ANODIZING OF ALUMINUM

by Charles A. Grubbs
Houghton Metal Finishing, Alpharetta, Ga.

An aluminum part, when made the anode in an electrolytic cell, forms an anodic oxide
on the surface of the aluminum part. By utilizing this process, known as anodizing, the
aluminum metal can be used in many applications for which it might not otherwise be
suitable. The anodizing process forms an oxide film, which grows from the base metal as an
integral part of the metal and when properly applied imparts to the aluminum a hard,
corrosion- and abrasion-resistant coating with excellent wear properties. This porous coating
may also be colored using a number of methods.
Many acidic solutions can be used for anodizing, but sulfuric acid solutions are by far the
most common. Chromic, oxalic, and phosphoric acids are also used in certain applications.
The morphology of the oxide fanned is controlled by the electrolyte and anodizing
conditions used. If the oxide is not soluble in the electrolyte, it will grow only as long as the
resistance of the oxide allows current to flow. The resultant oxide is very thin, nonporous, and
nonconductive. This particular property of the anodic oxide is useful in the production of
electrolytic capacitors using boric and/or tartaric acids.
If the anodic oxide is slightly soluble in the electrolyte, then porous oxides are formed,
As the oxide grows under the influence of the applied DC current, it also dissolves, and pores
develop. It is this property that allows us to color the oxide using organic dyes, pigment
impregnation, or electrolytic deposition of various metals into the pores of the coating.
By balancing the conditions used in the anodizing process, one can produce oxides with
almost any desired properties, from the thin oxides used in decorative applications to the
extremely hard, wear-resistant oxides used in engineering applications (hardcoating).
Colored anodized aluminum is used in a wide variety of applications ranging from
giftware and novelties through automotive trim and bumper systems. Such demanding
situations as exterior architectural applications or wear-resistant, abrasive conditions, such as
landing gears on airplanes, are not beyond the scope of anodized aluminum. Semiprecious and
precious metals can be duplicated using anodized aluminum. Gold, silver, copper, and brass
imitations are regularly fabricated. New and interesting finishes are constantly being
developed, which gain wide appeal across the spectrum of purchasers.
The utilization of electropolishing or chemical bright dipping in conjunction with a thin
anodic oxide produces a finish whose appeal cannot be duplicated by other means. Matte
finishes produced by etching the aluminum surface, affords the "pewter" look, which is
oftentimes desired. Matte finishes are also the finish of choice of most architects.
EQUIPMENT

Tanks
A wide variety of materials can and have been used to build anodizing tanks. Lead-lined
steel, stainless steel, lead lined wood, fiberglass-lined concrete, and plastic tanks have all been
used in the past. A metallic tank can be used as the cathode, but adequate distance between
the work and the tank must be maintained to prevoot shorting. Some problems are experienced
using metal tanks. For instance, the anode-to-cathode ratio is generally out of balance; also,
since the entire tank is an electrical conductor, uneven current flow is possible leading to
uneven oxide thickness formation, This uneven oxide formation causes wide color variations
in organically dyed materials and is not generally recommended.

476

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Generally, the use of inert materials in the construction (or lining) of the anodize tank is
recommended. PVC, polypropylene, or fiberglass are good inert materials for this application.

Cathodes
Cathodes can be aluminum, lead, carbon, or stainless steel. Almost all new installations
are using aluminum cathodes because of their ability to reduce the energy requirements of the
process. Because of the better conductivity of aluminum, the anode-to-cathode ratio becomes
extremely important. It has been found that an anode-to-cathode ratio of approximately 3: I is
best for most applications. Cathode placement is also of vital importance. It is recommended
that the cathodes be no longer (deeper) than the work being anodized. Placement of the
cathodes along the tank sides should be such that they extend no further than the normal work
length. For example most 30-ft long tanks can only handle 28-ft lengths; therefore, the
cathodes should be positioned at least I ft from either end of the tank to keep the work
material from "seeing" too much cathode and anodizing to a thicker oxide on the ends. The
depth of the cathodes in the tank should not exceed the normal depth of the work being
processed. If the cathodes extend deeper into the tank than the parts being anodized, there will
be excessive oxide growth on the parts in the lower portion of the anodizing tank. This will
result in color differences in the oxide and subsequently colored parts.
The correct alloy and temper for aluminum cathodes is vital, 6063 or 6101 alloys in the
T-6 or T-5 condition are best. The overaged T-52 temper should never be used! Cathode
material should be welded to an aluminum header bar using 5356 alloy welding wire. Bolted
joints are not recommended due to the possibility of "hot joints."
Employment of aluminum cathodes has done much to improve the overall quality of
anodized finishes in all areas of application.

