U.S. patent number 3,857,766 [Application Number 05/277,578] was granted by the patent office on 1974-12-31 for process for anodizing aluminum and its alloys.
This patent grant is currently assigned to Permaloy Corporation. Invention is credited to Jack L. Woods.
United States Patent |
3,857,766 |
Woods |
December 31, 1974 |
PROCESS FOR ANODIZING ALUMINUM AND ITS ALLOYS
Abstract
A method of anodizing aluminum and its alloys utilizing a
suitable anodizing electrolyte and a pulsed direct current. The
direct current used provides a substantially constant anodizing
current interspersed with at least six pulses per second of higher,
smoothly peaked, direct current. It has been found that the greater
the number of pulses per second, the more superior the anodic
coating obtained. The electrolyte used can be sulfuric acid (125 to
300 grams of sulfuric acid per liter of water) preferably
containing a 0.1 to 0.2 grams per liter of sodium lignosulfonate or
other such sulfonated organic compound as a stabilizer. A mixture
of sulfosalicylic acid and sulfuric acid or a mixture of sulfuric
and oxalic acid can be used.
Inventors: |
Woods; Jack L. (Ogden, UT) |
Assignee: |
Permaloy Corporation (Ogden,
UT)
|
Family
ID: |
23061482 |
Appl.
No.: |
05/277,578 |
Filed: |
August 3, 1972 |
Current U.S.
Class: |
205/108;
204/DIG.8; 205/331; 204/DIG.9 |
Current CPC
Class: |
C25D
11/04 (20130101); C25D 11/024 (20130101); C25D
11/08 (20130101); Y10S 204/08 (20130101); Y10S
204/09 (20130101) |
Current International
Class: |
C25D
11/04 (20060101); C23b 009/02 () |
Field of
Search: |
;204/58,DIG.9,DIG.8 |
Foreign Patent Documents
Other References
"The Anodic Treatment of Al," by E. Joyce,
Plating-Polishing-Finishing, Jan. 1932, page 29. .
"Anodizing of Al Alloys-Hardcoating," by L. F. Spencer, Metal
Finishing, Nov. 1968, page 61. .
Electroplating & Engineering Handbook, 2nd Ed., by A. K.
Graham, 1962, pages 666, 670; "Rectifiers," (L. W.
Reinken)..
|
Primary Examiner: Andrews; R. L.
Attorney, Agent or Firm: Criddle & Thorpe
Claims
I claim:
1. A process for anodizing an object of aluminum or aluminum alloy
comprising
placing said object as an anode in an anodizing electrolyte
contained within an electrolytic cell housing, said housing being a
cathode and being continually connected to a negative current
potential; and
subjecting the anode to a continually applied position direct
current having an average direct positive current voltage
interspersed with applied peaked pulses of higher level positive
current voltage, said peaked pulses having a wave pattern such that
the time from average current to peaked pulse current is greater
than the time from peaked pulse current back to average current,
for a period of time sufficient to anodize the object with a
coating of desired thickness.
2. A process as in claim 1, wherein the direct current is applied
through a pulsed constant current charger.
3. A process as in claim 1, wherein at least six peaked pulses
occur per second.
4. A process as in claim 3, wherein the pulses peak at a voltage
which is at least about twice the average direct current
voltage.
5. A process as in claim 3, wherein the electrolyte comprises an
aqueous solution of sulfuric acid containing between one hundred
twenty-five and three hundred grams of sulfuric acid per liter of
water and one-tenth to two tenths grams of sodium lignosulfonate
per liter.
Description
BRIEF DESCRIPTION OF THE INVENTION
1. Field of the Invention
This invention relates to methods of applying dense, hard, thick
oxide coatings as well as thin, dense, oxide coatings on aluminum
metal.
2. Prior Art
For many purposes, aluminum surfaces are protected by a decorative,
oxide coating produced on the surface by exposing it to controlled
electrolysis. Many processes have been developed in the past to
anodize aluminum metal objects by application of the dense oxide
coating. Most of these prior art processes use sulfuric acid,
oxalic acid, or organic acids, or combinations thereof as an
electrolyte and use standard direct current power for the
anodization process. A few of the processes involve the use of an
alternating current imposed on top of direct current or use a
surging, jagged, sharply peaked type of pulsating direct current.
