Aluminum Anodizing Process
Aluminum Anodizing Process
Aluminum Anodizing Process
Unlike most protective coatings, anodizing permanently changes the outer structure of the metal. When aluminum is exposed to air it
naturally develops a thin aluminum oxide film that seals the aluminum from further oxidation. The anodizing process makes the oxidized
surface much thicker, up to several thousandths of an inch thick. The hardness of the anodized aluminum oxide coating rivals that of
a diamond, enhancing the abrasion resistance of the aluminum. The added depth of the oxide layer improves the corrosion resistance of
the aluminum, while making cleaning of the surface easier. The porous nature of particular types of anodizing makes it possible to dye the
aluminum a variety of colors, making it more attractive.
Anodizing typically ranges up to 5 mils thickness. The three most common variations of aluminum anodizing include chromic (type I),
sulfuric (type II) and hard (type III).
Þ Chromic anodizing utilizes a chromic acid electrolyte and yields the thinnest coatings, only 0.02 to 0.1 mils thick (0.5 to 2.5
microns). 50% penetration into the substrate and 50% growth over original dimensions occurs. Chromic anodizing has the least effect on
fatigue strength and is less corrosive, thus ideal for complex and difficult to rinse parts. Excellent for coating aluminum castings, most
chromic anodized parts are used in military and aerospace applications and are more functional than decorative in nature.
Þ Sulfuric anodizing is the most common method of anodizing, utilizing sulfuric acid to yield coatings up to 1 mil (25 microns) thick. 67%
penetration into the substrate and 33% growth over original dimensions occurs. Due to its permeable nature, sulfuric anodizing is excellent
for color dyeing and provides a base for primers, bonding agents and organic coatings. Sulfuric anodizing provides corrosion resistance and
is very durable. Typical applications include architecture, aerospace, manufacturing automotive and computers.
Þ Hard anodizing (a.k.a. hardcoating) utilizes a higher concentration sulfuric acid electrolyte at a lower temperature resulting in a tough
outer skin with excellent abrasion resistance, corrosion resistance, color fade resistance, dielectric strength and surface hardness (Rockwell
C-Scale up to 70). 50% penetration into the substrate and 50% growth over original dimensions occurs for a total thickness of 0.5 to 4
mils. Hard anodized metals have heightened surface roughness. Common uses include non-decorative food packing equipment,
photocopier paper rolls, and exterior applications such as building storefronts and windows.
1. Aluminum part is dipped in a hot tank containing a soak cleaning agent to remove all surface dirt.
3. The next tank de-oxidizes the part with an acid solution (chromic, sulfuric, nitric or phosphoric) removing the thin, non-uniform aluminum
oxide surface.
5. Etching is performed by suspending the part in a tank containing a sodium hydroxide solution. Etching removes the natural shine of the
aluminum and provide a soft, matte, textured appearance.
6. The part is suspended in the anodizing tank, which contains a diluted acid and water mixture that is capable of permitting electrical
current flow. The type of acid, percent solution and temperature are all critical parameters and dependent on the desired finish and color. The
negative leg of the electrical circuit is connected to the rack of parts and the positive side of the circuit is connected to one or more
"cathodes" that introduce electricity into the tank. Quantity and placement of the cathodes varies with the size and shape of the part as well
as the total square footage of aluminum surface to be treated. Surfaces closest to the cathode will receive a thicker anodic coating. For
normal sulfuric anodizing a DC power source capable of producing up to 24 volts is used, with the voltage held generally between 18 and 24
volts. The amount of current applied to the anodizing tank will vary depending on the amount of surface to be treated, as a rule between 12
and 16 amps are required for each square foot of coverage. The electrolyte solution is agitated during the anodizing process to provide
uniform solution temperature. The anodizing tank process, under normal conditions, takes less than an hour.
7. To add color (dye), the part is dipped in a tank with a diluted, water soluble, organic dye. Each dye varies in the length of time and
temperature for this immersion.
8. The final consideration in the anodizing process is sealing the now dyed outer surface so it doesn't sunlight bleach or stain. Unsealed,
the porous outer surface has a lowered corrosion resistance. For non-dyed coatings, the anodized aluminum part is put into boiling de-
ionized water for 20 to 30 minutes. This converts the unstructured pores of the aluminum oxide to a more solid crystalline hydrate form. If the
anodized parts are dyed, the sealing process is performed for 3 to 5 minutes in a tank with a nickel acetate solution.
9. Hard anodizing, depending on the process, uses a mixture of sulfuric and oxalic acid. Relatively low temperatures are used along with
a higher current and a much higher voltage. The “gray” oxide layer produced is typically 2 to 3 mils and is very dense, wear and corrosive
resistant.
An alternative to racking is bulk anodizing which is more ideal for anodizing small, irregularly shaped parts such as rivets, ferrules and
medical hubs. Instead of racks, parts are processed in perforated aluminum, plastic or titanium baskets. Whether you need coil or batch
production, anodizing provides one of the best aluminum finishing options in the industry.