Temperature Control
This is one of the most important factors influencing the properties of the anodic oxide
and must be closely controlled to produce consistent quality. The temperature should be held
to plus or minus 2F. Most installations have some means of temperature control, since large
amounts of heat are generated in the anodizing process.
Lead cooling coils have been used in the past, but newer plants use external heat
exchangers. The external heat exchanger has been found to be more efficient in cooling the
solution while offering additional agitation. Again, as mentioned above, the presence of other
metals in the tank. in conjunction with the aluminum cathodes, can cause undo electrical
problems.
One of the added benefits of using a heat exchanger is agitation. Proper placement of the
intake and outlet piping can insure good agitation as well as minimization of temperature
variations within the tank. This type of acid movement assures one of better anodizing.
Recently, the use of acid "spargers" in the bottom of the anodize tank has become
popular. These spargers replace the more common air spargers now being used and give much
better acid circulation and temperature control.

Agitation
To prevent localized high temperatures, some form of agitation is required in the bath.
Low-pressure air, provided it is clean and oil-free, is often used. Mechanical agitation and
pumping of the electrolyte through external heat exchangers are also used. Generally,
compressed air is not recommended due to the presence of oils in the lines. Multiple filteTS
in the air lines when using compressed air have not proven to be completely effective in
keeping oil out of the anodize tank.

478

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Racks
The two most common rack materials are aluminum and titanium. If aluminum is used,
it should be of the same alloy as the work, or at least not be an alloy that contains copper (2xxx
series). Alloys 6063 and 6061 are excellent rack materials. It must be remembered that
aluminum racks will anodize along with the work and must be stripped before being used
again. Titanium racks are more expensive, initially, but do not require stripping and are
generally not attacked by the baths used in the anodizing process. Only commercially pure
titanium can be used as rack material.
Titanium racks are not suitable for low temperature anodizing (hardcoating) where high
voltages are required. The lower conductivity of the metal causes heating of the racks and
eventual burning of the aluminum parts being anodized.

Power EqUipment
For normal (Type II) sulfuric acid anodizing (68-72'P), a DC-power source capable of
producing up to 35 V and 10 to 24 Nft 2 should be suitable.
Some processes such as phosphoric acid, oxalic acid, hard coating, or integral color may
require voltages as high as 150 V.
Power supplies come with a variety of options. Such things as constant current control,
constant voltage control, adjustable ramping, end-of-cycle timers/signals/shut-offs, and a
variety of other options make the anodizing process easier and more controllable.
Power supplies for hardcoat anodizing require more stringent capabilities. Those used for
Type III low temperature anodizing (28-32'F) will require voltages approaching 90 V and
amperages equivalent to 48 Nfe. Power supplies used for "room temperature" hardcoating
(SQ-6S'F) will require only 36 V and sufficient current to reach 36 to 46 Nft 2

SURFACE PREPARATION
The type of surface preparation prior to anodizing gives the metal finisher a choice of
effects. By combining mechanical techniques, such as scratch brushing or sandblasting with
buffing and bright dipping, interesting effects can be achieved. Sandblasting and shot peening
have also been used to give interesting surface treatments.
The beauty of dyed anodized aluminum can be further enhanced by color buffing the
work after it is sealed and dried, using a lime-type composition, preferably containing some
wax. In addition to actually polishing the coating, this step removes any traces of the sealing
smut.
Irregular shaped parts, castings, etc. are best finished by brushing with a Tampico brush
or by tumbling with sawdust or other suitable media.

