogen fluoride, ammonium fluoride, and hydrogen fluoride, with hydrofluoboric acid, sodium fluoride, potassium fluoride, ammonium hydrogen fluoride, and ammonium fluoride being more preferred.
  • the metal displacement solution preferably contains at least one fluorine compound in an amount corresponding to a fluorine (F) concentration of 1.0 to 100 g/L, more preferably 5.0 to 50 g/L.
  • F fluorine
  • concentration of lower than 1.0 g/L the aluminum-dissolving action tends to be lowered, failing to ensure sufficient adhesion.
  • concentration of higher than 100 g/L excess aluminum tends to be dissolved, failing to ensure sufficient adhesion.
  • the zinc (metallic zinc (Zn)) concentration, nickel (metallic nickel (Ni)) concentration, and germanium (metallic germanium (Ge)) concentration in the metal displacement solution are measured by ICP (HORIBA, Ltd.).
  • the fluorine (F) concentration in the metal displacement solution is measured using a fluorine ion electrode.
  • the pH of the metal displacement solution is preferably 1.0 to 12.0, more preferably 2.0 to 10.0.
  • the metal displacement solution of the present invention may be used under either alkaline or acidic conditions.
  • excess aluminum may be eluted under alkaline conditions (e.g., Fig. 9 of Non-Patent Literature 3), which tends to form aluminum spikes, while under acidic conditions, no elution of excess aluminum occurs, but sufficient adhesion tends not to be ensured.
  • the metal displacement solution of the present invention even under acidic conditions, can ensure sufficient adhesion, and a more significant effect on improving adhesion is obtained when it is used under acidic conditions. Further, as no elution of excess aluminum occurs under acidic conditions, it is also possible to reduce aluminum spikes. However, when the pH is lower than 3.5, excess aluminum may be eluted.
  • the pH of the metal displacement solution is still more preferably 3.5 to 6.5, particularly preferably 4.0 to 6.5, most preferably 4.5 to 6.5.
  • a more significant effect on improving adhesion is obtained as described above, and it is also possible to reduce aluminum spikes as no elution of excess aluminum occurs.
  • excess aluminum is eluted to form aluminum spikes, many wedge-shaped depressions are formed on the aluminum surface, and in the subsequent plating film formation step, for example, a nickel plating may enter the depressions so that a plating film having poor smoothness is formed, which also affects the conductivity and greatly impairs the appearance.
  • the reduction of aluminum spikes enables the formation of a plating film having high smoothness and excellent plating appearance.
  • the pH of the metal displacement solution is measured at 25°C.
  • the pH of the metal displacement solution may be adjusted by selecting the type of the zinc compound, nickel compound, germanium compound, or fluorine compound.
  • An alkaline component or an acid component may also be added as necessary.
  • Non-limiting examples of the alkaline component include sodium hydroxide and ammonium.
  • Non-limiting examples of the acid component include sulfuric acid and phosphoric acid. These alkaline or acid components may be used alone or in combinations of two or more.
  • the metal displacement solution may contain a buffer to enhance the pH buffering capacity.
  • the buffer may be any compound having a buffering capacity, and examples of compounds having a buffering capacity around a pH of 4.0 to 6.5 include acetic acid, malic acid, succinic acid, citric acid, malonic acid, lactic acid, oxalic acid, glutaric acid, adipic acid, and formic acid. These may be used alone or in combinations of two or more.
  • the buffer concentration in the metal displacement solution is preferably 1.0 to 50 g/L, more preferably 5.0 to 30 g/L.
  • the metal displacement solution may contain, in addition to the above-described components, components that are generally used in metal displacement solutions, such as surfactants and brightening agents.
  • the metal displacement solution may also contain water-soluble salts of metals other than the above-described metals, such as iron, copper, silver, palladium, lead, bismuth, and thallium. These may be used alone or in combinations of two or more.
  • the metal displacement solution can be prepared by appropriately mixing the components using a solvent, preferably water.
  • a solvent preferably water.
  • other solvents such as methanol, ethanol, ethylene glycol, diethylene glycol, triethylene glycol, glycerol, or IPA may be used, or they may be used as a solvent mixture with water.
  • these solvents may be used alone or in combinations of two or more.
  • the metal displacement solution can be suitably used as a metal displacement solution for treating aluminum or an aluminum alloy.
  • the following describes a method for surface treatment of aluminum or an aluminum alloy of the present invention using the metal displacement solution of the present invention.
  • the method for surface treatment of aluminum or an aluminum alloy of the present invention includes bringing a workpiece having aluminum or an aluminum alloy on its surface into contact with the metal displacement solution of the present invention to remove the oxide film on the aluminum or aluminum alloy and displace the aluminum with the metals in the metal displacement solution to form a displacement metal film containing the metals on the surface of the workpiece.
  • the surface treatment method includes a pretreatment method prior to forming a plating film such as a nickel or palladium plating film on a workpiece.
  • This method brings a workpiece having aluminum or an aluminum alloy at least on its surface into contact with the metal displacement solution of the present invention to remove the oxide film adhered to the surface and form a displacement metal film, thereby increasing adhesion to a nickel plating film or other plating film to be formed in the subsequent treatment.
  • the metal displacement solution of the present invention removes the oxide film adhered to a workpiece (hereinafter also referred to as "aluminum substrate") having aluminum or an aluminum alloy at least on its surface, and allows the zinc, nickel, and germanium particles to deposit on the surface of the workpiece via a displacement reaction between the metals such as zinc and the aluminum which have different electrode potentials.