Another alternative is coil anodizing. Coiled aluminum is pre-anodized to lower finishing costs, save production time, and reduce material
handling. Advantages of pre-anodized aluminum can be applied to most products that are fabricated from sheet or coil stock. Products that
are made from extrusions, castings, rod bar, or plate are limited to piece anodizing processes such as racking or bulk.
Though most aluminum alloys will build aluminum oxide in an anodizing tank, they tend to anodize differently. Some alloys are more difficult
to anodize while others anodize to slightly different shades of color. When anodized, various alloys provide different levels of workability
(machining, grinding, polishing), environmental resistance properties, and dimensional stability.
Why Anodize?
Anodizing is a highly effective and desirable means of finishing aluminum. Some of the primary advantages of anodizing include:
Þ Durability - Most anodized parts experience no wear from handling, installation, usage and maintenance Adhesion - Anodizing is part of
the aluminum for total bonding and unmatched adhesion.
Þ Color – Anodized parts maintain good color stability when exposed to ultraviolet rays, do not have an applied coating that is subject to
chipping or peeling, and have a repeatable coloring process.
Þ Quality of original finish – Parts are not subject to marking from the original anodizing process.
Þ Maintenance - Mild soap-and-water cleaning usually will restore an anodized profile to its original appearance.
Þ Aesthetics - Anodizing offers a large number of gloss and color alternatives, while allowing the metallic appearance of the extruded
aluminum to show through.
Þ Cost - Anodizing is a very cost-effective value compared to other finishing methods. In addition to low processing and maintenance
costs, durability minimizes replacement costs.
Þ Environment, health and safety - Anodizing is favorable towards current governmental regulations because it is one of the most
environmentally friendly industrial processes and is typically not harmful to human health. An anodized finish is chemically stable, will not
decompose, is nontoxic, and is heat-resistant to the melting point of aluminum. Since the anodizing process is a reinforcement of a naturally
occurring oxide process, it is non-hazardous and produces no harmful or dangerous by-products. Chemical baths used in the anodizing
process often are reclaimed, recycled, and reused.
Why measure?
The anodizing process parameters have a significant influence on the properties of the oxide formed. If low temperatures and acid
concentrations are used, it yields a less porous and harder coating. Higher temperatures and acid content, along with longer immersion times
produces softer, more porous coatings. Minor changes to the alloy itself or any of these parameter can significantly affect the coating.
Through various process controls and measurement techniques, Anodizers are able to monitor, control and correct the anodized coating
application. One of the most critical quality controls for anodizing is thickness. Thickness of anodizing can be measured non-destructively
using an eddy current gage or by calculating weight per unit area. The simplicity of the eddy current method is not only more efficient than
the calculation method, but also enable the inspector to verify that adequate anodizing occurs across all surfaces of the part.
The most common way of checking chromic acid anodizing is by coating weight. MIL-A-8625
will give you details of the test. This is not done on every bath load, but usually on a monthly
basis to ensure a minimum film thickness is maintained.
Why Anodizing?
Anodizing is perhaps the most commonly specified finish for aluminum machined parts. Advantages of Anodizing
include:
1. A very thin coating (.0002-.0012" for Type II) compared to paints and powder coat. Coating thickness can often
be ignored for machined parts.
2. Extremely durable, hard, abrasion resistant and long lasting. Coating does not peel or chip. Much, much harder
surface than paint (harder than tool steel). Coating lasts indefinitely.
3. Some types (e.g., architectural anodizing) have colors which are fade resistant in sunlight nearly indefinitely.
4. Excellent corrosion protection. Withstands salt-spray and other tests extremely well.
5. Environmentally friendly finish. Can be readily recycled. Production involves simple inorganic chemicals which
have minimal environmental impact
6. Good electrical insulator. Combined with other coatings can be used for selective masking of low-voltage
currents.
7. Inexpensive. Very price competitive with painting and powder coating.
Conversion Coating: what it means
Anodizing is a "Conversion Coating", and is very different than paints, plating and other common coatings on metal.
While paints and plating sit on top of the surface of the aluminum, anodizing converts the outer layer of aluminum to
aluminum oxide, so the coating is fully integrated with the aluminum substrate. This is why anodizing doesn't chip or flake
like paint- is completely integral with the underlying metal.
Anodizing is a Conversion Coating because the surface aluminum is converted into aluminum oxide. In the same way
that charcoal on a charred fire log is integral to the log, the aluminum oxide layer is integral to the aluminum substrate.
The oxide coating is most commonly created by placing an aluminum part in a sulfuric acid bath while running a low-
voltage DC current through the part to cathodes on the side of the tank. The part acts as the anode in the electrical
circuit, hence the origin of the term "Anod-izing".
Types of Anodizing
Most anodizing on machined parts are of two commonly specified types: Type II (or "regular") sulfuric anodizing and
Type III Hardcoat or "hard" sulfuric anodizing. The Type II & III designators come from the common Military specification,
MIL-A-8625 (there is also a Type I anodizing, but this is done using environmentally-unfriendly chromic acid, and it is
rarely specified these days).