PRETREATMENT

Cleaning
Proper and thorough cleaning of the aluminum surface prior to anodizing is one of the
most important steps in the finishing process. Improperly cleaned material accounts for more
reruns and rejected parts than any other single factor.
It is essential that all machining oils, greases, body oils, and other surface contaminants
be removed prior to the continuation of the anodizing sequence. Both alkaline- and acid-based
proprietary cleaners are available that will do an adequate job. If the oils or greases are
specific in nature, some cleaners may need to be "customized" for adequate results.
What is clean? Generally, we speak of a part being clean if it exhibits a "water-breakfree" surface. This means that if the water rinses off of the metal surface in a continuous sheet,

480

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the work is considered to be clean. If, on the other hand, the water "beads" up or forms water
breaks, the part still has foreign matter on the surface and continued cleaning is necessary.
Once the part has been determined to be clean, subsequent finishing steps can proceed.

Etching
Etching is the removal of some of the aluminum surface from a part using chemical
solutions. There are a number of reasons for etching aluminum:
l.
2.
3.
4.

To impart a matte finish to the material (lower the specularity or gloss).

To remove surface contaminants.
To hide surface imperfections (scratches, die lines, etc.)
To produce an overall uniform finish.

Chemical etching is accomplished using both alkaline and acid solutions. The most
frequently used etch media is sodium hydroxide. Time, temperature, concentration, and
contaminant level will affect the type of finish possible in an etch bath. Many proprietary
solutions are available from the chemical suppliers. Close attention to the technical
information included with the chemicals is important.

Rinsing
Probably one of the most abused steps in the finishing of aluminum is rinsing. Most
anodizers practice some form of "water management," usually to the detriment of the other
process tanks. Improper rinsing causes poor surface finish due to cross reactions of chemicals
left on the surface from previous processing tanks reacting with the chemicals in further
processing tanks. Cross contamination of expensive solutions is another fallacy of "water
management." Cascading rinses, spray rings, or just cleaner rinse tanks with adequate
overflow will go a long way in reducing poor finish and cross contamination.

DeoxldizlngIDesmutling
After etching, a "smut" of residual metallic alloying materials is left on the aluminum
surface. This must be removed before further processing. The use of deoxidizer/desmutters
will accomplish this, leaving the treated surface clean for subsequent finishing steps.
Many alloys, during their heat treatment steps, will form heat treat oxides. If these oxides
are not removed prior to etching or bright dipping, a differential etch pattern can develop,
which will cause rejection of the parts. In this instance a deoxidizer must be used. The
deoxidizer is designed to remove oxides, but is also extremely good at removing smut. A
desmutter, on the other hand, will not remove oxides. It is apparent that a deoxidizer would
be the preferred solution to have in an aluminum finishing line. Remember, a deoxidizer will
desmut but a desmutter will not deoxidize.

Bright Dippingand Electrobrightenlng

A chemical or electrobrightening treatment is required where an extremely high luster is
to be obtained on the aluminum surface. The electrobrightening or electropolishing treatment
is particularly applicable to the super-purity aluminum now used extensively in the jewelry
and optical field. Proprietary chemicals for these treatments are available from a number of
suppliers. Chemical brightening is most commonly used for most applications because of it's
ease of operation. A number of companies offer proprietary solutions, which will give you the
bright finish you desire. Specifics on the makeup and use of these solutions is available from
the chemical suppliers.

482

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ANODIZING
Properties of the Oxide Film
The anodizing process conditions have a great influence on the properties of the oxide
formed. The use of low temperatures and acid concentration will yield less porous, harder
films (hardcoating). Higher temperatures, acid contents, and longer times will produce softer,
more porous, and even powdery coatings. It must be remembered that changing one parameter
will change the others, since they are all interrelated.
It should also be pointed out that the alloy being processed may significantly alter the
relationship between the voltage and current density, often leading to poor quality coatings.
This is particularly true when finishing assembled components, which may contain more than
one alloy.

