Recognizing and Dealing with General Anodizing Problems

by

Richard Mahn

Originally Published in:

PLATING AND SURFACE FINISHING

Journal of the American Electroplaters and Surface Finishers Society

July 1988

Topics covered in this article: Substrate Problems; Metallurgical Properties; Handling Steps;
Pretreatment Line; Anodizing Concerns; Sealing Process; Constant Current; Rinsing Stages;
and Troubleshooting.

Everything from the condition of the aluminum to the application of the seal can affect the
quality of sulfuric acid anodizing.

Anodizing is one of many steps in a process that begins with the alloying of pure metal in a
cast house and doesnt end until the product has been inspected and approved. In between
exists a multitude of opportunities for the emergence of problems that can affect finish
durability and appearance.

Such problems should be identified during the inspection of finished loads when parts are
unracked (if not before). Failure to pinpoint the culprit could lead to reject material in the
hands of the customer. Proper evaluation at inspection is crucial to determine if the
problem is unique to the individual workload or if something has developed in the system
that will affect other loads as well. That evaluation is dependent on a proper understanding
of anodizing.

Anodizing is the generation of an aluminum oxide film under controlled electrochemical

conditions to uniformly cover and protect the surface of bare aluminum metal. As oxidation
takes place, the quality of the film is influenced by the physical and chemical characteristics
of the aluminum basis metal from which it is formed. The anodized film is transparent and
does not have the capability to mask over metal surface defects, even when colored.
Therefore, the final finish appearance depends largely on the condition of the aluminum
workpiece.

Most anodizing-related problems arise from deficiencies in the quality of the basis metal or
the anodic film, or from a combination of the two. Hence, one of the most important skills in
troubleshooting is being able to visualize a problem as a result of the influence these factors
have on the chemical and physical uniformity of the finish. To do that effectively, the
troubleshooter must be knowledgeable about metal production, handling procedures,
racking techniques, cleaning and other pretreatment operations, the anodizing process
itself, sealing, rinsing, and testing. Some of the major considerations are addressed here.

Substrate Problems

The first source of trouble may be in the metal itself. One of the most common occurrences
is the inclusion of dross or bath particles in the ingot or billet. These particles can spread
through the surface of the metal during rolling or extrusion. In the case of rolled products,
the oxides may not have originated within the metal, but from oxides rolled into the
surface. These "zones" of pre-existing oxides do not take part in the anodizing process and
therefore become open areas in the anodized finish. If a post anodizing color step is
involved, quite often these zones will remain uncolored and appear as white or gray
streaks.

The most common alloy used for anodizing is 6063, and most anodizers are familiar with its
appearance after anodizing. This is not something that just happened, but is the result of
much experimentation to produce a finish that is attractive, whether natural or colored.

The alloying constituents (elemental metals) are finely dispersed throughout the aluminum
and, as with inclusions, they do not oxidize during the anodizing step. Instead, as the
oxidation of the aluminum takes place, the finely dispersed particles are lifted and become
a part of the transparent film or dissolve, leaving voids throughout (Fig. 1). Either can lead
to a dull or grayish appearance, a condition that becomes more pronounced with the
thickness of the film or the concentration of the alloying constituents. During the
pretreatment step of etching, alloys that have a high concentration of alloying constituents
can be identified by the heavy gray smut that forms.

Film uniformity is not affected as adversely by alloying constituents as by non-metallic

inclusions. However, abrasion and corrosion resistance of the anodized film may suffer
from alloying constituents because the particles and voids can reduce the integrity and
strength of the cellular structure of the aluminum oxide film. This condition is best
exemplified by the high-copper-containing alloys such as 2024. Because of the dissolution of
the copper particles during anodizing, a dull gray or gold finish that has low abrasion
resistance is the result.

Practically all aluminum alloys can be anodized in some form or another, but because of the
effects of the alloying elements on appearance and film quality, consideration has to be
given to the end use of the coating. Alloys to be used for extrusion and anodizing purposes
are generally formulated from primary metal and controlled during casting and subsequent
operations to produce the needed metal quality. However, it is common to encounter
secondary metal that will result in a more mat or gray appearance due to high
concentrations of alloying ingredients, especially silicon and iron. Therefore, if the final
anodized appearance is not the one expected, this could be an indication of improper alloy.

