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US3915811A - Method and composition for electroplating aluminum alloys - Google Patents

Method and composition for electroplating aluminum alloys Download PDF

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Publication number
US3915811A
US3915811A US515129A US51512974A US3915811A US 3915811 A US3915811 A US 3915811A US 515129 A US515129 A US 515129A US 51512974 A US51512974 A US 51512974A US 3915811 A US3915811 A US 3915811A
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acid
article
acetic acid
anodizing
weight
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US515129A
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Robert A Tremmel
Walter J Wieczerniak
Richard J Clauss
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OMI International Corp
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Oxy Metal Industries Corp
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Priority to US515129A priority Critical patent/US3915811A/en
Priority to CA223,195A priority patent/CA1043287A/en
Priority to FR7510318A priority patent/FR2288164A1/en
Priority to ES436285A priority patent/ES436285A1/en
Priority to SE7503826A priority patent/SE7503826L/en
Priority to IT48953/75A priority patent/IT1035197B/en
Priority to DE19752517779 priority patent/DE2517779A1/en
Priority to NL7504952A priority patent/NL7504952A/en
Priority to GB22802/75A priority patent/GB1506184A/en
Priority to BR4181/75A priority patent/BR7503268A/en
Priority to JP50071382A priority patent/JPS5147549A/ja
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Assigned to HOOKER CHEMICALS & PLASTICS CORP. reassignment HOOKER CHEMICALS & PLASTICS CORP. MERGER (SEE DOCUMENT FOR DETAILS). Assignors: OXY METAL INDUSTRIES CORPORATION
Assigned to OCCIDENTAL CHEMICAL CORPORATION reassignment OCCIDENTAL CHEMICAL CORPORATION CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). EFFECTIVE MARCH 30, 1982. Assignors: HOOKER CHEMICAS & PLASTICS CORP.
Assigned to OMI INTERNATIONAL CORPORATION reassignment OMI INTERNATIONAL CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: OCCIDENTAL CHEMICAL CORPORATION
Assigned to MANUFACTURERS HANOVER TRUST COMPANY, A CORP OF reassignment MANUFACTURERS HANOVER TRUST COMPANY, A CORP OF SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: INTERNATIONAL CORPORATION, A CORP OF DE
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used