Both Type II and Type III "hard" anodizing are very hard coatings. Type III "hard" anodizing is done at a lower
temperature, is more expensive, and a little harder than Type II, but you need special equipment to tell the difference in
practical terms. Type III, however, is much thicker than Type II, typically .002" vs. .0006" respectively, which makes it
more resistant to scratching and heavy wear.
There is another type of anodizing, commonly called "architectural" anodizing. It is essentially the same as Type II
anodizing above, but uses metallic ion dying which is completely colorfast in sunlight.
When specifying anodizing from a mechanical designer's perspective, it is extremely important to understand the terms
used by the anodizer, since these cause much confusion. Coating Thicknessis the actual thickness of the oxide layer.
This is not the same as Build-up, which is a common term for t he dimensional difference between the oxide layer and
the originally aluminum surface (see figure above).
Eddy current thickness testing meters are usually used to measure the anodized (oxide) layer. This will measure coating
thickness, but not build-up. Build-up must be measured by comparing a finished part to an uncoated sample, or by
calculation.
Calculating Build-up
Anodizers usually use a rule of thumb that the oxide layer penetrates 50% into the part and builds up 50%. The true
percentages, according to most sources, are closer to 67% in and 33% out for the common Type II anodizing, and 50%
in and 50% out for Type III, hardcoat anodizing. In any case, knowing the coating thickness and using these
percentages, a rough calculation of build-up is possible. Heavy etching before anodizing can also reduce buildup, by
removing up to a few tenths of aluminum before the anodic layer is formed.
Machining Tolerancing
With common Type II anodizing, the coating thickness will usually vary from .0002" to .0012". The thinnest coatings are
usually seen in clear anodizing, since anodizing dyes require at least .0004"- .0006" of coating thickness to dye properly.
With an average coating thickness of .0008", the build-up will typically be .0002"-.0003", which is small enough that it can
be effectively ignored in most machined and fabricated parts. This is not the case, however, with Type III, Hardcoat
anodizing, which can have coating thicknesses of up to .004", and build-up to .002".
The most common solution to this problem is to mask the features. This is done using soft plastic plugs, for round holes,
or plastic tape or painted-on liquid plastics for flat areas.
As noted above, masking is often not required for Type II anodizing. However, it should be noted on print call outs when
specifying thicker Type III coatings and when small thread or tight tolerance features exist.
Silicon rubber plugs, such as these, are often used to mask high tolerance holes prior to anodizing.
Variation in Coating Thickness
While general coating thickness can be specified on a print, most anodizers will be leery of certifying an exact uniform
coating thickness. This is because coating thickness will vary on a part due to part geometry, racking position, and the
electrical field variations that inevitably exist in every anodizing tank. A variation of .0001-.0003 in coating thickness on a
single part is common. While uniformity of thickness can be controlled to some degree by cathode placement, racking,
and positioning in the tank, it is still as much an art as a science, and tight thickness tolerancing can be extremely
expensive if even achievable.
The coating of these parts ranges from .0003" on the left to greater than .002" on the right- all are undyed.
Anodizing layers are commonly dyed with organic dyes by dipping the part into a hot dye tank directly after anodizing. A
wide variety of colors can be obtained through this process. By far the most commonly specified color is black, followed
by blues, reds and golds. Note that only Type II anodizing can be dyed a variety of colors. Type III "hard" anodizing,
which is quite dark even when undyed, is typically left clear or dyed black.
Photo: An example of anodized parts dyed red
Colors and Color Matching
The coating of these parts ranges from .0003" on the left to greater than .002" on the right- all are undyedIt is important
to note that colors obtained through dying are not as consistent as those obtained through painting or powdercoat. There
is no such thing as a pantone matched color in most commercial anodizing, and consistency in color and color matching
is extremely difficult. Generally colors are specified in a broader way than with painting, e.g., you would specify "blue" or
perhaps "light blue" or "dark blue" for an anodized part, not "deep sky blue" or "electric indigo blue". Note that colors
obtained through organic dyes are not absolutely colorfast, especially in high UV exposure situations. All organically
dyed parts will fade to some degree over time. Outdoors, the fading can be dramatic.
Common problems occur with welds, extrusions, cold or hot-worked areas, or poorly machined surfaces.
It is common for problems in the material or mechanical finish to have the appearance of a problem with the anodizing.
Often material defects will look like chemical spotting or streaking, when the issue is material based. GIGO (garbage in,
garbage out) is truer with anodizing than nearly any other finish. For the anodic layer to be perfect, the aluminum
substrate has to be perfect as well.
This blemish looks very much like a chemical spot, but it isn't. It's a location where a locating pin inadvertently pushed up the sheet
metal. The sheet was peened back into place by the machinist, but the cold work altered the material enough to change the color of
the anodizing.
This dark spotting looks like something amiss in the anodizing tank, but it was actually caused by overly dirty water in a vibratory
tumbler. The dirty media was imbedded into the aluminum finish, causing blotchy areas.