Factors Influencing Shade

In order to obtain reproducible results from batch to batch, a large number of variables
must be kept under close control. First to be considered are those that affect the nature of the
oxide.

Alloy
The particular aluminum alloy being used has a pronounced effect on shade, especially
with certain dyes. The brightest and clearest anodic oxides are produced on the purest form
of aluminum, the oxides becoming duller as the amount of alloying constituents are increased.
Super-purity aluminum (99.99% AI) and its alloys with small amounts of magnesium produce
an extremely bright oxide, which does not become cloudy upon being anodized for extended
periods.
Alloys containing copper, such as 2011, 2017, 2024, and 2219, although forming a
thinner and less durable oxide than the purer forms, produce a heavier and duller shade.
Magnesium in excess of 2% has a similar effect although not as pronounced. The presence of
silicon imparts a gray color to the coating; alloys containing more than 5% silicon are not
recommended for use with bright colors. Iron in the alloy can lead to very cloudy or "foggy"
oxides.
The majority of casting alloys contain appreciable amounts of silicon, ranging as high as
13%, and present difficulty in anodizing. Use of a mixed acid dip (normally containing
hydrofluoric and nitric acids) prior to anodizing is of value when high-silicon alloys are
encountered.
Since the various alloys produce different shades when anodized identically, the designer
of an assembled part must use the same alloy throughout if the shades of the individual
components are to match.

Anodizing Conditions
Other variables affecting the nature of the oxide i.e., its thickness, hardness, and porosity)
are the acid concentration and temperature of the anodizing bath, the current density (or the
applied voltage, which actually controls the current density), and the time of anodizing, These
factors must be rigidly controlled in order to achieve consistent results.
The "standard" sulfuric acid anodizing bath (Type II) produces the best oxides for
coloring. The standard anodizing solution consists of:
Sulfuric acid, 180-200 gIL
Aluminum, 4-12 gIL
Temperature, 68-n"p

484

As the anodizing temperature is increased, the oxide becomes more porous and improves
in its ability to absorb color; however, it also loses its hardness and its luster, due to the
dissolution action of the acid on the oxide surface. As the pore size increases, sealing becomes
more difficult and a greater amount of color is bled (leached) out into the sealing bath. The
ideal anodizing temperature, except where a special effect is desired, is 70"F.
Oxides produced by anodizing in chromic acid solutions may also be dyed. The opaque
nature of the oxide film produced in this manner has a dulling effect upon the appearance of
the dyed work. Consequently, some dyes, notably the reds, which produce pleasing shades on
sulfuric acid anodized metal, are unsuitable for use with a chromic acid coating. Fade
resistance of this type of dyed oxide is extremely poor, possibly because the oxide is not thick
enough to contain the amount of dye needed for good lightfastness. The best chromic acid
coatings for dyeing are produced with a 6 to 10% by weight solution operated at 120"F. A
potential of 40 to 60 V is used, depending upon alloy, copper- and silicon-bearing materials
requiring the lower voltage. The usual time is from 40 to 60 minutes.

DECORATIVE ANODIZING
Decorative anodic oxides are used in a great many applications, from lighting reflectors
to automotive trim. The thickness of the oxide might range from 0.1 to 0.5 mil (2.5 to 12
microns). As mentioned above the most common electrolyte is sulfuric acid and typical
conditions are listed below. Parts that are to be given bright specular finishes are usually
produced from special alloys formulated for their bright finishing capabilities.
Typical decorative anodizing conditions are:
Sulfuric acid, 165-180 gIL
Temperature, ~O"F
Current density, 10-15 Nfr
Voltage, depends on current density, temperature, and electrolyte
Time, 12-30 minutes depending on film thickness desired. Longer times produce thicker
coatings.

ARCHITECTURAL ANODIZING
The conditions used in architectural anodizing are not much different than those used for
decorative applications, except the anodizing time is usually longer and the current density
may be slightly higher. In general the thickness of the oxide will be greater than for decorative
coatings, and this relates to the treatment time.