Definitions

  • ABSTRACT A method of and a bath composition for conditioning the surface of an aluminum alloy article to substantially increase the adhesion to the conditioned surface of subsequently applied electrodeposited surface layer. More specifically the surface of the article is anodized in a solution having three components, i.e. phosphoric acid, sulfuric acid and an organic acid selected from the group consisting of acetic acid, hydroxy acetic acid and amino acetic acid (glycine).
  • the anodizing operation typically is followed by a nickel strike deposit, and this deposit may be subsequently electroplated under conventional operating conditions.
  • bumpers and other exterior automotive components be made from aluminum alloys, particularly alloys from the 7000 series.
  • Such alloys generally have the following typical analyses:
  • Such aluminum alloy components must be finished by electroplating with nickel-chromium or similar bright plating. Yet conventional electroplating techniques do not form completely adherent electrodeposited layers on such alloys.
  • adherent electrodeposited layers can be formed on such alloys by initially anodizing the aluminum surface in an anodizing bath containing a mixture of phosphoric acid, sulfuric acid, and an organic acid.
  • the surface of the aluminum alloy which is to be electroplated is first cleaned, acid etched and then rinsed.
  • the article surface is anodized in a three component bath containing from about to about 12% H PO plus from about 0.4% to about 2.0% H 50 plus from about 1% to about 7% of an aliphatic mono carboxylic acid or a hydroxy or amino derivative of such an acid having a solubility of at least 10 grams per liter in the inorganic acid mixture.
  • the three component bath contains, as a preferred ingredient, and in addition to the phosphoric acid and the sulfuric acid, from about 1% to about 7% of an organic acid selected from the group consisting of acetic acid, hydroxy acetic acid, and amino acetic acid.
  • anodizing treatment proposed by the present invention is a preliminary or conditioning treatment intended primarily for utilization as an undercoating for a subsequently applied electrodeposited final layer or coating.
  • the present treatment differs substantially from the earlier proposed anodizing treatments which are intended to form integral colored anodic coatings on the surface of aluminum or its alloys.
  • a final hard coat is provided by anodizing aluminum or its alloys in a bath containing a mineral acid, an organic acid, and organic acid salts.
  • mixtures of either sulfuric acid or phosphoric acid together with certain organic acids have been proposed to achieve a hard, dense, anodic coating as a final surface treatment in U.S. Pat. No. 3,524,799.
  • the baths are utilized as totally different concentrations than in the present invention and for entirely different purposes. Also it has been proposed in US. Pat. No. 3,349,014
  • the anodizing conditions of the present invention typically carry out the treatment at a temperature of from about to about F., at a voltage of from 25 to 30 volts and at a current density of from about 15 to about .20 amperes per square foot for a period of time of from about 5 to about 10 minutes.
  • the surface is subsequently plated with nickel and chromium or with any other surface treatment which may be desired.
  • the surface may be plated with one mil of semi-bright nickel, 0.5 mils of bright nickel, or 0.01 mils of chromium.
  • the resulting deposit is uniformly bright and smooth, and the adhesion of the final electrodeposition to the surface is excellent.
  • Another important object of the present invention is to provide a bath composition for subjecting an aluminum surface to a pre-electrodeposition treatment, the bath containing from about 5% to about 12% phosphoric acid, from about 0.4 to about 2% sulfuric acid, and from about 1 to about 7% of an organic acid selected from the group consisting of aliphatic mono carboxylic acids, hydroxy derivatives and amino derivatives of such acids having a solubility of at least 10 grams per liter in the phosphoric and sulfuric acid mixture.
  • the present invention proposes a specific anodizing treatment for aluminum alloys as a pre-treatment for a subsequent plating operation. It has been found that such initial anodizing greatly increases the adherence of the subsequently applied electrodeposit to the underlying aluminum alloy surface.
  • the anodizing solution consists of three components, namely phosphoric acid (H PO at a concentration of from 5 to about 12%, and at a preferred concentration of about 7%.
  • the second ingredient is sulfuric acid (H 80 at a concentration ranging from about 0.4% to about 2% and at a preferred concentration of about 1%.
  • the third ingredient is a saturated aliphatic mono carboxylic acid or a hydroxy derivative of such an acid or an amino derivative of such an acid, any one of these third ingredients necessarily having a solubility of at least 10 grams per liter in the acid solution.
  • Preferred specific saturated aliphatic mono carboxylic acids and derivatives are acetic acid (CI-I COOH), hydroxy acetic acid (l-IOCI-I COOI-I) and glycine or amino acetic acid (Nl-I Cl-I COOI-I).
  • the saturated aliphatic mono carboxylic acid or its derivative is present in an amount ranging from about 1% to about 7% of the solution with a preferred composition containing about 3.5%.
  • the anodizing operation is carried out under operating conditions which generally include a temperature of from about 100F. to about 110F., and preferably 105F.; at a voltage of from about 25 to 30 volts; at a current density of from about to about amperes per square foot, and for a period of time of from about 5 to about 10 minutes, preferably for a period of about 7 to 8 minutes.
  • the surface must be initially cleaned, which can be carried out by either soaking or by power spraying with an alkaline solution or by any other preferred cleaning method.
  • the surface is rinsed and preferably is acid etched. This etching is carried out at room temperature for a sufficient period of time, on the order of 1.5 to 2 minutes and the etching solution preferably contains 50% by volume nitric acid (HNO and 50 grams per liter of ammonium bifluoride (Nl-I F-HF).
  • the article to be anodized, after cleaning and etching, is immersed in the anodizing solution, and a direct current is passed between the aluminum article as the anode and a cathode immersed in the solution.
  • the anodizing is carried out under the conditions set forth above.
  • the panel is rinsed and then plated.
  • the plating can be carried out in a number of different ways.
  • a nickel strike may be made from a low chloride Watts nickel bath, and subsequent plating with semi-bright nickel, bright nickel and chromium may be applied.
  • the anodized article may be plated directly with nickel using a Watts nickel solution, preferably containing coumarin, to produce a semi-bright deposit, followed by a bright nickel deposit. Subsequent chrome plating onto the bright nickel deposit results in an adhesive, integral, composite electrodeposited layer.
  • the panel was rinsed and plated in a low chloride Watts nickel strike containing 2 ounces per gallon of NiCL .6I-I O. This operation was carried out at a pH of 4.5, at 105F. for 5 minutes. After the nickel strike, the panel was subsequently plated with 1 mil of semibright nickel, 0.5 mils of bright nickel, and 0.01 mils of chromium. The resulting deposit was uniformly bright and smooth, and the adhesion of the total electrodeposit to the panel was excellent.
  • EXAMPLE II A 6 inch by 4 inch aluminum panel of 7046 alloy was cleaned, rinsed and etched as explained in Example I.
  • the bath was operated at 25 volts and at a current density of 15 to 20 amperes per square foot.
  • the work piece was rinsed with water and plated directly with nickel.
  • An initial plate was made from a Watts nickel solution containing coumarin to produce a semi-bright deposit which constituted of the total desired nickel deposit. Following the semi-bright deposit, a bright nickel deposit was made incorporating the remaining 30% of the total nickel deposit. After nickel plating, the work piece was rinsed with water and chromium plated.
  • Example III The procedure of Example I was followed except that the aqueous anodizing solution had a volumetric composition comprising 7% I-I PO 1% H and 50.0 g/l of amino acetic acid.
  • the panel was then anodized for 6 minutes at a temperature of F. at a constant potential of 25 volts.
  • the panel was next rinsed and placed in a low chloride (2 oz/gal NiCl .6I-I O) Watts nickel strike for 5 minutes at a pH of 4.5 and 105F. After the nickel strike, the panel was plated with one mil of acid copper, 0.5 mils of bright nickel, and 0.01 mils of chromium. The resulting deposit was uniformly bright and smooth, and the adhesion of the total electrodeposit was excellent.
  • the present invention provides a new, novel, and effective processing cycle for the plating of aluminum alloys, particularly aluminum alloys of the 7000 series.
  • the processing cycle includes the anodizing of the aluminum surface which is subsequently electroplated, this anodizing treatment being carried out as a preliminary to the final electroplating operation.
  • the method of electroplating articles made from aluminum alloys having a zinc content of at least 3% by weight and a copper content of not more than about 1.2% by weight comprising the steps of acid etching the surface of the article, anodizing the article in a three component aqueous bath containing from about 5% to about 12% phosphoric acid, from about 0.4% to about 2% sulfuric acid, and from about 1 to 7% of an organic acid selected from the group consisting of a saturated aliphatic mono carboxylic acid, saturated aliphatic mono carboxylic amino acids and saturated aliphatic mono carboxylic hydroxy acids, the organic acid being sufficiently soluble in the bath to provide at least 10 grams per liter, and electroplating the anodized article.
  • organic acid ingredient is selected from the group consisting of acetic acid, hydroxy acetic acid and amino acetic acid.
  • a method of electroplating an article made from an aluminum alloy having a zince content of at least 3% by weight and a copper content of not more than about 1.2% by weight the improvement of anodizing the article as a pre-plate prior to electrodeposition by the steps of (l) placing the article as an anode in an aqueous bath consisting essentially of from about 5% to about 12% phosphoric acid, from about 0.40% to about 2% sulfuric acid, and from about 1% to about 7% of an organic acid selected from the group consisting of acetic acid, hydroxy acetic acid, and amino acetic acid, and (2) anodizing the article at a temperature of from about F. to F., at a voltage of from about 25 to 30 volts, and at a current density of from about 15 to about 20 amperes per square foot, for a period of time of from about 5 to about 10 minutes.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Electrochemical Coating By Surface Reaction (AREA)