Uncharacteristically, the welds on this bike frame caused little change in the anodizing color. However, poor sanding and left over
spots of bondo create a surface finish that shows unanodized blotches and mechanical scratches.
Aluminum Alloys and their Effects on Anodizing Color
Aluminum alloys can also have an effect on anodizing. Remember, that alloying elements such as copper do not
anodize, so high-copper alloys such as 7075 or 2024 will give noticeably different colors than lower copper alloys such
as 6061, both with dyed parts and with clear anodizing. Generally, 6061, the 3000 and 5000 series alloys will anodize
reasonably consistently with each other. 7075 and 2024 will show a yellow tint in clear anodizing, due to the high copper
content, and black will not be as deep. 1000 series, while rarely specified, actually anodizes the best of all, being the
closest to pure aluminum.
The smaller part on the left is machined from 7075, while the larger circular part is 6061. Note the distinctive yellowish tint of the
left hand part, which is characteristic of clear anodizing of 7075 or 2024 alloys.
The Anodic Layer
Ever wondered why anodizing dyes so well? It has to do with the microscopic structure of the anodizing layer.
The oxide or "anodic" layer formed in the anodizing process consists of microscopic hexagonal oxide columns with holes
or "pores" which extend nearly the entire length of each column. It is these pores which hold the dye
The anodic layer is extremely hard- usually between 60-70 Rockwell C. The layer is also an excellent insulator, with a .
002"hardcoat layer having a breakdown voltage of 1500-2000 volts.
The characteristic hexagonal structure of anodizing (hypothetically about 40,000x magnification). Note the hexagonal oxide columns
have been sliced through to show the structure. An actual layer would be much thicker, with the height of the columns 200 or more
times higher than their diameter.
The anodic layer grows outward from the aluminum surface as a part is anodized. As such, very sharp inside or outside corners on a
part can cause gaps or voids to develop- especially with thick anodic layers such as Type III hardcoat anodizing. Avoid very sharp
inside or outside corners when possible, and allow a radius of at least.015"(1/64th").
Mil Spec MIL-A-8625
US Military Specification MIL-A-8625 is the most common specification for anodizing in use. Although the specification is
somewhat out of date, especially in regards to the environmental impact of some of the processes (e.g., Type I chromic
acid anodizing), it still is used as a model for much of the anodizing specified for military and aerospace products, and
forms the basis for many proprietary company specifications.
The most common types and classes of anodizing found in MIL-A-8625 are:
As an example, a standard blackpart designated by MIL-A-8625 would be called out on a drawing as follows:
Rack marks can be controlled by specifying on a drawing allowable locations for gripping a part. If rack marks are critical,
discuss possible racking options in advance with your anodizer.
This photo shows several different racking approaches for parts of different sizes and shapes. Parts can be wired through holes,
gripped on the edges, or gripped inside cavities with "spring" grippers. Anywhere there is metal to metal contact, there will be small
unanodized areas.
Assemblies and Anodizing
In general, multi-part assemblies must be anodized before assembly. Because parts are dipped in both a strong alkaline
(sodium hydroxide) and sulfuric acid, any studs, threaded inserts, pins, standoffs, etc., are in danger of corrosion and will
cause problems in the anodizing tanks. Even stainless steel components can corrode in the tanks during anodizing, and
can affect current flow during electrolytic processes. Gaps between components can also trap chemicals and cause
problems by bleeding of the corrosives after anodize. As a rule of thumb- assemble after anodizing.
Set a volt-ohm meter to measure resistance, and touch the probes to the surface of a part you suspect of being clear anodized. If
there is high resistance, the part is likely anodized.
Marking and Engraving Anodizing
Anodizing is an excellent background finish for either mechanical or laser engraving. Using carbide tooling, e.g. a small
90ochamfer mill, letters, numbers or other symbols can engraved directly through the anodic layer with a CNC mill or
router. The aluminum substrate gives an excellent contrast to the characters.
Laser Engraving also produces excellent results. Rather than burn through the anodic layer, a laser engraver will bleach
the dye in the layer, generally giving an excellent contrast to the characters. An advantage of laser engraving on colored
anodizing, is that no additional chemicals need be added to the surface to accentuate the marking, which is not the case
with bare aluminum, stainless steel, or most other metals
An example of laser engraved characters on a black anodized part.
2. Think through whether masking will be required (especially with Type III hard anodizing). Call out masking
locations on print.
3. Remember to call out acceptable racking locations if racking marks are a concern.
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Units
It is important to be consistent in the use of units – failure to do so can have disastrous consequences!
The SI unit of measurement used for coating thickness in the majority of standards, throughout our website and on any
documentation we produce, is the micrometre or micron (µm) which is one-thousandth of a millimetre.
Older (outdated) engineering drawings or standards, or those originating from the US, may use imperial units such as mil
(not the same as millimetres) or thou.