Metallurgical Properties

The function of an alloy is dependent on its metallurgical properties. The most important is
that of structural strength, which for architectural applications must be coupled with a
quality anodized finish. Both are dependent on grain structure.

If the alloying ingredients are not finely and uniformly distributed or chemically combined,
the resulting surface pattern after etching will be in one of two conditions. First, it could be
coarse and grainy because of the selective dissolution of aluminum from around the large,
non-dispersed particles. Or it could exhibit a frost-like pattern as a result of slow crystalline
growth of the aluminum and its constituents. This can occur as a result of improper
homogenization of billet, poor quenching during extruding, or improper heat treatment of
extruded parts.

A common problem is the hot/cold spot, which may occur in a random or regular pattern
along an extrusion. This is usually due to contact between the part and the run out table
during extruding, thus interfering with the cooling process. Cooling is generally slower at
that spot, and as a result, the grain structure is larger and the particles less well dispersed.
After etching, this shows up with a darker coating of smut, and after anodizing the spot will
become grayer and more mat. This is due to the large localized particulate concentrations
and cannot be corrected or hidden by the anodizing process.
Now a word about heat treatment. The designation that relates the desired metallurgical
qualities to the degree of post-extrusion heat treatment required is called temper. Generally,
the higher the temper the fine will be the grain structure and the better the anodizing
response, producing a brighter, smoother, and less gray finish (Fig. 2). Different structural
requirements dictate a wide variety of tempers, so it is important to be aware of what is
being anodized and what kind of response is expected.

Handling Steps

From the time parts are extruded or sheet is rolled, several handling steps are employed.
The material is cut to length, stacked on carts, heat treated, stored for cool down,
dismounted, possibly stored again until ready for anodizing, and finally racked. In each
step, the mill-finished, unprotected metal is handled with hands (clean or greasy, with or
without gloves), stacked in contact with wood or cardboard (wet or dry), stored outside
exposed to the elements or inside close to the anodizing line with its inherent fumes, and
eventually racked (again with gloved or bare hands).

In one case, an individual had been working on a greasy crane motor and came over to
"help" the rackers for a few minutes. Of course, every piece that he handled ended up after
anodizing with his gloved finger and/or palm prints. The grease, which was not only heavy
but impregnated with fine metallic particles, left a residue and surface blemishes that the
cleaning solution could not remove, so selective rather than uniform etching took place.
Generally, any type of hand prints will show up as etch patterns (distinct or unrecognizable)
after anodizing. Again, the anode coating cannot hide such blemishes.

Another problem is in the storage of mill-finished material. Over time, a normal, uniform
oxide film will build up, and this usually does not present a problem. However, in contact
with moisture, a humid atmosphere or chemical fumes, the surface may become more
oxidized in certain spots. Cleaning/degreasing alone cannot deal with this type of oxidation,
and the result after etching is pitting or a galvanized appearance. Once this occurs, there is
little that can be done to salvage the metal. Passing the load to the desmutting solution
(using it as a deoxidizer) prior to degreasing sometimes can reduce the incidence of the
problem; however, it is not a cure-all for poorly handled or stored material.

Racking Procedures

It is important to remember that racking is used to make electrical contact, not just to
suspend parts for passage through various solutions. Good racking practices cannot be
overemphasized. The contact, once made, has to endure severe attempts to break it loose,
not the least of which occurs during the anodizing step with the tremendous force exerted
by the growing aluminum oxide film, which can then act as an electrical insulator.

The results of poor contact are readily measurable using coating thickness testers or by
observing the contact point on the end of the part. Burned or gray-looking areas may
indicate overheating (Fig. 3). Thickness non-uniformity on a load of parts is an indicator of
random rack contact. (In electrolytic coloring, this is readily visible as color variation, or
"light ends," on workpieces.)