  • aluminum substrate aluminum or an aluminum alloy at least on its surface
  • a double zincate process is performed in which zinc displacement is performed twice.
  • the process includes: (1) a first zinc displacement of an aluminum substrate, (2) pickling, and then (3) a second zinc displacement.
  • the double zincate treatment is followed by (4) plating such as electroless nickel plating.
  • the method for surface treatment of aluminum or an aluminum alloy of the present invention using the metal displacement solution of the present invention requires no double zincate treatment and can provide good adhesion by a single zincate treatment.
  • (1) metal displacement of an aluminum substrate is performed, and this single zincate treatment is followed by (4) plating such as electroless nickel plating.
  • (2) pickling followed by (3) a second metal displacement are not performed between the metal displacement and the plating.
  • the aluminum substrate which is a workpiece to be plated, may be any substrate that has aluminum or an aluminum alloy at least on its surface.
  • Examples of such aluminum substrates include various articles made of aluminum or aluminum alloys, articles in which an aluminum or aluminum alloy film is formed on a non-aluminum material (e.g., various substrates such as ceramic substrates and wafers), hot-dip aluminized articles, castings, and die castings.
  • the aluminum substrate may also have any shape and may be in the form of a typical plate (including a film, a sheet, or other thin film) or in the form of any formed article of any of various shapes.
  • the plate is not limited to a plate made of aluminum or an aluminum alloy alone, and may include, for example, an aluminum film that is formed on (integrated with) a substrate such as a ceramic substrate or a wafer by sputtering, vacuum deposition, ion plating, or other conventional techniques.
  • the aluminum alloy may be, but is not limited to, for example, any of various alloys containing aluminum as a main metal component.
  • applicable alloys include A1000 series quasi-aluminum, A2000 series aluminum alloys containing copper and manganese, A3000 series aluminum-manganese alloys, A4000 series aluminum-silicon alloys, A5000 series aluminum-magnesium alloys, A6000 series aluminum-magnesium-silicon alloys, A7000 series aluminum-zinc-magnesium alloys, and A8000 series aluminum-lithium alloys.
  • the aluminum purity of the aluminum or aluminum alloy is preferably 98% or higher, more preferably 98.5% or higher, still more preferably 99% or higher, from the standpoint of plating smoothness.
  • the aluminum substrate which is a workpiece to be plated, can be prepared by coating a non-aluminum material such as a silicon plate with an aluminum layer using well-known techniques such as sputtering.
  • the aluminum layer may fully or partially coat the non-aluminum material, and the coated aluminum layer usually has a thickness of 0.5 ⁇ m or more, preferably 1 ⁇ m or more.
  • the method for preparing the aluminum substrate is not limited to sputtering and may include vacuum deposition, ion plating, or other techniques.
  • the thus-prepared aluminum substrate may be cleaned in a well-known manner, for example, by degreasing, rinsed with water as appropriate, and then subjected to a well-known etching process using alkali or acid.
  • the degreasing process may be carried out by immersion in a degreasing solution for aluminum or by electrolytic degreasing.
  • the etching process may be carried out, for example, by immersion in an about 1-10% alkaline solution or an about 1-20% acidic solution having a liquid temperature of about 25 to 75°C for about 1 to 15 minutes.
  • the aluminum substrate may be immersed in an acidic solution for a predetermined period of time in order to remove the residues (smuts) produced by etching using alkali or acid.
  • the aluminum substrate after etching may be immersed in an aqueous nitric acid solution having a concentration in the range of about 10 to 800 ml/L, preferably about 100 to 600 ml/L and a liquid temperature of about 15 to 35°C for about 30 seconds to 2 minutes to remove the smuts.
  • the thus-treated (e.g., desmutted) aluminum substrate may be rinsed with water and then immersed in the metal displacement solution of the present invention (zincate treatment solution) to perform metal displacement.
  • the aluminum substrate may be immersed in a zincate treatment solution having the composition described above and a liquid temperature of 10 to 50°C, preferably 15 to 30°C. This liquid temperature is preferred because when the temperature of the zincate treatment solution is 10°C or higher, the displacement reaction does not become too slow and a metal film without irregularities can be formed, while when the temperature is 50°C or lower, the displacement reaction is not excessively enhanced and the surface of the displacement metal film can be prevented from becoming rough.
  • the conditions of the immersion period are not limited and can be set appropriately in consideration of, for example, the thickness of the aluminum oxide film to be removed.
  • the immersion period is usually about five seconds or longer, preferably 10 seconds or longer, and the upper limit thereof is five minutes or shorter. With too short an immersion period, the displacement does not proceed enough to cause sufficient removal of the oxide film, while with too long an immersion period, the treatment solution may penetrate through the small holes in the displacement metal layer to cause elution of the aluminum or aluminum alloy. Thus, the conditions need to be set in consideration of these points.
  • Such immersion of the aluminum substrate in the zincate treatment solution makes it possible to remove the oxide film adhered to the substrate surface and also to further coat the surface with a displacement metal film containing Zn, Ni, and Ge to activate the aluminum surface, thereby enabling the formation of a plating film having good adhesion to the workpiece.