Coating thickness and surface growth
Anodising is an electrolytic conversion coating – it transforms aluminium on the surface of components into aluminium
oxide. Since aluminium converts rather than deposits, some of the thickness of the coating is ingress into the material
and some of the thickness is growth out of the material. For most alloys, the anodised coating is approximately 50%
ingress and 50% growth. The growth of coating from the original surface is therefore half the stated coating thickness.
Internal diameters will get smaller by approximately the coating thickness and external diameters will grow. See
illustrations below.
You can use our anodising growth calculator to estimate the size of a feature after anodising. We recommend that you let
us check your calculations.
Anodised coating thickness may vary dependent on alloy and treatment specification. Typical coating thicknesses are as
follows:
Up to 5µm for chromic acid anodising
5 to 15µm for clear (natural) sulphuric acid anodising
10 to 25µm for dyed (coloured) sulphuric acid anodising
20 to 70µm for hard anodising, with thicknesses up to 100µm achievable on some alloys.
How will strip and reanodise affect the dimensions?
In order to reanodise a part, for example when refurbishing a damaged item, it is necessary to strip the existing anodised
coating first. This will result in a loss of material from the original surface, as shown in the illustrations below.
Repeated strip and redo operations will increase the amount of material lost. It can sometimes be possible, dependent
on alloy and thickness of original coating, to give re-anodised parts a thicker coating to restore original dimensions.
Please contact us for advice.
9.4.3 Anodizing
Anodizing is the general name applied to methods of treating metals in which the work piece is made the anode in
an electrolytic cell, usually to form oxide coatings for the purpose of increasing the performance of the surface. The
nature of the electrolyte, the reaction produced and operation parameters determine the structure and properties of
the formed oxide film. In the case of aluminium, the anodizing process forms a layer of aluminium oxide – Al2O3 –
or corundum, which is very hard, relatively inert and electrically insulating and can absorb dyes to colour the film.
The anodic film itself grows at the aluminium/aluminium oxide interface by the continuous formation and
dissolution of a layer of oxide: this is the so-called barrier layer and its thickness is a function of the process starting
voltage. A porous, more structured layer forms on top of the barrier layer, making up the rest of the coating. All
anodizing processes are sealed unless the film is used as a primer for paint or adhesives. The most common
anodizing processes on aluminium use chromic acid, sulfuric acid or oxalic acid (Wernick et al., 1987). Other acids,
such as phosphoric acid and boric sulfuric acid mix, are now used in the market for anodizing in the aerospace
industry.
Chromic acid anodizing (CAA) is currently used in the aerospace industry in order to treat high-strength aluminium
alloys such as AA 2024-T3. However, the process uses chemicals that contain Cr (VI), which is contra-indicated
from the health and environmental points of view since it is toxic and carcinogenic. The corrosion resistance is
excellent relative to the thickness of the coating, which normally lies in the range of 2 to 5 μm. Sulfuric acid
anodizing is the most frequently used aluminium anodizing process. It produces coatings up to 25 μm for
conventional coatings and up to 100 μm for hard coatings. Conventional coatings are primarily decorative or
protective. Hard coat anodizing is processed at higher voltages and current densities and is mostly used
for engineering applications.
Boric sulfuric acid anodizing was developed by Boeing Company as a chromic acid anodizing replacement for non-
critical fatigue parts. Paint adhesion is equal or superior to chromic acid, and the process is more energy-efficient
than chrome-based processes. However, anodic coatings made in non-chromate containing electrolytes cannot
provide self-healing of defects when the coating is damaged. Therefore, the coating must be sealed by an inhibitive
compound in order to enhance the corrosion protective properties of anodic films.
Read full chapter
Protection Against Corrosion
Christian Vargel, http://www.corrosion-aluminium.com, in Corrosion of Aluminium, 2004
5.3.3 Hard anodising
Hard anodising refers to a number of low-temperature processes that produce thick (50–100 μm) and dense oxide
layers. They have better abrasion resistance than the best treated steels, and their electrical insulation properties are
on a par with those of porcelain.
Hard anodising is used in the electrical and mechanical industries. The friction coefficient is reduced by a number
of impregnationproducts: lanolin, teflon, molybdenum disulphide, etc. Given the thickness of these layers, it may be
necessary in some cases to allow for dimensional variations after anodising.
Read full chapter
Plasma electrolytic oxidation treatment of magnesium alloys
C. Blawert, P. Bala Srinivasan, in Surface Engineering of Light Alloys, 2010
6.1 Introduction
Anodizing is an electrolytic process for producing a thick, stable oxide film on metals and alloys that can mitigate
the substrate corrosion or be used as a base for paint adhesion or dyeing. It is a well-known industrial technology for
surface protection of light metals, especially aluminium, successfully used for many decades. However, the anodic
behaviour of magnesium and magnesium alloys is strongly influenced by the voltage applied. Generally, different
passive and active states influencing the coating formation are found, dependent on applied voltage, and the alloy
and electrolyte compositions. However, due to the specific characteristics of magnesium alloys (see Chapter 1), the
low voltage anodizing of these alloys was never successful enough to provide sufficient resistance to wear and
corrosion. Currently, most of the anodizing processes use spark discharges to convert the magnesium surface into a
ceramic oxide.