Abstract

A method of and a bath composition for conditioning the surface of an aluminum alloy article to substantially increase the adhesion to the conditioned surface of subsequently applied electrodeposited surface layer. More specifically the surface of the article is anodized in a solution having three components, i.e. phosphoric acid, sulfuric acid and an organic acid selected from the group consisting of acetic acid, hydroxy acetic acid and amino acetic acid (glycine). The anodizing operation typically is followed by a nickel strike deposit, and this deposit may be subsequently electroplated under conventional operating conditions.

Description

United States Patent 11 1 Tremmel et al.
1 51 Oct. 2 1975 METHOD AND COMPOSITION FOR ELECTROPLATING ALUMINUM ALLOYS [73] Assignee: Oxy Metal Industries Corporation,
Warren, Mich.
22 Filed: Oct. 16,1974
21 Appl. No.:515,129
[52] U.S. Cl. 204/33; 204/35 N; 204/38 A; 204/42; 204/58 [51] Int. C1. C25D 5/44; C25D 11/20 [58] Field of Search 204/33, 35 N, 38 A, 42,
[56] References Cited UNITED STATES PATENTS 1,971,761 8/1934 Travers 204/3 2,473,163 6/1949 McCoy 3,098,804 7/1963 Wittrock 3,222,266 12/1965 Page 3,349,014 10/1967 Hyter....
3,524,799 8/1970 Dale 3,622,473 1l/l97l Ohta et al. 204/38 A FOREIGN PATENTS OR APPLICATIONS 447,420 5/1936 United Kingdom 204/58 OTHER PUBLICATIONS A. Akiyama et al., Plating on Anodized Aluminum, Plating, June 1971, pages 594598.
Wernick and Pinner, Surface Treatment of Aluminum and Its Alloys," 3rd. ed. (1964), Teddington, England, pages 594-607.
Primary E.\'aminer.lohn I-I. Mack Assistant Examiner-Aaron Weisstuch Attorney, Agent, or FirmB. F. Claeboe [57] ABSTRACT A method of and a bath composition for conditioning the surface of an aluminum alloy article to substantially increase the adhesion to the conditioned surface of subsequently applied electrodeposited surface layer. More specifically the surface of the article is anodized in a solution having three components, i.e. phosphoric acid, sulfuric acid and an organic acid selected from the group consisting of acetic acid, hydroxy acetic acid and amino acetic acid (glycine). The anodizing operation typically is followed by a nickel strike deposit, and this deposit may be subsequently electroplated under conventional operating conditions.
4 Claims, N0 Drawings METHOD AND COMPOSITION FOR ELECTROPLATING ALUMINUM ALLOYS BRIEF DESCRIPTION OF THE INVENTION It has recently been proposed that bumpers and other exterior automotive components be made from aluminum alloys, particularly alloys from the 7000 series. Such alloys generally have the following typical analyses:
Such aluminum alloy components must be finished by electroplating with nickel-chromium or similar bright plating. Yet conventional electroplating techniques do not form completely adherent electrodeposited layers on such alloys.
It has now been discovered that adherent electrodeposited layers can be formed on such alloys by initially anodizing the aluminum surface in an anodizing bath containing a mixture of phosphoric acid, sulfuric acid, and an organic acid.
As used hereinafter, all percentages given are expressed as volume percent.
More specifically, the surface of the aluminum alloy which is to be electroplated is first cleaned, acid etched and then rinsed. Next, the article surface is anodized in a three component bath containing from about to about 12% H PO plus from about 0.4% to about 2.0% H 50 plus from about 1% to about 7% of an aliphatic mono carboxylic acid or a hydroxy or amino derivative of such an acid having a solubility of at least 10 grams per liter in the inorganic acid mixture. To be more precise, the three component bath contains, as a preferred ingredient, and in addition to the phosphoric acid and the sulfuric acid, from about 1% to about 7% of an organic acid selected from the group consisting of acetic acid, hydroxy acetic acid, and amino acetic acid.
It should be emphasized that the anodizing treatment proposed by the present invention is a preliminary or conditioning treatment intended primarily for utilization as an undercoating for a subsequently applied electrodeposited final layer or coating.
Thus, the present treatment differs substantially from the earlier proposed anodizing treatments which are intended to form integral colored anodic coatings on the surface of aluminum or its alloys. For example, in British Pat. No. 1,022,423, a final hard coat is provided by anodizing aluminum or its alloys in a bath containing a mineral acid, an organic acid, and organic acid salts. Similarly, mixtures of either sulfuric acid or phosphoric acid together with certain organic acids have been proposed to achieve a hard, dense, anodic coating as a final surface treatment in U.S. Pat. No. 3,524,799. In each of these instances, the baths are utilized as totally different concentrations than in the present invention and for entirely different purposes. Also it has been proposed in US. Pat. No. 3,349,014
that a mixture of phosphoric acid, acetic acid and sulfuric acid be utilized to impregnate a porous pad which is then incorporated into an anodizing circuit and rubbed over a previously damaged surface of an aluminum alloy part. Here again, the intent is to form a final anodized coating, and the ingredients are utilized in proportions and amounts entirely outside the range of the present invention.
The anodizing conditions of the present invention typically carry out the treatment at a temperature of from about to about F., at a voltage of from 25 to 30 volts and at a current density of from about 15 to about .20 amperes per square foot for a period of time of from about 5 to about 10 minutes.