Another source of problems is parts spacing. Anodizing followed by coloring must conform
to certain spacing rules if uniform coating thickness and color are to be achieved. Either
single- or double-spine designs may be employed, optionally with a center cathode in the
anodizing and electro-coloring tanks. For clear anodizing, racking is relatively dense with
multiple parts across. But this can lead to non-uniform coating thickness because the inside
parts receive less energy for film growth with distance from the cathodes and because they
are shielded by outside pieces. Thus, parts in the center will have a thinner coating than
those at the outside. For most applications of commercial and residential clear-anodized
products, the thickness may be adequate to protect the aluminum, though it may not
actually meet the required specification.

Returning to electrical contact, a significant problem that can occur in a very random
fashion, depending on the operators attention to detail, concerns inadequate rack stripping
between loads, especially if Class 1 and Class 2 architectural coatings are being produced. If
any film is left on the spline, it will act as an insulator for the next load of parts, preventing
contact altogether or causing a high resistance contact point that can result in the same
burning or discoloration problems discussed above.

Pretreatment Line

Deoxidizing, degreasing, etching, and desmutting are among the chief pretreatment steps
that have an impact on finish quality and appearance (Fig. 4). We will consider each one in
this section.

Deoxidizing: As pointed out previously, if handling or storage of the aluminum workpiece

results in hand prints or other problematic conditions (e.g., corrosion), it is a good idea to
add a deoxidizer step at the beginning of the pretreatment sequence.

Cleaning/Degreasing: The importance of this step in the chain of events is often

overlooked. If the temperature is too cold, the concentration of the soap additives too weak,
or the formulation not correct for the needs of the plant, cleaning will be inadequate. The
result is selective etching, leaving mottled patterns on the metal surface.

If allowed to become too old and contaminated, the soap solution can cause a pitting action
if the load is left in for more than 5 min. When working properly, it should be possible to
leave loads in the solution for up to 30 min without experiencing problems.

The degreasing agents in cleaners are formulated to be non-etching, but are either slightly
caustic (common for architectural anodizing) or slightly acidic (usually for special
applications such as automotive anodizing where buffing compounds are difficult to
remove with a single cleaner).

Etching: The basic purpose of etching is to dissolve the surface of the metal to: remove
ground-in impurities, diminish or eliminate extrusion die lines and mild scratches, impart a
smooth, uniform appearance, and change the natural brightness to a mat condition. The
important control criteria are: solution temperature; concentration of caustic, chelator, and
grain refiner; degree of air agitation; and rate of load transfer.

Variations in chemical concentrations and temperature can result in insufficient etching

(apparent by brightness and appearance of die lines) to over-etching, which results in a very
grainy texture and too dull a finish. Air agitation and transfer time can cause streaking from
the abrasive action of air bubbles traveling upward or from rundown and continued
etching during transfer. It is important to use well-distributed, low-pressure air, to keep the
temperature moderate to avoid dry-on during transfer, and to transfer quickly.

If dry-on occurs, salt deposits resultóspecifically, aluminum hydroxide, which is not

removed in the rinse tank or the desmutting solution. These deposits not only look bad on
the finished product but represent sites where anodizing will not occur (similar to the effect
of metallic inclusions) and can become corrosion zones on exterior exposure. Many etch
formulations, referred to as "never dump" solutions, are designed to function with a high
rate of drag-out to control the buildup of aluminum in the solution and allow for rapid
transfer.
Desmutting: Most of the principal alloying constituents (silicon, iron, copper, and
manganese) are not soluble in or reactive with the etch solution. As a result, particles of
these elements are left on the surface in a form called smut. It is necessary to remove these
particles because they will contaminate the anodizing tank.

The solution formulated to accomplish this is based on mineral acid, which readily dissolves
all but the silicon.

