U.S. patent number 3,915,811 [Application Number 05/515,129] was granted by the patent office on 1975-10-28 for method and composition for electroplating aluminum alloys.
This patent grant is currently assigned to Oxy Metal Industries Corporation. Invention is credited to Richard J. Clauss, Robert A. Tremmel, Walter J. Wieczerniak.
United States Patent |
3,915,811 |
Tremmel , et al. |
October 28, 1975 |
Method and composition for electroplating aluminum alloys
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.
Inventors: |
Tremmel; Robert A. (Woodhaven,
MI), Wieczerniak; Walter J. (Sterling Heights, MI),
Clauss; Richard J. (Allen Park, MI) |
Assignee: |
Oxy Metal Industries
Corporation (Warren, MI)
|
Family
ID: |
24050086 |
Appl.
No.: |
05/515,129 |
Filed: |
October 16, 1974 |
Current U.S.
Class: |
205/172; 205/325;
205/213; 205/330 |
Current CPC
Class: |
C25D
11/06 (20130101); C25D 5/44 (20130101) |
Current International
Class: |
C25D
11/04 (20060101); C25D 11/06 (20060101); C25D
5/34 (20060101); C25D 5/44 (20060101); C25D
005/44 (); C25D 011/20 () |
Field of
Search: |
;204/33,35N,38A,42,58 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Other References
A Akiyama et al., "Plating on Anodized Aluminum," Plating, June
1971, pages 594-598. .
Wernick and Pinner, "Surface Treatment of Aluminum and Its Alloys,"
3rd. ed. (1964), Teddington, England, pages 594-606..
|
Primary Examiner: Mack; John H.
Assistant Examiner: Weisstuch; Aaron
Attorney, Agent or Firm: Claeboe; B. F.
Claims
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 (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.degree.F.
to 110.degree.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.
Description
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:
Alloy 7046 Alloy 7016 ______________________________________ Si 0.4
max 0.3 max Fe 0.35 max 0.1 max Cu 0.1 (0.25 max) 1.0 Mn 0.3 0.3
max Mg 1.3 1.1 Cd 0.12 -- Zn 6.6 - 7.6 4.0 - 5.0 Zr 0.12 -- Ti 0.03
0.03 max Al Balance Balance
______________________________________
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 5% to about 12% H.sub.3 PO.sub.4, plus from
about 0.4% to about 2.0% H.sub.2 SO.sub.4, 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 U.S.
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 100.degree. to
about 110.degree.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.degree. to about 110.degree.F. 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.sub.3 PO.sub.4) at a concentration of
from 5 to about 12%, and at a preferred concentration of about 7%.
The second ingredient is sulfuric acid (H.sub.2 SO.sub.4) 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 (CH.sub.3 COOH), hydroxy acetic acid (HOCH.sub.2 COOH)
and glycine or amino acetic acid (NH.sub.2 CH.sub.2 COOH). 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 100.degree.F.
to about 110.degree.F., and preferably 105.degree.F.; at a voltage
of from about 25 to 30 volts; at a current density of from about 15
to about 20 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.sub.3) and 50
grams per liter of ammonium bifluoride (NH.sub.4 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
A 4 inch by 6 inch panel of 7046 aluminum alloy was soaked and
cleaned in an alkaline cleaner for one-half hour. Next, the panel
was etched for 2 minutes in an acid solution containing 50% by
volume nitric acid and 50 grams per liter of ammonium
bifluoride.
The panel was then prepared for electroplating by placing it, as
the anode, in an aqueous anodizing solution having the following
volumetric composition:
H.sub.3 PO.sub.4 7% H.sub.2 SO.sub.4 1% Acetic acid 3%
The panel was then anodized in the solution for 6 minutes at a
temperature of 105.degree.F. 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.sub.2
.6H.sub.2 O. This operation was carried out at a pH of 4.5, at
105.degree.F. for 5 minutes. After the nickel strike, the panel was
subsequently plated with 1 mil of semi-bright 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 g/l Hydroxy acetic acid 33.6 g/l
During anodizing, the panel was immersed in the bath for 10 minutes
at 105.degree.F. 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 70% 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%
H.sub.3 PO.sub.4, 1% H.sub.2 SO.sub.4 and 50.0 g/l of amino acetic
acid.
The panel was then anodized for 6 minutes at a temperature of
105.degree.F. at a constant potential of 25 volts. The panel was
next rinsed and placed in a low chloride (2 oz/gal
NiCl.sub.2.6H.sub.2 O) Watts nickel strike for 5 minutes at a pH of
4.5 and 105.degree.F. 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.
* * * * *