Following the surface treatment of the present invention, the surface is subsequently plated with nickel and chromium or with any other surface treatment which may be desired. Typically, the surface may be plated with one mil of semi-bright nickel, 0.5 mils of bright nickel, or 0.01 mils of chromium. The resulting deposit is uniformly bright and smooth, and the adhesion of the final electrodeposition to the surface is excellent.
OBJECTS OF THE PRESENT INVENTION It is, therefore, an important object of the present invention to provide an improved method for electroplating articles made from aluminum alloys, and wherein the surface of the article is anodized prior to electroplating in a bath containing a mixture of phosphoric acid, sulfuric acid, and an aliphatic mono carboxylic acid or the hydroxy or amino derivatives of such an acid.
Another important object of the present invention is to provide a bath composition for subjecting an aluminum surface to a pre-electrodeposition treatment, the bath containing from about 5% to about 12% phosphoric acid, from about 0.4 to about 2% sulfuric acid, and from about 1 to about 7% of an organic acid selected from the group consisting of aliphatic mono carboxylic acids, hydroxy derivatives and amino derivatives of such acids having a solubility of at least 10 grams per liter in the phosphoric and sulfuric acid mixture.
It is a further important object of the present invention to provide a method of electroplating articles made from aluminum alloys by anodizing the article in a three component aqueous bath containing phosphoric acid, sulfuric acid, and an organic acid selected from the group consisting essentially of acetic acid, hydroxy acetic acid and amino acetic acid, and then electroplating the anodized article.
It is yet another object of the instant invention to provide a method of electroplating an article made from an alumimum alloy by anodizing the article prior to electrodeposition by placing the article as an anode in an aqueous bath consisting of from about 5 to about 12% phosphoric acid, from about 0.4 to about 2% sulfuric acid, and from about 1 to about 7% of an organic acid selected from the group consisting of acetic acid, hydroxy acetic acid and amino acetic acid, and anodizing the article at a temperature of from about 100 to about 110F. at a voltage of about 25 to about 30 volts, at a current density of about 15 to about 20 amperes per square foot, for a period of time of from about 5 to about 10 minutes.
DETAILED DESCRIPTION OF THE INVENTION As above explained, the present invention proposes a specific anodizing treatment for aluminum alloys as a pre-treatment for a subsequent plating operation. It has been found that such initial anodizing greatly increases the adherence of the subsequently applied electrodeposit to the underlying aluminum alloy surface.
Specifically, the anodizing solution consists of three components, namely phosphoric acid (H PO at a concentration of from 5 to about 12%, and at a preferred concentration of about 7%. The second ingredient is sulfuric acid (H 80 at a concentration ranging from about 0.4% to about 2% and at a preferred concentration of about 1%. The third ingredient is a saturated aliphatic mono carboxylic acid or a hydroxy derivative of such an acid or an amino derivative of such an acid, any one of these third ingredients necessarily having a solubility of at least 10 grams per liter in the acid solution. Preferred specific saturated aliphatic mono carboxylic acids and derivatives are acetic acid (CI-I COOH), hydroxy acetic acid (l-IOCI-I COOI-I) and glycine or amino acetic acid (Nl-I Cl-I COOI-I). The saturated aliphatic mono carboxylic acid or its derivative is present in an amount ranging from about 1% to about 7% of the solution with a preferred composition containing about 3.5%.
The anodizing operation is carried out under operating conditions which generally include a temperature of from about 100F. to about 110F., and preferably 105F.; at a voltage of from about 25 to 30 volts; at a current density of from about to about amperes per square foot, and for a period of time of from about 5 to about 10 minutes, preferably for a period of about 7 to 8 minutes.
Of course, the surface must be initially cleaned, which can be carried out by either soaking or by power spraying with an alkaline solution or by any other preferred cleaning method. After cleaning, the surface is rinsed and preferably is acid etched. This etching is carried out at room temperature for a sufficient period of time, on the order of 1.5 to 2 minutes and the etching solution preferably contains 50% by volume nitric acid (HNO and 50 grams per liter of ammonium bifluoride (Nl-I F-HF).
The article to be anodized, after cleaning and etching, is immersed in the anodizing solution, and a direct current is passed between the aluminum article as the anode and a cathode immersed in the solution. The anodizing is carried out under the conditions set forth above.
Next, the panel is rinsed and then plated. The plating can be carried out in a number of different ways. For example, a nickel strike may be made from a low chloride Watts nickel bath, and subsequent plating with semi-bright nickel, bright nickel and chromium may be applied. Alternatively, the anodized article may be plated directly with nickel using a Watts nickel solution, preferably containing coumarin, to produce a semi-bright deposit, followed by a bright nickel deposit. Subsequent chrome plating onto the bright nickel deposit results in an adhesive, integral, composite electrodeposited layer.
