U.S. patent number 3,639,221 [Application Number 04/887,145] was granted by the patent office on 1972-02-01 for process for integral color anodizing.
This patent grant is currently assigned to Kaiser Aluminum & Chemical Corporation. Invention is credited to Geoffrey Austin Dorsey, Jr..
United States Patent |
3,639,221 |
Dorsey, Jr. |
February 1, 1972 |
PROCESS FOR INTEGRAL COLOR ANODIZING
Abstract
A process for integral color anodizing of aluminum and aluminum
alloys wherein the aluminum piece is subjected as an anode to
electrolysis in an aqueous solution containing sulfuric acid, and
at least one compound selected from the group consisting of
molybdates, tungstates, vanadates and manganates, a portion of
which exists in a polyacid species.
Inventors: |
Dorsey, Jr.; Geoffrey Austin
(Danville, CA) |
Assignee: |
Kaiser Aluminum & Chemical
Corporation (Oakland, CA)
|
Family
ID: |
25390529 |
Appl.
No.: |
04/887,145 |
Filed: |
December 22, 1969 |
Current U.S.
Class: |
205/328;
205/333 |
Current CPC
Class: |
C25D
11/14 (20130101) |
Current International
Class: |
C25D
11/14 (20060101); C25D 11/04 (20060101); C23b
009/02 () |
Field of
Search: |
;204/58,35,38A |
Foreign Patent Documents
|
|
|
|
|
|
|
1,022,927 |
|
Mar 1966 |
|
GB |
|
662,063 |
|
Apr 1963 |
|
CA |
|
Primary Examiner: Mack; John H.
Assistant Examiner: Andrews; R. L.
Claims
What is claimed is:
1. A process for forming an integrally colored oxide coating on an
aluminum article comprising anodizing said aluminum article as the
anode in an aqueous electrolyte consisting essentially of from
about 0.1 to about 0.8 percent sulfuric acid, at least 0.03
gram-mols/liter of a compound selected from a group consisting of
molybdates, vanadates, tungstates and manganates, at least 0.01
gram-mols/liter of said compound existing as a free polyacid
species, and the balance water.
2. The process according to claim 1 wherein the sulfuric acid
concentration is from about 0.1 to 0.8 percent by weight and the
concentration of a compound selected from the group consisting of
molybdates, vanadates, tungstates and manganates is from about 0.03
to 0.5 gram-mols/liter.
3. The process according to claim 2 wherein the compound is
selected from the group consisting of molybdates and
tungstates.
4. The process according to claim 3 wherein a portion of a compound
selected from the group consisting of molybdates and tungstates is
complexed with oxalic acid.
Description
BACKGROUND OF THE INVENTION
In many circumstances it is desirable to have a colored or hued
surface on aluminum articles, particularly in architectural
applications where aesthetic considerations are quite important.
Several processes have been developed to produce colored oxide
coatings; however, only one has met with any real commercial
success, that being the integral color anodizing process basically
described in U.S. Pat. No. 25,566, assigned to the present
assignee. Methods such as dyeing a previously anodized surface with
organic dyes or introducing metallic salts or oxides into a
previously prepared anodic oxide coating suffer from the inherent
disadvantage of requiring additional process coloring steps after
the aluminum article has been anodized, which increase the cost as
well as the inconvenience of the process. The dyeing of the anodic
oxide coating has the additional disadvantage of producing a color
which fades when exposed to ultraviolet light and also a color
which is difficult to reproduce from batch to batch. The color
anodizing process described in U.S. Pat. No. Re. 25,566 involves
the anodization of the aluminum article in an aqueous electrolyte
containing sulfosalicylic acid and sulfuric acid. Other sulfonic
acids such as sulfophthalic acid have also been proven to be
efficient in producing integral color anodized coatings. In
general, the colors produced are uniform, reproducible and have a
high aesthetic appeal necessary for architectural applications. In
addition, these integrally colored anodic oxide coatings are also
lightfast and highly abrasion resistant. However, the color ranges
obtainable with the prior art electrolytes were generally dependent
upon the alloy anodized.
SUMMARY OF THE INVENTION
The present invention is related to a novel electrolytic bath and
the process of forming integrally colored anodic oxide coatings on
the surface on an aluminum article. More particularly the invention
is directed to the anodizing of aluminum and aluminum alloys in an
aqueous electrolyte containing sulfuric acid and a free polyacid
species selected from the group consisting of molybdic, tungstic,
vanadic and manganic acids. The process is advantageously operated
by subjecting the aluminum surface as the anode in an electrolytic
cell to a current density between 10 and 50 a./sq.ft. until a final
peak voltage across the cell between 40 and 80 volts is reached and
then maintaining this peak voltage at a substantially constant
level until the desired color density and oxide thickness is
obtained.