Interior
For interior applications the coating will be probably 0.4 mil thick (10 microns). This
means an anodizing time of about 20 minutes at IS Nft2

Exterior
For exterior uses the coating will be a minimum of 0.7 mil thick (18 microns) and this
means an anodizing time of about 39 minutes at IS Nft2

INTEGRAL COLOR ANODIZING

This process, used mainly for architectural applications, requires the use of specially
formulated electrolytes, usually containing organic sulfo acids with low contents of sulfuric

485

acid and aluminum content, to produce a series of bronze to black shades. The color produced
is dependent upon the time of treatment and the final voltage used. Specially formulated alloys
are also required . Large amounts of heat are generated in the process due to the high current
densities employed (up to 45 Nft2 ) , so efficient heat exchange equipment is needed to keep
the bath cool.

HARDCOATING
Hardcoating (Type III) is a name used to describe a special form of anodizing . The
process, which usually employs higher acid concentrations, lower temperatures. and higher
voltages and current densities is sometimes referred to as an "engineering hardcoat.' This is
due to the fact that hardcoating imparts a very hard, dense. abrasion-resistant oxide on the
surface of the aluminum. A dense oxide is formed due to the cooling effect of the cold
electrolyte (usually 30--40'F). At these temperatures. the sulfuric acid does not attack the
oxide as fast as at elevated temperatures. Because of the lower temperature. the voltages
needed to maintain the higher current densities also help form smaller, more dense pores. thus
accounting for the hardness and excellent abrasion resistance .
Normal low temperature hardcoating is carried out under the following conditions:
Acid concentration. 180-225 gIL
Aluminum content. 4-15 gIL
Temperature. 28-32'F
There have been a number of organic additives developed in the past few years that allow
the anodizer to hardcoat at elevated temperatures (50-70'F). These additives, by virtue of their
chemical reaction in the oxide pores. help cool the material being anodized and retard acid
dissolution of the coating.

COLORING OF ANODIC COATINGS

The coloring of anodic oxides is accomplished by using organic and inorganic dyes.
electrolytic coloring, precipitation pigmentation, or combinations of organic dyeing and
electrolytic coloring. After the anodizing step. the parts are simply immersed in the subject
bath for coloring .
The thickness of the anodic oxide can range from 0.1 mil for pastel shades up to 1.0 mil
for very dark shades and blacks. Application of electrolytic coloring will be discussed below.
Suffice it to say. the combination of organic dyeing and electrolytic coloring gives a more
complete palette of colors from which to choose.

Organic Dyes
The actual process of dyeing the aluminum oxide is very simple. A water solution of
0.025 to 1.0% of dyestuff at a temperature of J40'F composes the dyebath. The aluminum.
previously anodized, is simply immersed in this bath for a short period of time. usually 10 to
30 minutes. The work is then sealed and is resistant to further dyeing or staining .
The equipment required, in addition to that needed for the actual anodizing operation.
consists of rinse tanks with clean. flowing water; a dye tank for each color desired; and a
sealing bath preferably equipped with continuous filtration.
The dye tanks must be of stainless steel. plastic, fiberglass. or some other inert substance;
never of copper or steel. They must be supplied with means of maintaining a constant 140'F
temperature and should be equipped with some form of agitation. Usual plant practice is to
use air agitation; however, with proper filtration. the filter itself can be used as the source of
agitation. With air agitation the use of water and oil traps. plus a filter on the air supply. is