The following examples point out specific operating conditions and illustrate the practice of the invention, but these examples are not to be considered as limiting the scope of the invention.
EXAMPLE I H PO H 80 Acetic acid The panel was then anodized in the solution for 6 minutes at a temperature of 105F. The anodizing was carried out at a constant potential of 25 volts.
Next, the panel was rinsed and plated in a low chloride Watts nickel strike containing 2 ounces per gallon of NiCL .6I-I O. This operation was carried out at a pH of 4.5, at 105F. for 5 minutes. After the nickel strike, the panel was subsequently plated with 1 mil of semibright nickel, 0.5 mils of bright nickel, and 0.01 mils of chromium. The resulting deposit was uniformly bright and smooth, and the adhesion of the total electrodeposit to the panel was excellent.
EXAMPLE II A 6 inch by 4 inch aluminum panel of 7046 alloy was cleaned, rinsed and etched as explained in Example I.
The panel was then anodized in a solution having the composition:
Phosphoric acid 97,4 /l Hydroxy acetic acid 33.6 g/l Sulfuric acid 19.3 g/l During anodizing, the panel was immersed in the bath for 10 minutes at 105F. The bath was operated at 25 volts and at a current density of 15 to 20 amperes per square foot.
After anodizing, the work piece was rinsed with water and plated directly with nickel. An initial plate was made from a Watts nickel solution containing coumarin to produce a semi-bright deposit which constituted of the total desired nickel deposit. Following the semi-bright deposit, a bright nickel deposit was made incorporating the remaining 30% of the total nickel deposit. After nickel plating, the work piece was rinsed with water and chromium plated.
Adhesion tests were made by grinding the panel, and these tests showed that the deposit adhered very well to the basic metal.
EXAMPLE III The procedure of Example I was followed except that the aqueous anodizing solution had a volumetric composition comprising 7% I-I PO 1% H and 50.0 g/l of amino acetic acid.
The panel was then anodized for 6 minutes at a temperature of F. at a constant potential of 25 volts. The panel was next rinsed and placed in a low chloride (2 oz/gal NiCl .6I-I O) Watts nickel strike for 5 minutes at a pH of 4.5 and 105F. After the nickel strike, the panel was plated with one mil of acid copper, 0.5 mils of bright nickel, and 0.01 mils of chromium. The resulting deposit was uniformly bright and smooth, and the adhesion of the total electrodeposit was excellent.
EXAMPLE IV The above tests were repeated using the identical conditions mentioned except that 5% formic acid was used instead of the glycine (amino acetic acid). The resulting deposit was uniformly bright and smooth and the overall adhesion was again excellent.
It will be seen from the foregoing that the present invention provides a new, novel, and effective processing cycle for the plating of aluminum alloys, particularly aluminum alloys of the 7000 series. The processing cycle includes the anodizing of the aluminum surface which is subsequently electroplated, this anodizing treatment being carried out as a preliminary to the final electroplating operation.
What is claimed is:
1. The method of electroplating articles made from aluminum alloys having a zinc content of at least 3% by weight and a copper content of not more than about 1.2% by weight, comprising the steps of acid etching the surface of the article, anodizing the article in a three component aqueous bath containing from about 5% to about 12% phosphoric acid, from about 0.4% to about 2% sulfuric acid, and from about 1 to 7% of an organic acid selected from the group consisting of a saturated aliphatic mono carboxylic acid, saturated aliphatic mono carboxylic amino acids and saturated aliphatic mono carboxylic hydroxy acids, the organic acid being sufficiently soluble in the bath to provide at least 10 grams per liter, and electroplating the anodized article.
2. The method as defined in claim 1, wherein the organic acid ingredient is selected from the group consisting of acetic acid, hydroxy acetic acid and amino acetic acid.
3. In a method of electroplating an article made from an aluminum alloy having a zince content of at least 3% by weight and a copper content of not more than about 1.2% by weight, the improvement of anodizing the article as a pre-plate prior to electrodeposition by the steps of (l) placing the article as an anode in an aqueous bath consisting essentially of from about 5% to about 12% phosphoric acid, from about 0.40% to about 2% sulfuric acid, and from about 1% to about 7% of an organic acid selected from the group consisting of acetic acid, hydroxy acetic acid, and amino acetic acid, and (2) anodizing the article at a temperature of from about F. to F., at a voltage of from about 25 to 30 volts, and at a current density of from about 15 to about 20 amperes per square foot, for a period of time of from about 5 to about 10 minutes.
4. In a method of electroplating an article made from an aluminum alloy having a zinc content of at least 3% by weight and a copper content of not more than about 1.2% by weight, the improvement of anodizing the article as a pre-plate prior to electrodeposition by anodizing the article in an aqueous bath consisting essentially of from about 5% to about 12% phosphoric acid, from about 0.40% to about 2% sulfuric acid, and from about 1 to 7% of an organic acid selected from the group consisting of acetic acid, hydroxy acetic acid, and amino