DETAILED DESCRIPTION
In accordance with the present invention, it has been found that an
aqueous solution of sulfuric acid and at least one soluble compound
selected from a group consisting of molybdates, tungstates,
vanadates and manganates a portion of which is in the polyacid form
can be advantageously utilized in an electrolyte for the integral
color anodizing of aluminum and aluminum alloys. Moreover, it has
been found that the electrolyte produces a full range of lightfast
architecturally desirable colors which are considerably more
independent of the alloy composition of the workpieces than prior
art electrolytes.
The sulfuric acid concentration can range from 0.1- 1.5 percent.
However, it is preferred to maintain this level between 0.1 and 0.8
percent by weight. The soluble molybdates, tungstates, vanadates,
and manganates can range from 0.03 gram-mols/liter up to the limit
of solubility; however, it is preferred to maintain the content of
these compounds between 0.03 and 0.5 gram-mols/liter. At least 0.01
gram-mols/liter of the compounds must exist in free polyacid form.
The term "polyacid" is used herein to include the dimers and
trimers up to and including the higher molecular weight species.
Although any molybdate, tungstate, vanadate and manganate or
combinations thereof which are soluble within the limits set forth
above can be utilized, it is preferred to use potassium, sodium and
ammonium compounds, particularly the latter. The basic integral
color range of light gold to black is obtainable with almost any
aluminum alloy with the electrolytes of the present invention.
In the process of the present invention, the aluminum article is
preferably subjected as the anode to a substantially constant
current density between 5 and 50 a./ft. until a final peak voltage
between 30 and 110 volts is reached and this final peak voltage is
maintained at a substantially constant level until the desired
integrally colored anodic oxide coatings are obtained. Integral
color generation is very slow at peak voltages below 50 volts. Bath
temperatures may range from 0.degree. to 100.degree. C., although
for commercial applications it may be desirable to maintain these
temperatures between 15.degree. and 35.degree. C. Other anodizing
programs can be employed but the "constant current density followed
by a constant voltage" program is the most efficient.
Electrolytes containing sulfuric acid and a molybdate or tungstate
compound when subjected to electrolysis have a tendency to form
high molecular weight polyacids. To a certain extent these
polyacids tend to be somewhat colloidal in nature and thus
incorporate themselves into the anodic oxide coating during
anodizing in colloidal as well as anionic form. This incorporation
introduces an additional advantage with the polymolybdic acid in
that this incorporation tends to modify the basic integral color
obtained during the anodizing process. The molybdates tend to give
dark green and dark blue anodic oxide coatings. However, with
polytungstic acid the incorporation phenomenon does not
substantially change the basic integral color of light gold to
black.
However, as the anodizing process proceeds the buildup of this
colloidal species tends to reduce the efficiency of the
electrolyte. To overcome this tendency to produce large amounts of
high molecular weight species, it has been found that small
quantities of oxalic acid, when introduced into the electrolyte
will apparently complex with these compounds to form
oxalato-molybdic acid and oxalato-tungstic acid and thus reduce the
quantity of colloidal material in the electrolyte. However, the
oxalic acid concentration should never equal or exceed the amount
necessary to complex all of the polymolybdic and polytungstic acids
for this removes the effectiveness of these compounds in the
electrolyte and the electrolyte tends to behave as if only oxalic
acid and sulfuric acid were present. At least an excess of 0.01
gram-mols/liter of free polymolybdic acid or polytungstic acid
(i.e., not complexed with oxalic acid) must be in solution in the
electrolyte at all times. During the course of anodizing, the
concentration of free polymolybdic acid in solution is reduced due
to the incorporation of this material into the anodic oxide coating
and due to the reduction at the cathode of the dissolved compound
during anodizing. However, during anodizing the complexed oxalic
acid is oxidized to carbon dioxide and the complexed molybdate is
reduced to approximately the +5 valence state, i.e., to the desired
polymolybdic acid; and therefore free polymolybdic acid is
continually released to the bath. If the polymolybdic acid is
complexed with oxalic acid, the bath can be utilized almost to the
point of complete exhaustion of the molybdate concentration in the
bath.