486

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necessary to prevent contamination of the dye solution. A few drops of oil spread on the
surface of the dyebath is very often the cause of streaked and spotted work. Typically, the use
of blower air agitation is preferred over compressed air.
Rinsing after anodizing, followed by immediate dyeing, is of prime importance. Since
some dyes will not dye aluminum in the presence of sulfate ion, poor rinsing can cause streaks
and discolorations. Even in the case of dyes not affected by sulfates, any carry-over of acid
causes a lowering of the pH of the dyebath, which means shade variations in succeeding
batches of work.
In the design of parts to be color anodized, care must be taken to avoid the use of closed
heads or seams, which are impossible to rinse. In the case of parts containing recesses, which
are difficult to rinse, a neutralizing bath of sodium bicarbonate is of value. In working with
coated racks, care must be taken that the rack coating does not separate, thereby forming
pockets that can entrap sulfuric acid, later allowing it to seep out into the dye bath. Work must
not be allowed to stand in the rinse tanks between anodizing and dyeing, but should be dyed
immediately, following a thorough rinsing. For most effective rinsing, three tanks should be
used. In this way the final tank, usually deionized water, will remain relatively free of acid.
The variables in the dyebath are time, temperature, concentration, and pH. Time and
temperature are readily controlled in plant practice; however, regulation of concentration
presents some difficulties. Fortunately, in the case of most single component dyes, concentration control is not very critical, a variation of 100% causing little change in depth of shade.
The usual dyebath concentration for full shades is 2 gIL except for black, which requires
from 6 to 10 gIL. In the case of pastel shades concentrations of considerably less than 2 gIL
may be required in order that the shade does not become too deep. This reduction in
concentration will have a negative effect on the dye Iightfasmess.
Control of pH is important and a daily check (more often in smaller tanks or where high
volume is a factor) should be made. The pH range between 6.0 and 7.0 gives the best results
with the majority of dyes; however, a few are more effective at values close to 5.0. Initial
adjustments should always be made since it is not practical for the manufacturer to standardize
the dyes with respect to the pH of their solutions. These adjustments are made by addition of
small amounts of acetic acid to lower the pH value and dilute sodium hydroxide or acetate to
raise it. Solutions may be buffered against possible carry-in of sulfuric acid by adding I gIL
of sodium acetate and adding sufficient acetic acid to reduce the pH to the desired value.

COLORFASTNESS OF THE DYED COATING

Of the many dyes that color anodized aluminum, possibly several hundred, it should be
understood that only a few possess sufficient inherent resistance to fading to be considered for
applications where exposure to direct sunlight is intended. Where items of long life
expectancy are involved, for example, architectural components, even greater selectivity must
be imposed, since all organic colorants now known will exhibit some fading when subjected
to sunlight of sufficient intensity and duration. Also, the parameters of application as well as
the colorant are involved in the resistance to premature loss or change of color. The following
additional factors are considered by most authorities as affecting the Iightfastness of the dyed
coating.

Coating Thickness and Penetration of the Dyestuff

Accelerated and long-term exposure tests and practical experience both here and abroad
verify that an anodic oxide thickness in the order of 0.8 mil (20 microns) and its complete
penetration by the colorant is required for optimum resistance to fading and weathering. This
means that, in some applications, the dye time may be extended to 30 minutes for complete
dye saturation.

488

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Intensity of Shade
Usually, the greater the amount of dye absorbed, the better its resistance to fading. Also,
whatever fading may occur will be less apparent to the observer. Pastel shades may, therefore,
be expected to exhibit inferior light and weather fastness as compared to full strength dyeing.

Type and Degree of Sealing

Those dyes that are reactive with the nickel or cobalt salts present in the sealing bath
usually require this treatment for optimum performance. It is reported that certain selected
dyestuffs benefit from after-treatment with other heavy metals; for example, lead, copper,
zinc, or chromium. Generally, such treatments are not utilized because of the requirement of
an individual sealing tank for each dye.
In the case of extremely porous anodic oxides, for example, those formed on alloys of
high copper content, effective sealing is particularly important with certain dyes to prevent
color loss from sublimation of the dye or by chemical reaction in oxidizing or reducing
environments.

ELECTROLYTIC COLORING (2-STEP)

This electrolytic coloring process consists of conventional sulfuric acid anodizing
followed by an AC treatment in a bath containing tin, nickel, cobalt, or other metal salts to
produce a series of bronze to black colors as well as blues, greens, burgundies, and golds. The
most common bath is one containing tin. The colors produced are not alloy or thickness
dependent and are easier to control. The process is not as energy intensive as the integral color
process. It is for this reason that this process has almost entirely replaced the integral color
process in recent years. Unlike sulfuric acid anodizing, the coloring process is controlled by
voltage and time, rather than by current density. Depending upon the bath used, the coloring
time can range from 20 sec for champagne to 10 min for black. The use of specially built AC
power supplies, using electronic timing and voltage control. helps produce a finish that is
reproducible time after time. Proprietary baths containing bath stabilizers. color enhancers,
and other additives are being marketed and used throughout the finishing industry.