Claims (4)

1. THE METHOD OF ELECTROPLATING ARTICLES MADE FROM ALUMINUM ALLOYS HAVING A ZINC CONTENT O AT LEAST 3% BY WEIGHT AND A COPPER CONTENT OF NOT MORE THAN ABOUT 1.2% BY WEIGHT, COMPRISING THE STEPS OF ACID ETCHING THE SURFACE OF THE ARTICLE, ANODIZING THE ARTICLE IN A THREE COMPONENT AQUEOUS BATH CONTAINING FROM ABOUT 5% TO ABOUT 12% PHOSPHORIC ACID, FROM ABOUT 0.4% TO ABOUT 2% SULFURIC ACID, AND FROM ABOUT 1 TO 7% OF AN ORGANIC ACID SELECTED FROM THE GROUP CONSISTING OF A SATURATED ALIPHATIC MONO CARBOXYLIC ACID, SATURATED ALIPHATIC MONO CARBOXYLIC AMINO ACIDS AND SATURATED ALIPHATIC MONO CARBOXYLIC HYDROXY ACIDS, THE ORGANIC ACID BEING SUFFICIENTLY SOLUBLE IN THE BATH TO PROVIDE AT LEAST 10 GRAMS PER LITER, AND
2. The method as defined in claim 1, wherein the organic acid ingredient is selected from the group consisting of acetic acid, hydroxy acetic acid and amino acetic acid.
3. In a method of electroplating an article made from an aluminum alloy having a zince content of at least 3% by weight and a copper content of not more than about 1.2% by weight, the improvement of anodizing the article as a pre-plate prior to electrodeposition by the steps of (1) placing the article as an anode in an aqueous bath consisting essentially of from about 5% to about 12% phosphoric acid, from about 0.40% to about 2% sulfuric acid, and from about 1% to about 7% of an organic acid selected from the group consisting of acetic acid, hydroxy acetic acid, and amino acetic acid, and (2) anodizing the article at a temperature of from about 100*F. to 110*F., at a voltage of from about 25 to 30 volts, and at a current density of from about 15 to about 20 amperes per square foot, for a period of time of from about 5 to about 10 minutes.
4. In a method of electroplating an article made from an aluminum alloy having a zinc content of at least 3% by weight and a copper content of not more than about 1.2% by weight, the improvement of anodizing the article as a pre-plate prior to electrodeposition by anodizing the article in an aqueous bath consisting essentially of from about 5% to about 12% phosphoric acid, from about 0.40% to about 2% sulfuric acid, and from about 1 to 7% of an organic acid selected from the group consisting of acetic acid, hydroxy acetic acid, and amino acetic acid.
US515129A 1974-10-16 1974-10-16 Method and composition for electroplating aluminum alloys Expired - Lifetime US3915811A (en)