The core part of the anodizing process is the formation of an anodized layer that is normally about 5–30 μm thick,
hard, dense, electrically insulating and wear resistant. The layers contain pores whose dimensions and distribution
are a function of the electrolyte properties, temperature, anodizing current density and voltage. Depending on
the aggressiveness of the environment, an anodized coating can also be additionally sealed and/or painted for
optimal protection. Although the initial investment for an anodizing treatment is relatively low, the ongoing costs of
anodizing processes are rather high. Therefore, the use of this technique for surface protection of Mg alloys is
limited in comparison to conversion coatings, e.g. for applications in the automotive industry (Hillis, 2001).
Nevertheless, applied to many niche products, the coatings have already proven how beneficial they can be under
wear and corrosive conditions. Ongoing research will most likely lead to cheaper processes, thus providing more
competitive anodizing solutions.
Looking at the electrochemical conversion treatments available for Mg alloys, there are two different groups
existing, which can be distinguished by the processing voltage as the driving force for the surface conversion
process. The first group operates below the breakdown voltage – i.e. conventional anodizing (see Chapter 4), using
the voltage mainly to accelerate and enhance the natural passive film formation in the specific electrolytes. The
second group operates above the breakdown voltages, using mainly discharges at the electrolyte/metal interface to
enhance film formation, and modify the composition, phases and density of the thick oxide films. The high energy in
the discharges is able to melt substrate and passive films and convert them to hard ceramic types of coatings by
incorporation of components from the electrolyte. The boundaries between the processes are not fixed, as the start of
the appearance of micro-discharges, often denoted as breakdown potential, varies with the type and composition of
the substrate alloy, electrolyte concentration and composition, and most importantly the type of power (pulse, AC,
DC). A typical breakdown potential for PEO processing of magnesium alloys lies in the range between 100 and
200 V, and the final operating voltages are in the range of 300 to 600 V; thus much higher voltages than in
conventional anodizing are normally used.
Read full chapter
Substrates and Substrate Preparation
Laurence W. McKeen, in Fluorinated Coatings and Finishes Handbook (Second Edition), 2016
8.8 Anodization
Aluminum anodizing is the electrochemical process by which aluminum is converted into aluminum oxide on the
surface of a part. This coating is desirable in specific applications due to the following properties imparted by the
anodization process:
•
Increased corrosion resistance
•
Electrical insulation
•
Excellent base or primer for secondary coatings.
The process of anodizing is fairly simple. It consists of an anodizing solution typically made up of sulfuric acid. A
cathode is connected to the negative terminal of a voltage source and placed in the solution. An aluminum
component is connected to the positive terminal of the voltage source and also placed in the solution. When
the circuit is turned on, the oxygen in the anodizing solution will be liberated from the water molecules and
combined with the aluminum on the part forming an aluminum oxide coating. It is the stability of the aluminum
oxide that accounts for all of the protective properties of the coating.
There are three types of anodizing:
•
Chromic anodizing
•
Sulfuric anodizing
•
Hardcoat anodizing.
Each of these has advantages and disadvantages depending on the application.
Chromic anodizing is commonly referred to as type I anodizing, and is formed by using an electrolytic solution of
chromic acid that is about 100°F (38°C). It utilizes a chromic acid electrolyte and yields the thinnest coatings, only
0.05 to 0.1 mils (1.25–5 μm) thick. Chromic anodizing is often chosen when a part is complex and difficult to rinse.
Chromic acid is less corrosive than sulfuric acid used in other anodizing methods. The process takes about 40–
60 min. It produces a clear to gray coating, depending on the sealing and the alloy used. Chromic anodize offers a
minimum of 336 h (5%) salt spray resistance per ASTM B117 without a coating on top.
Sulfuric anodizing is commonly referred to as type II anodizing, and is formed by using an electrolytic solution of
sulfuric acid at room temperature. The process will run for 30–60 min depending on the alloy used. This will
produce a generally clear coating at thickness of 0.3–1.0 mils (8–25 μm). It offers abrasion resistance, hence it is
more durable than chromic anodize. Like most anodizes, corrosion resistance is excellent.
Hardcoat anodizing is commonly referred to as type III anodizing, and is formed by using an electrolytic solution of
sulfuric acid at approximately 32°F (0°C). The process will run for 20–120 min depending on the alloy and the
desired coating thickness. This process produces a generally gray coating. Hardcoat anodizing's great advantage is
hardness and wear resistance. This anodize has a hardness on Rockwell C-scale rating of 60–70. The hardness makes
it an excellent candidate for many applications that require low wear. It also offers good corrosion resistance.
Fluorinated coatings and primers often need formulation adjustments to optimize adhesion to anodization treatments.