PIGMENTATION BY PRECIPITATION OF INSOLUBLE COMPOUNDS

Before the development of special organic dyes for coloring anodized aluminum. the
precipitation of various insoluble metal compounds within the anodic oxide was used
commercially. The treatment consisted of alternatively immersing the anodized surface in
concentrated solutions of suitable metal salts until a sufficient amount of the pigment was
precipitated to produce the desired color. Although seldom used in today's state of the art, a
number of these reactions are listed below;
Lead nitrate (or acetate) with potassium dichromate-yellow
Lead nitrate (or acetate) with potassium permanganate-red
Copper sulfate with ammonium sulfide-green
Ferric sulfate with potassium ferrocyanide-blue
Cobalt acetate with ammonium sulfide-black

Ferric oxalates (ferric ammonium oxalate or ferric sodium oxalate) applied to conventional
anodic oxides in the same manner as organic dyes are, under proper conditions, hydrolyzed
to deposit ferric hydroxide within the coating pores. imparting a gold to orange color of
outstanding resistance to fading. Special proprietary chemicals are available for this treatment.

490

The deposit of ferric oxide produced in the above manner may, in addition. be convened
to ferric sulfide, the resultant shade of which is black. Alternatively. a bronze shade may be
formed by reduction of the ferric oxide with pyrogallic acid.
Cobalt acetate reduction. although commercially used in Europe, is not well known in
the U.S. It consists of saturating a conventional anodic oxide with the cobalt solution and then
reacting this with potassium permanganate to produce a cobalt-manganese dioxide complex .
The resultant bronze shade has excellent lightfastness and offers some potential for
architectural applicat ions.

MULTICOLOR ANODIZING
The application of two or more colors for the production of nameplates. instrument
panels, automotive and appliance trim, etc. has now achieved sufficient commercial
importance that a number of large firms deal exclusi vely with such items.
The following methods of multicolor anodizing are possible:
The multiple anodi zing process , which entails a complete cycle of anodizing, dyeing, and
sealing; application of a resist to selected areas; stripping of the entire anodic oxide from the
remaining unprotected surfaces; and repetition of this entire procedure for each color.
The single anodizing method. wherein an anodic oxide of sufficient thickness and
POrosity to absorb the dye required for the darkest shade is first applied . This oxide is then
dyed and left unsealed, a resist applied, and the dye alone discharged or bleached out with a
solution that leaves the anodic oxide intact. The operation is then repeated for each successive
shade. Finally, the resist is removed with a suitable solvent, and the entire surface sealed. In
certain cases, where a dark shade is to be applied after a pastel shade. a modification of this
teChniqueomits the bleaching step with the supplementary dye being applied directly over the
preceding color.
The use of a specialized combination ink-and-resist enables information or designs to be
printed directly on the previously formed anodic oxide in several colors. The background
color may then be applied by conventional dyeing methods. while the ink serves as a stop-off
for the printed areas.
Preanodized, photo-sensitized aluminum alloy material is available , wherein the image.
in black, may be produced by photographic methods , and the background colored by the
conventional dye immersion method.

SEALING OF ANODIC COATINGS

HYdrothermal Sealing (20Q-212'F)

To achieve the maximum protective qualities and corrosion resistance required for
finished articles, the anodic oxide must be sealed after it is formed and/or colored. The sealing
process consists of immersing the anodized pans in a solution of boiling water or other
SOlution such as nickel acetate, wherein the aluminum oxide is hydrated . The hydrated form
of the oxide has greater volume than the unhydrated form and thus the pores of the coating
are filled or plugged and the coating becomes resistant to further staining and corrosion . The
use of nickel containing seals will, in most cases, prevent leaching of dyes during the sealing
operation.
When sealing with the nickel acetate bath, a smutty deposit may form on the work. This
ean be minimized by the addition of 0.5% boric acid to the bath or by the use of acetic acid
to lower the pH of the solution to 5.3 to 5.5. Too Iowa pH. however, causes leaching out of
the dye. Use of 0.1 % wemng agent in this bath also aids in preventing formation of the smut.
Proprietary sealing materials designed to completely eliminate this smut are now available
from chemical suppliers .