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US515129A US3915811A (en) 1974-10-16 1974-10-16 Method and composition for electroplating aluminum alloys
CA223,195A CA1043287A (en) 1974-10-16 1975-03-25 Method and composition for electroplating auminum alloys
FR7510318A FR2288164A1 (en) 1974-10-16 1975-04-02 METHODS AND COMPOSITIONS FOR THE ELECTROLYTIC COATING OF ARTICLES OR INDUSTRIAL PRODUCTS IN ALUMINUM ALLOY
ES436285A ES436285A1 (en) 1974-10-16 1975-04-03 Method and composition for electroplating aluminum alloys
SE7503826A SE7503826L (en) 1974-10-16 1975-04-03 METHOD AND COMPOSITION FOR ELECTROLICATION OF ALUMINUM ALLOYS
IT48953/75A IT1035197B (en) 1974-10-16 1975-04-07 METHOD AND BATH FOR ELECTROLYTICALLY PLATING ALUMINUM OBJECTS
DE19752517779 DE2517779A1 (en) 1974-10-16 1975-04-22 METHOD AND BATH FOR ELECTRIC PLATING OF ALUMINUM ALLOYS
NL7504952A NL7504952A (en) 1974-10-16 1975-04-25 METHOD AND COMPOSITION FOR GALVANIZING ALUMINUM ALLOYS.
GB22802/75A GB1506184A (en) 1974-10-16 1975-05-23 Method and composition for electroplating aluminium alloy
BR4181/75A BR7503268A (en) 1974-10-16 1975-05-23 PROCESS FOR ELECTRIC-COATING OF ARTICLES FORMED OF ALUMINUM ALLOYS AND ANODIZATION BATH EMPLOYED IN THE PROCESS
JP50071382A JPS5147549A (en) 1974-10-16 1975-06-12

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4049504A (en) * 1976-02-23 1977-09-20 Polychrome Corporation Method of producing lithographic printing plates
FR2472468A1 (en) * 1979-12-26 1981-07-03 Gould Inc PROCESS FOR PRODUCING A DETACHABLE COPPER LAYER ON AN ALUMINUM SUPPORT AND ARTICLE THUS OBTAINED
US4793903A (en) * 1986-10-24 1988-12-27 The Boeing Company Method of cleaning aluminum surfaces
US4968389A (en) * 1985-02-06 1990-11-06 Fujitsu Limited Method of forming a composite film over the surface of aluminum materials
US4976827A (en) * 1984-03-16 1990-12-11 Swiss Aluminium Ltd. Process for pretreating strips and foils of aluminum or aluminum alloys
US5230965A (en) * 1990-01-02 1993-07-27 General Electric Company High density interconnect with electroplated conductors
US5234574A (en) * 1991-01-30 1993-08-10 Sumitomo Metal Industries, Ltd. Process for direct zinc electroplating of aluminum strip
US5245847A (en) * 1991-02-07 1993-09-21 Sumitomo Metal Industries, Ltd. Process for zinc electroplating of aluminum strip
US5436081A (en) * 1991-02-18 1995-07-25 Sumitomo Metal Industries, Ltd. Plated aluminum sheet having improved spot weldability
US5478414A (en) * 1992-01-31 1995-12-26 Aluminum Company Of America Reflective aluminum strip, protected with fluoropolymer coating and a laminate of the strip with a thermoplastic polymer
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US5637404A (en) * 1992-01-31 1997-06-10 Aluminum Company Of America Reflective aluminum strip
US5955147A (en) * 1992-01-31 1999-09-21 Aluminum Company Of America Reflective aluminum trim
US20070066503A1 (en) * 2005-08-19 2007-03-22 Mores Basaly Methods and compositions for acid treatment of a metal surface
US20070105376A1 (en) * 1993-12-14 2007-05-10 Kabushiki Kaisha Toshiba Copper-based metal polishing solution and method for manufacturing semiconductor device
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Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4525247A (en) * 1982-07-12 1985-06-25 Rogers Corporation Microwave circuit boards and method of manufacture thereof
DE19812951C2 (en) * 1998-03-24 2002-12-19 Heckler & Koch Gmbh Firing pin safety in the lock