This would seem to be straight forward and, in fact, is probably the least problematic step in
the process. However, if thorough rinsing is not carried out before the workpiece enters the
desmutting solution, the reaction between the acid and the caustic can result in the
formation of aluminum hydroxide scum, which entraps smut particles. At the least, this
increases the time required to dissolve the smut in the desmutting solution. At worst, it
leaves a film that may selectively dissolve in the anodizing solution, leaving insoluble
particles such as silicon on the surface. These particles will not prevent anodizing as theyre
not in the metal. However, they will neither dissolve in the anodizing solution nor be
incorporated in the cellular structure of the anode coating, so the particles end up as a film
or residue on the finish.

With the standard anodizing-quality alloys, the silicon concentration is controlled or

coupled with magnesium such that the silicon is removed with the other elements in the
desmutting solution. However, primary alloys like 6061 or secondary 6063 alloys, which
have a high silicon concentration and which have been heavily etched, can present
problems. Clear finishes may not show this residue or may exhibit a slightly gray
appearance, but this can be a serious problem for colored finishes, and removal is difficult.

Anodizing Concerns

In this section, we will look at anodizing related concerns involving contact, coating
thickness, and current distribution.

Contact: There are three important contact systems, the first of which was discussed briefly
under "racking." There must be good contact between the parts and the splines, between the
splines and the flight beam, and between the flight beam and the power saddles located on
the tank. Well refer to this as the workload. The workload has to receive power from the
rectifier via bussing, which may have several connections between it and the power saddle.
This constitutes the supply. The workload then has to pass the power through the electrolyte
to the cathodes, which are connected to a system of bussing that (also having several
connections) returns the power back to the rectifier, thus completing the circuit. This well
call the return.

Breakdowns at any of these connection points will cut off the circuit and no power will flow.
The obvious result is no anodizing, resulting in the need for immediate action to get the
power flowing again so that production may resume. (There is, however, a far more subtle
problem, the insulation effect, which can lead to serious and varied problems in coating
uniformity. Well talk about that effect in our discussion of current distribution.)

Film Thickness: One of the most simple and useful tools in anodizing is the non-destructive
thickness tester that can be used right on the production line. With it, the operator can
determine how thick the coating is and how well it is distributed over the workload. The
most common problems in this category involve thickness variations from one workload to
another, from top to bottom, from end to end, and from inside to outside. Some of these, as
suggested above, are the result of racking techniques, but they can also occu r d ue to
contact problems.
Current Distribution: Coating variations within a workload are generally a function of
how the current is distributed once the parts enter the tank. The current flows off the
workload through the electrolyte to the cathodes, which have to receive it in the proper
manner. It must be remembered that the current doesnt care where it goes; it simply
follows the path of least resistance.

An example of this is when thicker coatings form on parts at the bottom than on parts at the
top of a workload. The problem source may be a lead-lined anodizing tank or a large
cathode surface area at or near the tank bottom. In these cases, more current is drawn
through parts near the bottom of the load, generating a thicker anodic film. It is advisable to
mask off or cover the bottom, ends, and portions of the side walls of a metal-lined tank to
obtain better current distribution.

In designing new systems, the tank lining is usually made of a special inert rubber, plastic
or fiberglass material with cathodes suspended along the sides. Experience has shown that
the cathode area, properly distributed along the side walls, can be one-third to half the
surface area of the largest routine workload and still be sufficient for most anodizing needs,
especially if made of aluminum. In cases where film uniformity is critical for inside
surfaces, a center cathode can be added.

Another problem, not as common but far more serious when it does occur, is end-to-end or
totally random variation in film thickness. The cause can be the contact between the
cathodes and the bussing along the top of the tank. Acid solution aspirated by air agitation
from below Of dripping off loads passing overhead can penetrate between buss surfaces
and form oxides that ultimately insulate the connection. Current flow is then reduced or cut
off entirely to that cathode

section. The current, seeking the path of least resistance, will flow from workload zones
closest to the cathode areas that are functioning better. Quite often, the insulation effect
develops at the end of the tank where most of the drag-out drainage occurs and on the side
over which the workload passes for rinsing.

This problem was encountered in a plant producing Class 1 films, which are supposed to be
0.7 mil thick. Workloads exhibited variations of 0.3 mil at the drainage end to 1.2 mil at the
opposite end. A check of the cathode plates demonstrated that less than half were
functioning properly. The problem arose because the cathode/buss connections were
unprotected from acid drainage of workloads.