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Current and advanced coating technologies for industrial applications
A.S.H. Makhlouf, in Nanocoatings and Ultra-Thin Films, 2011
1.3.3 Anodizing
Anodizing is an electrolytic process which is used to produce a thick oxide layer on the surface of metals and alloys.
These films are used to improve corrosion resistance and paint adhesion to the substrate.23
The anodizing process includes the following stages: (i) mechanical treatment; (ii) degreasing, cleaning
and pickling; (iii) electropolishing; (iv) anodizing using AC or DC current; (v) dyeing or post-treatment; and (vi)
sealing.24 The anodized films formed consist of a thin barrier layer at the metal–coating interface and a relatively
thick layer of a cellular structure. Each cell contains a pore the size of which is determined by the type of electrolyte
and the experimental conditions. The pore size and density in turn determine the quality of the anodized film.23
Electrochemical inhomogeneity due to phase separation in the material to be coated is one of the main challenges
faced in the production of uniform anodic coatings. The presence of flaws, porosity and inclusions from mechanical
treatment can also result in uneven deposition which, in turn, can enhance corrosion.25
Another disadvantage of anodizing is that the fatigue strength of the materials to be coated can be affected by
localized heating at the surface during the treatment,25 especially in thicker films. Moreover, the anodized film
formed is made of a brittle ceramic material that may not have the appropriate mechanical properties to fulfill the
requirements of some industrial applications.
Read full chapter
Improvements in bonding metals (steel, aluminium)
KwakernaakA. , ... BenedictusR. , in Advances in Structural Adhesive Bonding, 2010
Anodizing surface treatments
A number of anodizing treatments have been developed that outperform all other treatments. Generally an etching
process is used to remove old oxide scales before anodizing.
Boeing developed a chromic acid anodizing process containing hydrofluoric acid.34 Anodizing is performed in a
solution of 50 g l–1chromic acid during 25 minutes at 5 V at room temperature. The hydrofluoric acid is added to
obtain sufficient current density (0.2 A dm–2) in the process. This process results in surfaces with a
fine microstructure and good adhesion, and bonded joints show excellent durability.
Fokker uses a chromic acid solution (40 g l–1) like that used for anodizing aluminium alloys without adding fluorides.
Anodizing is performed at 50°C for 40 minutes at 15 V and bonded joints also show excellent durability.
Anodizing in alkaline peroxide solutions has also been used successfully as a surface treatment for durable bonded
joints. Further research35 indicates that anodizing in a solution of sodium hydroxide(200 g l–1) without hydrogen
peroxide showed excellent durability. the anodizing in this process is performed at 10 V at room temperature.
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European Symposium on Computer Aided Process Engineering-12
A.F. Batzias, F.A. Batzias, in Computer Aided Chemical Engineering, 2002
1 Introduction
Anodizing of aluminium articles is an electrochemical process for producing thin decorative and protective films. In
the industrial terminology, anodizing is actually a series of processes, not always the same in their nature and/or
order. E.g., for aluminium which will be used in the building construction industry, this series is: cleaning, etching,
polishing, electrolytic brightening, sulphuric acid anodizing, dyeing, sealing, finishing; for aluminium which will be
used in the aerospace industry, the pre-anodizing process should be changed according to the specifications set by
the client, while anodizing is usually carried out in chromic acid bath and sealing precedes dyeing. In many cases,
like in anodising of Aluminium, the reveal of a defect in the product may lead to the determination of a fault in an
upstream process as the cause of the problem.
For analytical purposes, we can distinguish three artificial intelligence(AI) approaches for fault/defect diagnosis in
the domain of Computer-Aided Process Engineering (CAPE). The first one of them is the expert system approach
through knowledge acquisition/processing/structuring within a dynamic base, possibly incorporating both, swallow
and deep knowledge (Kramer, 1987; Petti et el., 1990). The second approach is application of artificial neural
networks, possibly incorporating fuzzy logic (Sorsa and Koivo, 1993; Schmitz and Aldrich, 1998). The third
approach is a mixed one, trying to incorporate swallow/deep knowledge into a neural fuzzy system, i.e. to combine
an expert with a neuro-fuzzy system either in an integrated form or in interactively cooperating subsystems (Ozyurt
and Kandel, 1996; Ruiz et al., 2001).
The aim of this work is to present an original computer aided control procedure which guides the industrial user to
avoid failure or specific defects during one of the processes described above. This control procedure is based on (i)
neuro-fuzzy networking and (ii) independent data processing (shallow knowledge acquired by means of quality
control measurements) mainly with cluster analysis. These two sub-procedures should run in parallel but in close
interaction and under feedback corrective mechanisms.
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COATINGS
Zaki Ahmad, in Principles of Corrosion Engineering and Corrosion Control, 2006
7.20 ANODIZED COATINGS
Anodizing is the formation of a relatively thick coating and a coherent oxide film on the surface of a metal by
making the metal the anode in an electrolytic cell. The most common electrolytes used are chromic acid, sulfuric
acid, phosphoric acid and mixtures of theirs. The following are the typical compositions of the bath for anodizing of
aluminum.