491

The sealing tank should be of stainless steel or other inert material and must be
maintained at 200F. Use of a filter enables a number of colors to be sealed in the same bath
without danger of contamination.

Mid-Temperature Sealing (16D-190'F)

Due to the higher energy costs inherent in hydrothermal sealing, chemical manufacturers
have developed "mid-temperature" seals (160-190F). These seals, which contain metal salts
such as nickel, magnesium, lithium, and others, have become very popular due to the lower
energy costs and their ease of operation.
One disadvantage of the lower temperature is the tendency of organically dyed parts to
leach during sealing. This can be compensated for by a slight increase in the bath
concentration and by operating the solution at the upper temperature limits (l90'F).
"Nickel-free" seals (or more "environmentally friendly" seals, as they are called) are fast
becoming the seal of choice where clear or electrolytically colored parts are concerned.
Because there is nothing to leach, these mid-temperature seals accomplish hydration of the
oxide without the use of the heavy metal ions. When the seals become contaminated or are no
longer effective, they can be discharged to the sewer without subsequent treatment (except
possible pH adjustment). This offers the finisher a safer alternative to the effluent treating
necessary with heavy metal containing seals.

Room Temperature (Cold) Seals (7D-90'F)

A significant modification in the sealing of anodized aluminum was the development of
"room temperature sealing" (70-90'F). Unlike the high temperature and mid-temperature
seals, which depend on hydration for sealing, the cold seals rely on a chemical reaction
between the aluminum oxide and the nickel fluoride contained in the seal solution.
Unfortunately, this reaction is slow at ambient temperatures and the sealing process can
proceed up to 24 hours; however, it has been found that a warm water rinse (l60'F) after the
cold seal immersion will accelerate the sealing process, allowing for handling and packing of
the sealed parts. The sealing of organically dyed parts in cold seals has been found to be
advantageous. Light stability testing (fade resistance) has shown that parts sealed in cold seals
gain additional lightfastness.

OTHER ELECTROLYTES
A number of other electrolytes are used for specialized applications.

Chromic acid is used in marine environments, on aircraft as a prepaint treatment, and in

some cases when finishing assemblies where acid may be entrapped. Although the film
produced is extremely thin, it has excellent corrosion resistance and can be colored if desired.
A typical bath might contain from 50 to 100 gIL of chromic acid, and be run at about 95
to 105'F. There are two main processes, one using 40 V and a newer process using 20 V. The
equipment needed is similar to that used in sulfuric acid processes.
Oxalicacid is sometimes used as an anodizing electrolyte using similar equipment. This
bath will produce films as thick as 2 mils without the use of very low temperatures and usually
gives a gold or golden bronze color on most alloys. The typical concentration is from 3 to 10%
oxalic acid at about 80 to 90'F, using a DC voltage of about 50 V.
Phosphoric acid baths are used in the aircraft industry as a pretreatment for adhesive
bonding. They are also very good treatments before plating onto aluminum. A typical bath
might contain from 3 to 20% of phosphoric acid at about 90'F, with voltages as high as 60 V.

492

SUMMARY
Aluminum is a most versatile metal. It can be finished in a variety of ways. It can be
made to resemble other metals, or can be finished to have a colorful as well as a hard, durable
finish unique unto itself. Only the imagination limits the finish and colors possible with
anodized aluminum.

Anodic Coating Defects - Their Causes and Cures

by A. W. Brace 168 pages $150.00
This book provides guidelines and examples for troubleshooting defects in anodic
coatings. Chapter one outlines an approach to identifying a defect. Here one finds a
photo and description of each defect (for instance, fine pitting) with a remedy for
curing it; a simple and straightforward approach to problem-solving.
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493