For positive identification of the insulation effect in any shop, the operator places a
workload in the anodizing tank and allows it to stabilize for about 5 min. At that point, the
air agitation is shut off and the evolution of gases from the cathodes observed. Gassing
should be uniform from all surfaces opposite the workload and should exhibit equal
flowing action from both sides to the center of the tank. If this is not the case, the cathodes
may be partially or totally insulated.

In any event, steps should be taken to protect and regularly maintain the cathode/buss
connections and all others in the anodizing circuit to prevent the insulation effect.

Constant Current

Many anodizers operate with constant voltage control, which is used exactly the same way
on every workload regardless of size or shape. The assumption is that the result will be the
same each time.

For some applications, this may be adequate, but it certainly will not give identical results.
The problem is that the total system (supply, workload, and return) is erroneously thought
of as an integral unit that has one large voltage drop. Actually, the system operates as a
series of small voltage drops that begin at the rectifier and accumulate as the current passes
through every connection point. And, as we have discussed, the connections that are in a
fixed position can be attacked by solutions splashed during transfer or from fumes and can
suffer from the insulation effect. Over time, resistance may build and the current available
for anodizing can be slowly reduced. So if constant voltage is used, the anodizing time will
likely have to be increased or the coating thickness will gradually diminish as current flow
is reduced.

In the same system, there are many connections (as in racking) that change with every
workload. If those connections do not have the same voltage characteristics each time, there
will be current variation from workload to workload and consequent differences in film
thickness.

Because electrochemical oxidation in anodizing occurs as a function of current and not

voltage, maintaining the same current density to each workload and freeing the voltage to
respond to the resistance variations results in a more uniform film from one load of parts to
the next. Control by constant current density is based on a predetermined current per unit
of surface area (e.g., ft2) and requires a calculation of total workload area, including racks.
This is a somewhat tedious procedure; however, if there is a problem of load-to-load non-
uniformity, it may be advisable to consider changing to constant current control, even if
making workload area calculations may not be the easiest way to go. Though tedious at the
outset, once put into practice as a routine part of the job, it can become a very effective tool.

Sealing Process

The sealing process follows anodizing and requires contact with hot water, hydrolyzing the
aluminum oxide to form a hydrate that increases the volume of the cell structure. It
effectively closes pores and prevents film penetration by staining or corrosive materials.

A destructive test for ascertaining seal quality (and coating weight if necessary) utilizes a
solution of chromic and phosphoric acids at selected temperatures. Because it dissolves the
film but not the aluminum metal, the test can reveal if a problem originates in the anodic
coating or in the basis metal. The test can be set up easily in the lab and used as an
important measure of quality control.

Factors that affect sealing include water quality, pH, temperature, and time. Negligence in
their control will impair seal quality and generate some appearance problems resulting
from smut, residue, and powder.

Smut: If the temperature and/or pH of the seal are too low (less than 200 F and 5.5,
respectively), the hydrate that forms is not the desired one. Instead of a hard, smooth, clear
finish, the result is a soft, rough, chalky or hazy film. If the surface is then wiped, this causes
the film to transform to a white powder, which, if removed, considerably reduces the
thickness of the sealed coating.

This is true seal smut and is a direct result of sealing problems. In recent years, with an
understanding of this problem, conditions have been controlled or low-temperature nickel
based seals have been substituted, almost eliminating it. As a result, "smut" has come to be
used to describe two other surface problems that do not necessarily relate to the quality of
the seal.

Residue: Deposits of alloying constituents such as silicon can end up as a residue on the
film after sealing. This is not smut and is not generated by poor seal conditions, but may be
confused as such. The difference is that, although uniformly deposited on all part surfaces,
it can be removed by wiping. The surface underneath, if sealed properly, will be hard and
smooth .