  • the metal displacement process is not limited as long as it is an embodiment in which the surface of the aluminum substrate can be brought into contact with the metal displacement solution of the present invention.
  • Examples of such contact methods include, in addition to immersion, application and spraying.
  • the plating process may be carried out by electroless plating or electrolytic plating on the zincated aluminum substrate.
  • an appropriate metal plating solution such as an electroless nickel plating, electroless palladium plating, or copper plating bath may be used to form a plating having a desired final film thickness.
  • an electroless nickel plating solution contains a water-soluble nickel salt such as nickel sulfate, nickel chloride, or nickel acetate, which provides nickel ions at a concentration of, for example, about 1 to 10 g/L.
  • the electroless nickel plating solution may further contain, for example: a nickel complexing agent such as an organic acid salt (e.g., acetate, succinate, or citrate), an ammonium salt, or an amine salt at a concentration in the range of about 20 to 80 g/L; and hypophosphorous acid or a hypophosphite such as sodium hypophosphite as a reducing agent at a concentration in the range of about 10 to 40 g/L.
  • a nickel complexing agent such as an organic acid salt (e.g., acetate, succinate, or citrate), an ammonium salt, or an amine salt at a concentration in the range of about 20 to 80 g/L
  • hypophosphorous acid or a hypophosphite such as sodium hypopho
  • the plating solution containing these compounds may be prepared to have a pH of about 4 to 7 before use. Further, this plating solution may be prepared to have a liquid temperature of 60 to 95°C, and the aluminum substrate may be immersed in the plating solution for about 15 seconds to 120 minutes to perform plating. Moreover, the thickness of the plating film can be varied by changing this plating period as appropriate.
  • the plating process is not limited to electroless plating and may be carried out by electrolytic plating, as described above. Besides the above-mentioned types of metals, other plating metals such as Cu and Au may also be used. Moreover, the plating process may be performed by displacement plating or other techniques to form two or more layers.
  • a workpiece having aluminum or an aluminum alloy on its surface is brought into contact with the metal displacement solution of the present invention to remove the oxide film on the aluminum or aluminum alloy and displace the aluminum with the metals in the metal displacement solution.
  • Zn may co-deposit with Ni and Ge to form a displacement metal film containing Zn, Ni, and Ge on a surface of the aluminum or aluminum alloy.
  • the Zn, Ni, and Ge present in the displacement metal film may act synergistically between the aluminum or aluminum alloy and the plating film (metal film, e.g., nickel film), thereby providing good adhesion to the plating film (metal film) to the aluminum or aluminum alloy.
  • the aluminum or aluminum alloy provided with a plating film (metal film) according to the present invention can be used in various electronic components.
  • the electronic components include electronic components used in home appliances, in-vehicle equipment, power transmission systems, transportation equipment, and communication equipment.
  • Specific examples include power modules such as power control units for air conditioners, elevators, electric vehicles, hybrid vehicles, trains, and power generation equipment, general home appliances, and personal computers.
  • the present invention when the metal displacement solution has a pH of 4.0 to 6.5, pre-plating treatment can be performed to also reduce aluminum spikes and form a plating film having high smoothness and excellent plating appearance.
  • the present invention is suitable for semiconductor applications, preferably for wafer applications.
  • the present invention is suitable as a metal displacement solution for treating aluminum or an aluminum alloy which is effective for pretreatment prior to forming an under-bump metal or bump on a wafer, or as a method for surface treatment of aluminum or an aluminum alloy using the metal displacement solution.
  • An aluminum substrate was subjected to the treatments according to the conditions shown in Tables 1 to 3 to form a plating film.
  • a 1 cm ⁇ 2 cm Al-Cu TEG wafer was used as the aluminum substrate.
  • the thus-prepared plating films and substrates provided with the plating films were evaluated as described below. The evaluation results are shown in Tables 2 and 3.
  • Each of the substrates provided with the plating films was dried by air-blowing, and cellophane tape was put on the plated surface. Then, the center of the wafer with the tape was cut and broken into two pieces. The tape was peeled off from the broken center, and the amount of removal between the Al substrate and the Ni film was determined in percentage.
  • the cutting and breaking test is schematically illustrated in Fig. 1 .
  • Fig. 2(a) shows an exemplary case where no Al spikes are observed
  • Fig. 2(b) shows an exemplary case where Al spikes are observed.
  • a case where no Al spikes are observed as shown in Fig. 2(a) is considered good.
  • Tables 2 and 3 show that the metal displacement solutions of the examples containing a zinc compound, a nickel compound, a germanium compound, and a fluorine compound provided good adhesion to a plating film (metal film). It is also shown that the metal displacement solutions having a pH of 3.5 to 6.5 also reduced aluminum spikes.
  • Tables 2 and 3 show the results when an Al-Cu TEG wafer was used as the aluminum substrate, similar results were also obtained when an Al-Si TEG wafer was used as the aluminum substrate.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Chemically Coating (AREA)
  • Electroplating Methods And Accessories (AREA)
EP22204326.7A 2021-11-08 2022-10-28 Metal displacement solution and corresponding method for surface treatment of aluminum or aluminum alloy Pending EP4177376A1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2021182009A JP2023069841A (ja) 2021-11-08 2021-11-08 金属置換処理液、アルミニウム又はアルミニウム合金の表面処理方法