Anodizing in a sulfuric acid polymolybdic acid electrolyte produces
oxide coatings which can range from light golds to browns to blacks
and also to greens and blues. However, when these anodized articles
are sealed in an aqueous solution the greens and blues tend to
disappear, leaving the anodic oxide coating ranging in color from
light gold to black depending on the base color. It has been found
that if these anodic oxide coatings are sealed in a nonaqueous
solution such as a mixture of mineral oil and stearic acid or in a
lanolin bath that the green and blue colors can be sealed into the
anodic oxide coating and thus rendered permanent. These green and
blue colors are lightfast and the nonaqueous sealed anodic oxide
coatings have a corrosion and abrasion resistance comparable to
those coatings which have been sealed in an aqueous solution. The
oxide coating produced in a sulfuric acid polytungstic acid tend to
become darker upon aqueous sealing. The nonaqueous sealing bath
mentioned above also functions efficiently with all of the sulfuric
acid, polyacid produced anodic oxide coatings.
In the preferred embodiment of the present invention, the
electrolyte is prepared by adding about 20 grams/liter ammonium
molybdate and about 5 grams/liter sulfuric acid to water which
produces a clear and colorless solution. Apparently the sulfuric
acid converts the ammonium molybdate to a molybdic acid of the
formula H.sub.2 MoO.sub.4 ; however, this is recognized as only a
barrier layer electrolyte which does not produce integral colored
coatings. A workpiece, which can be aluminum or any conductive
material, is immersed in this electrolyte and subjected to
anodization which transforms (at the cathode) this molybdic acid
solution into a blue polymolybdic acid solution which is the form
needed to produce the integral colored anodic oxide coatings. The
exact form of this polymolybdic acid species is not known, but it
is believed to have an average oxidation state of probably closer
to +5 than to +6. Having generated the proper acidic species of
polymolybdic acid, the electrolyte is ready for anodizing.
Anodizing in a polymolybdic acid electrolyte has the unique feature
that the peak voltage is reached twice during the anodizing
process. With a constant current density, constant-voltage program,
the anodizing is advantageously carried out employing a
constant-current, constant-voltage power supply whereby the desired
current and peak or maximum voltage can be preset and automatically
controlled at the desired levels. As illustrated in the drawing, a
constant current density, constant-voltage anodizing program,
results in the voltage reaching a peak value twice during the
program. For example, in the anodizing operation the maximum
voltage is first set at the desired peak level such as 60 volts.
After a short run in period at low-current density and low voltage,
the current density is set at the desired level such as 20
a./sq.ft. Thereafter no operator attention need be given to the
anodizing. The voltage and current density will rise rapidly but
the voltage will usually reach the maximum preset value before the
current density will reach the preset value. The voltage will
remain at the peak value for a few minutes then decrease to a
minimum value of about 40 volts during which time current density
will reach the desired maximum level. The voltage will rise during
the constant current density stage until the peak value is reached
a second time and thereafter remain at that value until the desired
current quantity has passed through the workpiece. As shown in the
drawings, the current density decays from the maximum value during
the constant voltage period.
The peculiar features of the aforedescribed current density voltage
relationships are a consequence of both the manner in which the
current density and voltage controls are applied and the particular
anodic reaction mechanisms resulting from the use of polymolybdic
acid containing electrolytes. The color of the anodic oxide coating
can be controlled in part by selecting a termination time during
the final constant-voltage period. In the operation as described
above, the anodizing program is substantially automatic and
self-regulated with the consequent benefits of improved uniformity
and reproducibility of color. Manual control may be employed and
the program may be adjusted to produce the coating thickness and
color desired.
To prepare a sulfuric acid polytungstic acid electrolyte, the
pretreatment given above to form the polymolybdic species is
necessary. However, with vanadate and manganate compounds the
pretreatment is unnecessary because the proper polyacid species is
obtained by merely adding the compound to the sulfuric acid
solution. The vanadate- and manganate-containing electrolytes do
not have a tendency to form the higher molecular weight species or
colloidal species and thus little or no polyacid material is
incorporated into the oxide coating.
The examples in the table are given to illustrate embodiments of
the present invention. ##SPC1## ##SPC2## Each of the specimens were
cleaned in an inhibited alkaline cleaner, etched in a NaOH
solution, desmutted in a nitric acid solution and anodized as shown
in the table. All reported colors are for the unsealed specimen
except as otherwise noted. The compositions of the above aluminum
alloys are given in Metals Handbook, Eighth Edition, Volume I, page
917.
* * * * *