U.S. Pat. No. 3,597,339, uses a special circuit to produce a
pulsating current wherein various levels of negative current are
applied to a normally positive anode. The process disclosed in U.S.
Pat. No. 3,597,339 appears to have limited utility, since it uses a
single phase power input and is limited to about 500 amps direct
current output. This severely limits the size of production parts
that can be processed and makes the system impractical for use
except in a laboratory or for small scale type use.
SUMMARY OF THE INVENTION
None of the processes with which I am familiar anodize using a
combination of proper electrolyte and a pulsed form of direct
current electrical energy. As a result, the prior processes are
limited as to the types of aluminum alloys that can be anodized and
the thickness and hardness of the coating obtained. It is an object
of the present invention to provide a process of anodizing aluminum
wherein a superior anodic coating is obtained.
Another object of the present invention is to provide an anodizing
process wherein a relatively simple electrical circuit is used and
where serious tank and cooling equipment corrosion is avoided.
Still other objects are to provide a process that can be used to
hard coat even high copper bearing aluminum alloys which have been,
in the past, very difficult or impossible to hard anodize.
It is also an object of the invention to provide a process that can
be used to provide thick anodic coatings at a much lower cost that
has been heretofore possible and without destruction of the part or
object being anodized.
Principal features of the invention include the use of a pulsed
direct current in combination with a selected anodizing
electrolyte. The pulsed electric current is obtained by using a
conventional alterating current source, rectified through a pulsed
constant current charger of the type commercially available from
the Utah Research and Development Company, Inc. for use in charging
nickel cadmium batteries, to the anode, of the electrolytic cell in
which the anodization is to take place.
Additional objects and features of the invention will become
apparent from the following detailed description, taken together
with the accompanying drawings.
THE DRAWINGS
FIG. 1 is a schematic circuit diagram showing the control circuitry
of the process; and
FIG. 2 is a schematic diagram showing the wave form of the circuit
used in the process.
DETAILED DESCRIPTION
Referring now to the drawings:
In the illustrated preferred embodiment, a pulsed current charger
10, of the type normally used in the re-charging of nickel cadmium
batteries and commercially available in rated capacities from Utah
Research and Development Company, Inc., Salt Lake City, Utah,
receives a current input from a conventional alternating power
source 11 and puts out a direct current having the wave form shown
in FIG. 2. The positive output of the pulsed current charger 10 is
connected to the anode 12, which may constitute or which is
connected directly to the object being anodized, of an electrolytic
tank shown generally at 13 and applies a positive current having
the wave form of FIG. 2 to the anode.
Tank 13 has a housing, which may be of stainless steel, for
example, and the housing forms the cathode of the electrolytic
tank. The cathode is electrically connected to the negative
potential of the pulsed constant current charger 10 and is
maintained negative at all times. As a result, tank corrosion is
greatly reduced over systems wherein the cathode is subjected to
alternately positive or negative current or to some positive
current leakage. Furthermore since the corrosion normally incident
to anodization is greatly reduced the refrigeration or cooling
coils 14 and line 15 conventionally used to keep the anodizing
electrolyte temperature below predetermined temperatures and in the
ideal anodization range below about forty-five degrees fahrenheit
can also be advantageously made of stainless steel. With the prior
known processes positive current is applied to the cathode and it
has been necessary to make the tank housing and cooling structure
of lead so that is will not severely corrode.
The pulsed current charger supplies a positive current having an
average positive direct current 16, FIG. 2, to the anode and pulses
17 of high level positive direct current. It has been found that
the more frequent the pulses the more effective the current is for
anodization procedures. It has also been found that at least six
pulses per second are required to effectively anodize aluminum and
aluminum alloys. In practice, anodization occurs rapidly when an
average positive direct current 16 of 1,000 amps is applied, with
pulses 17 smoothly peaking at from 2,000 to 10,000 amps. When an
average positive direct current of 5,000 amps is applied to the
anode, the pulses 17 smoothly peak at from 10,000 to 25,000 amps.
The pulses stabilize the formation of the oxide coating, allow
thick coatings to be produced at reduced voltages and high current
densities and enable aluminum alloys, even those with copper
content, to be readily anodized.