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1971761A (en) * 1929-09-05 1934-08-28 William J Travers Protection of metals
US2473163A (en) * 1945-06-25 1949-06-14 Ewald H Mccoy Plating nickel on aluminum
US3098804A (en) * 1960-03-28 1963-07-23 Kaiser Aluminium Chem Corp Metal treatment
US3222266A (en) * 1958-08-20 1965-12-07 Kaiser Aluminium Chem Corp Method of enameling anodized aluminum
US3349014A (en) * 1964-08-28 1967-10-24 Mc Donnell Douglas Corp Method and composition for the treatment of an aluminum surface
US3524799A (en) * 1969-06-13 1970-08-18 Reynolds Metals Co Anodizing aluminum
US3622473A (en) * 1964-10-15 1971-11-23 Honny Chemicals Co Ltd Method of providing aluminum surfaces with coatings

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE412098A (en) * 1934-11-17

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1971761A (en) * 1929-09-05 1934-08-28 William J Travers Protection of metals
US2473163A (en) * 1945-06-25 1949-06-14 Ewald H Mccoy Plating nickel on aluminum
US3222266A (en) * 1958-08-20 1965-12-07 Kaiser Aluminium Chem Corp Method of enameling anodized aluminum
US3098804A (en) * 1960-03-28 1963-07-23 Kaiser Aluminium Chem Corp Metal treatment
US3349014A (en) * 1964-08-28 1967-10-24 Mc Donnell Douglas Corp Method and composition for the treatment of an aluminum surface
US3622473A (en) * 1964-10-15 1971-11-23 Honny Chemicals Co Ltd Method of providing aluminum surfaces with coatings
US3524799A (en) * 1969-06-13 1970-08-18 Reynolds Metals Co Anodizing aluminum

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US4049504A (en) * 1976-02-23 1977-09-20 Polychrome Corporation Method of producing lithographic printing plates
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US4293617A (en) * 1979-12-26 1981-10-06 Gould Inc. Process for producing strippable copper on an aluminum carrier and the article so obtained
US4976827A (en) * 1984-03-16 1990-12-11 Swiss Aluminium Ltd. Process for pretreating strips and foils of aluminum or aluminum alloys
US4968389A (en) * 1985-02-06 1990-11-06 Fujitsu Limited Method of forming a composite film over the surface of aluminum materials
US4793903A (en) * 1986-10-24 1988-12-27 The Boeing Company Method of cleaning aluminum surfaces
US5230965A (en) * 1990-01-02 1993-07-27 General Electric Company High density interconnect with electroplated conductors
US5234574A (en) * 1991-01-30 1993-08-10 Sumitomo Metal Industries, Ltd. Process for direct zinc electroplating of aluminum strip
US5245847A (en) * 1991-02-07 1993-09-21 Sumitomo Metal Industries, Ltd. Process for zinc electroplating of aluminum strip
US5436081A (en) * 1991-02-18 1995-07-25 Sumitomo Metal Industries, Ltd. Plated aluminum sheet having improved spot weldability
US5478414A (en) * 1992-01-31 1995-12-26 Aluminum Company Of America Reflective aluminum strip, protected with fluoropolymer coating and a laminate of the strip with a thermoplastic polymer
US5637404A (en) * 1992-01-31 1997-06-10 Aluminum Company Of America Reflective aluminum strip
US5955147A (en) * 1992-01-31 1999-09-21 Aluminum Company Of America Reflective aluminum trim
US20070105376A1 (en) * 1993-12-14 2007-05-10 Kabushiki Kaisha Toshiba Copper-based metal polishing solution and method for manufacturing semiconductor device
EP0689096A1 (en) 1994-06-16 1995-12-27 Eastman Kodak Company Lithographic printing plates utilizing an oleophilic imaging layer
US8252195B2 (en) 2005-08-19 2012-08-28 Houghton Technical Corp. Methods and compositions for acid treatment of a metal surface
US9732428B2 (en) 2005-08-19 2017-08-15 Houghton Technical Corp. Methods and compositions for acid treatment of a metal surface
US20090090635A1 (en) * 2005-08-19 2009-04-09 Houghton Metal Finishing Company Methods and compositions for acid treatment of a metal surface
US10260153B2 (en) 2005-08-19 2019-04-16 Houghton Technical Corp. Methods and compositions for acid treatment of a metal surface
US8518286B2 (en) 2005-08-19 2013-08-27 Houghton Technical Corp. Methods and compositons for acid treatment of a metal surface
US20070066503A1 (en) * 2005-08-19 2007-03-22 Mores Basaly Methods and compositions for acid treatment of a metal surface
EP1826297A2 (en) * 2006-02-23 2007-08-29 Greatbatch Ltd. Anodizing electrolytes using a dual acid system for high voltage electrolytic capacitor anodes
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CA1043287A (en) 1978-11-28
FR2288164B1 (en) 1979-06-29
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JPS5147549A (en) 1976-04-23
BR7503268A (en) 1976-10-05
DE2517779A1 (en) 1976-04-22
SE7503826L (en) 1976-04-20
NL7504952A (en) 1976-04-21
IT1035197B (en) 1979-10-20
FR2288164A1 (en) 1976-05-14
ES436285A1 (en) 1977-05-16

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