Publications (1)

Publication Number Publication Date
EP4177376A1 true EP4177376A1 (en) 2023-05-10

Family

ID=82512418

Family Applications (1)

Application Number Title Priority Date Filing Date
EP22204326.7A Pending EP4177376A1 (en) 2021-11-08 2022-10-28 Metal displacement solution and corresponding method for surface treatment of aluminum or aluminum alloy

Country Status (6)

Country Link
US (1) US20230151493A1 (zh)
EP (1) EP4177376A1 (zh)
JP (1) JP2023069841A (zh)
KR (1) KR20230067550A (zh)
CN (1) CN114807918A (zh)
TW (1) TW202336272A (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4293136A1 (en) * 2022-06-16 2023-12-20 C. Uyemura & Co., Ltd. Etchant and method of surface treatment of aluminum or aluminum alloy

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3930081A (en) * 1972-11-06 1975-12-30 Oxy Metal Industries Corp Composition and process for displacement plating of zinc surfaces
JP2000256864A (ja) 1999-03-05 2000-09-19 Okuno Chem Ind Co Ltd アルミニウム又はアルミニウム合金表面の亜鉛置換方法、そのための置換液及び亜鉛置換皮膜を有するアルミニウム又はアルミニウム合金
US20050008788A1 (en) * 2003-06-26 2005-01-13 Joshi Nayan H. Aqueous acidic immersion plating solutions and methods for plating on aluminum and aluminum alloys
JP2009127101A (ja) 2007-11-26 2009-06-11 C Uyemura & Co Ltd アルミニウム又はアルミニウム合金上の金属置換処理液及びこれを用いた表面処理方法
JP2010163640A (ja) * 2009-01-13 2010-07-29 Nippon Parkerizing Co Ltd 金属表面処理用処理液、金属表面処理方法および金属材料
JP2020196914A (ja) 2019-05-31 2020-12-10 奥野製薬工業株式会社 めっき前処理方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07188971A (ja) * 1993-12-28 1995-07-25 Nkk Corp アルミニウムおよびアルミニウム合金板の亜鉛系めっき 方法
JP2001026896A (ja) * 1999-07-16 2001-01-30 Nisshin Steel Co Ltd 表面処理金属板
JP5136746B2 (ja) * 2007-01-12 2013-02-06 上村工業株式会社 アルミニウム又はアルミニウム合金の表面処理方法
JP4605409B2 (ja) * 2008-08-21 2011-01-05 上村工業株式会社 アルミニウム又はアルミニウム合金の表面処理方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3930081A (en) * 1972-11-06 1975-12-30 Oxy Metal Industries Corp Composition and process for displacement plating of zinc surfaces
JP2000256864A (ja) 1999-03-05 2000-09-19 Okuno Chem Ind Co Ltd アルミニウム又はアルミニウム合金表面の亜鉛置換方法、そのための置換液及び亜鉛置換皮膜を有するアルミニウム又はアルミニウム合金
US20050008788A1 (en) * 2003-06-26 2005-01-13 Joshi Nayan H. Aqueous acidic immersion plating solutions and methods for plating on aluminum and aluminum alloys
JP2009127101A (ja) 2007-11-26 2009-06-11 C Uyemura & Co Ltd アルミニウム又はアルミニウム合金上の金属置換処理液及びこれを用いた表面処理方法
JP2010163640A (ja) * 2009-01-13 2010-07-29 Nippon Parkerizing Co Ltd 金属表面処理用処理液、金属表面処理方法および金属材料
JP2020196914A (ja) 2019-05-31 2020-12-10 奥野製薬工業株式会社 めっき前処理方法