Another source of residue comes from dissolved solids, salts or minerals that remain on the
surface after drying. These can accumulate in the seal tank through drag-in contamination
or prolonged use of the seal water. This residue is also removable by wiping. The surface
underneath may be properly sealed or, because of the mineral content, only partially
sealed, but will still be hard, clean, and smooth after wiping. This condition indicates the
need for a change of the seal bath.

Powders: The other type of deposit that can arise is loose powder, which wipes off with
very little effort. It results from undissolved solids that come from the neutralization of
soluble metal salts to form insoluble metal hydroxides in the rinse tanks. Powders can also
be a problem with the precipitation of nickel hydroxide in low temperature seal baths if
conditions are not properly controlled. Filtration of the seal bath can help control this
problem .

Rinsing Stages

It is unfortunate that rinses are often the least considered operation on the anodizing line,
with the possible exception of their water quality as they leave the plant. Too little water
flow leads to many residue and powder

problems as well as contamination of the various working solutions. Excessive water flow is
a waste and may result in unnecessarily high water and sewer costs.

Most of these situations can be mitigated or ameliorated by using counterflow rinses and
conductivity probes in the rinse tanks to control the chemical concentrations as a function
of pH. For example, many of the metal hydroxides remain water soluble at a pH of 2.5 to 3.0,
which is "clean" enough for a first rinse after most operations. This can be followed by a
second, cleaner rinse maintained at a pH of 5.5 to 6.5 and which counterflows to the first
rinse. The water flow through both tanks is then controlled by placing a conductivity probe
in the first rinse to actuate a valve that adds water to the second.

Besides the residue-type problems, over-contaminated rinse tanks can lead to surface
imperfections on the basis metal (Fig. 5). For instance, pitting or galvanic corrosion may
arise because of the chemical interaction between the contaminating salts and the bare,
unprotected aluminum. Also, because rinse tanks are considered inert, workloads are
sometimes left hanging on the crane without having been electrically isolated or left
touching metallic parts of the tank. This may result in a galvanic action that can destroy the
surface condition of the basis metal in a very few minutes.

Troubleshooting

Three of the major steps in the troubleshooting procedure are objective identification,
source determination, and patient investigation. Lets discuss each one briefly.

1. Objective Identification: How should a problem be defined, isolated, and eliminated? First
and most important, the anodized (and colored) workload must be examined and tested
carefully and objectively so that the problem is accurately defined. This has to be done
without looking to place blame on any particular individual or department. There have
been many situations in which problems were made more difficult to resolve because of
someones unwillingness to accept the responsibility for correcting the problem. This can
seriously interfere with making a good assessment. So be objective, open minded, and not
defensive!
2. Source Determination: Once determined, the location or source must be pinpointed. This
can be achieved by taking note of the steps that can create the problem. For instance, pitting
of the aluminum under the final finish can occur before or during anodizing. The type of
pitting (e.g., star shapes, sharp pits or galvanic frost) can give a clue, but not the answer.

The first step in solving the problem is to run another workload. It may seem expensive to
sacrifice a load of metal in this manner, but if anything is changed at this point, it will be
difficult to determine if the condition was just a one-time occurrence or if it will affect
subsequent work. If the problem does not repeat, it should be noted if it recurs in a random
fashion. If it does repeat, then it is necessary to start changing variables and running more
loads.

Do not change more than one variable at a time! This will only lead to confusion about
which variable caused or corrected the problem.

With respect to a pitting problem, good, fresh metal should be processed. If pitting is still
evident, then an examination of pitting sources on the anodizing line should be
investigated. A check of rinses and process solutions, as well as electrical contacts between
the workload and ground, should be checked. If the workload emerges without pits, run
some more loads. If pits again appear on the workpieces, examine the storage practices and
age of the aluminum and consider using the deoxidizing step before further processing.

3. Patient Investigation: An important factor in resolving anodizing problems is patience.

When under pressure to maintain production, a problem is often dealt with hastily and is
rarely properly resolved. Troubleshooting requires time and a stepwise investigation. Once
the source and location of the problem have been determined, steps should be taken to
eliminate it. Unless completely corrected, it cannot be expected that the anodizing line will
run smoothly and consistently.