The anodizing electrolyte used in the present process may be an
aqueous solution of sulfuric acid (125 to 300 grams of sulfuric
acid per liter of water) preferably containing 0.1 to 0.2 grams per
liter of sodium lignosulfonate or a comparable amount of any other
such sulfonated organic compound as a stabilizer. Alternatively, an
electrolyte comprising an aqueous solution of sulfuric and oxalic
acid having from one percent by weight oxalic acid fifty percent
sulfuric acid to one percent sulfuric acid and oxalic acid to
saturation or an electrolyte comprising an aqueous solution of from
about five to fifty percent by weight sulfosalicyclic acid and not
more than about fifteen percent by weight sulfuric acid or
equivalent amount of metal sulfates can be used. This latter
identified electrolyte solution is well known in the art, having
been disclosed in U.S. Pat. No. 3,031,387.
The effectiveness and advantages of the present process have been
demonstrated in practice. For example, while U.S. military
specification MIL-A-8625 C prohibits the hard anodization of
aluminum alloys containing over 5 percent by weight of copper,
because prior known processes would cause rapid destruction of the
object being anodized, Aluminum Company of America alloy No. 2219,
which contains 6.3 percent copper has been hard anodized according
to the present invention with a very thick dense oxide coating. No
physical deterioration of the object was noted as a result of the
anodization.
While heretofore known hard anodizing processes have required
approximately twenty minutes and forty volts at a current density
of thirty-six amps per square foot to produce a hard coat having a
thickness of 0.0001 inches, the present process applies a 0.001
inch thick coat in twelve to fifteen minutes at a voltage of
approximately twenty-eight volts and a density of thirty-six amps
per square foot.
Because the present process utilizes a relatively low voltage
application, while developing relatively high current densities,
objects that in the past were subject to destruction during
anodization can be safely hard coated. For example, it has been
found that with Aluminum Company of America alloy 2024, and using
the method of the present invention, it is possible to apply 0.0025
inches of hard coating in approximately six minutes, with a maximum
voltage of about 36 volts and a current density of 144 amps per
square foot. Such treatment caused no apparent structural damage to
the object coated. With processes heretofore used alloy 2024 could
be hard coated only with great caution and strict temperature
control of the electrolyte and with use of voltages in the range of
50 to 65 volts. Such prior processing generally has required about
one hour to complete.
Previously known anodizing processes have also been limited in that
the coatings they produce could only be of limited thickness and
frequently would spall off or crack when bent. Using the process of
the present invention, and using an aqueous solution of sulfuric
acid and lignosulfonate as above described, 1/8 inch by 2 inch
wide, bright cleaned, strips of Aluminum Company of America alloy
No. 5052 were hard anodized to a coating thickness of 0.0015
inches. The coated strips were thereafter bent 180.degree. around a
one inch diameter rod and were examined for cracking or spalling.
No cracking or spalling was present on either the compression or
tension sides of the strips.
While the prior known anodization processes with which I am
familiar have all had a practical limit of about 0.004 inches as to
the thickness of the coat they could produce, the present system
appears to have no such limitation, or at least a much higher
limitation dependent only on the voltage limitations of the
available power supply. Coatings of over 0.010 inches have been
produced. For example, bright cleaned production parts of Aluminum
Company of America alloy No. 6061 were hard coated to a thickness
of 0.012 inches in fifty-five minutes. A voltage of 75 amps maximum
and a current density of 100 amps per square foot were used and the
electrolyte was an aqueous solution of sulfuric acid and sodium
lignosulfonate as heretofore described.
The present invention provides a unique method of anodizing all
aluminum and aluminum alloys more rapidly and with less power for
anodizing and consequently with less power required for cooling
than has theretofore been possible. As a result, the present
process results in lower costs as a result of electrical and labor
savings while giving superior anodization of objects and
anodization of objects that heretofore could not be satisfactorily
coated.
Although preferred methods of my invention have been herein
disclosed, it is to be understood that the present disclosure is by
way of example and that variations are possible without departing
from the subject matter coming within the scope of the following
claims, which subject matter I regard as my invention.
* * * * *