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
JOURNAL OF THE SURFACE FINISHING SOCIETY OF JAPAN, vol. 47, no. 9, 1996, pages 802 - 807
JOURNAL OF THE SURFACE FINISHING SOCIETY OF JAPAN, vol. 64, no. 12, 2013, pages 645 - 649
JOURNAL OF THE SURFACE FINISHING SOCIETY OF JAPAN, vol. 66, no. 12, 2015, pages 658 - 665

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4293136A1 (en) * 2022-06-16 2023-12-20 C. Uyemura & Co., Ltd. Etchant and method of surface treatment of aluminum or aluminum alloy

Also Published As

Publication number Publication date
KR20230067550A (ko) 2023-05-16
TW202336272A (zh) 2023-09-16
CN114807918A (zh) 2022-07-29
US20230151493A1 (en) 2023-05-18
JP2023069841A (ja) 2023-05-18

Similar Documents

Publication Publication Date Title
US8414711B2 (en) Method of surface treatment for aluminum or aluminum alloy
US9139915B2 (en) Solution for removing aluminum oxide film and method for surface treatment of aluminum or aluminum alloy
US8163400B2 (en) Plated article having metal thin film formed by electroless plating, and manufacturing method thereof
US8394508B2 (en) Plated article having metal thin film formed by electroless plating
WO2014207975A1 (ja) めっき材の製造方法及びめっき材
TW201213606A (en) Aluminum oxide film remover and method for surface treatment of aluminum or aluminum alloy
KR20090054379A (ko) 알루미늄 또는 알루미늄 합금 상의 금속 치환 처리액 및 이것을 사용한 표면처리 방법
EP4177376A1 (en) Metal displacement solution and corresponding method for surface treatment of aluminum or aluminum alloy
KR102280838B1 (ko) 추가 금속의 존재 하에 구리를 선택적으로 처리하는 방법
MX2013003935A (es) Proceso para deposicion por via quimica de metales utilizando baño de chapado altamente alcalino.
US20160108254A1 (en) Zinc immersion coating solutions, double-zincate method, method of forming a metal plating film, and semiconductor device
EP4293136A1 (en) Etchant and method of surface treatment of aluminum or aluminum alloy
CN117248215A (zh) 蚀刻处理液、铝或铝合金的表面处理方法
JP2023184437A (ja) エッチング処理液、アルミニウム又はアルミニウム合金の表面処理方法
JP2001262390A (ja) パラジウムめっき液
KR100752504B1 (ko) 무전해 도금을 이용한 패턴 내 금속배선 형성방법
JPH08158060A (ja) アルミニウムの無電解ニッケルめっき方法
US20130216721A1 (en) Process for Electroless Deposition on Magnesium Using a Nickel Hydrate Plating Bath
US8231743B2 (en) Composition and process for improved zincating magnesium and magnesium alloy substrates
JP2022183021A (ja) 無電解Ｃｏ－Ｗめっき皮膜、および無電解Ｃｏ－Ｗめっき液
JP4475282B2 (ja) 無電解金めっき液及び無電解金めっき方法
JPH0715149B2 (ja) 耐糸▲錆▼性に優れたアルミニウム板

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

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

Free format text: STATUS: THE APPLICATION HAS BEEN PUBLISHED

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC ME MK MT NL NO PL PT RO RS SE SI SK SM TR

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

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20230919

RBV Designated contracting states (corrected)

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC ME MK MT NL NO PL PT RO RS SE SI SK SM TR