(a)
Alumilite Bath
Sulfuric acid, 15 wt%
Water, 85 wt%
Current density, 1.3 A/dm2
A number of trade names have been associated with anodized coatings. Often dyes are applied on anodized coatings
before the sealing process. The drying materials are generally hydroxide of copper, cobalt and aluminum.
Bright anodizing is a process in which aluminum is polished followed by the protection of the shining aluminum
surface with the deposition of a thin film of oxide. Bright anodizing is carried out on aluminum alloys containing
some magnesium. No impurity of any kind should be present in the alloy. For bright anodizing a mixture of
phosphoric acid and nitric acid containing some acetic acid is used.
Reaction:[Al⇄Al3++3e(Anodic)H2⇄2H++2e(Cathodic)]
(10-3)2Al+3O2→2AlO3
As aluminum atoms are extracted from the surface of the metal, pits are formed. As well, the surfaces of the pits are
particularly reactive, probably because of the availability of electrons for covalent bonding. The aluminum
oxide that is in the process of forming also has available electrons; therefore, aluminum oxide bonds with the “raw”
metal surface of the pits, forming a relatively stable complex.
The desired properties of the electrolyte are that it conducts electric current efficiently and is a good solvent for the
metal species (aluminum ions, partially formed aluminum oxides) involved in the electrolysis process. It should not,
however, be a solvent for the final coating product, which is the aluminum oxide-aluminum metal complex.
The electric current intensity, electrolyte characteristics, temperature, and process duration all influence the
characteristics of the pitting and the thickness and integrity of the coating. Higher applied voltage increases the
speed of oxidation, the size of the pits, and the thickness of the coating. Longer duration increases coating thickness.
Temperature and electrolyte characteristics influence the rate of dissolution of the metal surface. Electrolyte
characteristics affect pore density. For instance, use of sulfuric acid will result in more than twice the number of
pores generated, compared with use of chromic acid.
The size and density of the pores affect abrasion resistance as well as the capacity of the coating to absorb dyes for
coloring and paints for desired surface characteristics. Generally, coatings with a higher density of smaller pores
have higher resistance to abrasion.
Alodizing
Alodizing produces a protective oxide coating on metal surfaces similar to that produced by electrolysis, but the
process is purely chemical. Often, the metal to be coated is “dipped” in an acid solution containing
chromate, phosphate, and fluoride ions. Alternatively, coatings can be applied by brushing or swabbing. The acid
acts to dissolve metal from the surface, which then reacts with oxygen in the alodizing bath to form the metal oxide,
which then reacts with the newly exposed metal surface to result in the protective metal oxide coating. The coating
formed by alodizing is characteristically thinner and has less abrasion resistance than does the coating formed
by anodizing. Alodizing is an economical alternative to anodizing if resistance to abrasion is not required.
Processing Steps and Wastes Generation
The anodizing and alodizing processes have similar steps that produce wastes. The basic production steps are:
cleaning, rinsing, deoxidizing, rinsing, etching, anodizing or alodizing, rinsing, coloring, rinsing, and sealing. All
steps produce wastes, described as follows.
Cleaning
The cleaning of metal objects to be processed produces various wastes. If degreasing is required, an important waste
that must be managed is the waste solvent, as well as the substance removed. In general, the most appropriate way to
manage the waste solvents is to regenerate for reuse, then dispose of the residuals. For instance, if a chlorinated
solvent is used for degreasing, regeneration is accomplished by use of a still. The still bottoms are then treated and
disposed of by one of the methods described in Chapter 7.
Rinsing
In general, rinsing after any of the five processing steps (cleaning, deoxidizing, etching, anodizing or alodizing, and
coloring) produces wastes that are simply dilute forms of the wastes produced directly by those processing steps.
Often, rinsing wastes are best managed by operating the rinsing process in a counter-current mode, where two or
more rinsing baths are used for each of the processing steps. Clean makeup water is continually added to the final
rinse tank, which overflows in the rinse tanks that precede it in the processing steps, and so on, if more than two
rinse tanks are used. The overflow from the first rinse tank after each processing step, anodizing, for instance, is then
used as makeup water for the process itself.
Deoxidizing and Etching
Deoxidizing and etching are both done with either caustic or acid solutions. Deoxidizing may use both, in series, if
the metal to be anodized or alodized is badly oxidized. The purpose of deoxidizing is to remove oxides that have
formed naturally but in an undesirable manner. The purpose of etching is to expose a clean, fresh metal surface for
the anodizing or alodizing process. Wastes contain spent acid or caustic solutions and ions of the metal being coated.
Anodizing or Alodizing
The spent acid baths from the anodizing or alodizing process constitute the major waste from the coating process.
These solutions must be maintained above a certain quality for the coating processes to be satisfactory. Build-up of
metal salts (from the metal being coated) must be kept below a level where they interfere with the anodizing or
alodizing process. Also, as the solution is weakened by drag-in from the previous rinse process, the active
ingredients must be made up to maintain a required minimum concentration. In continuous flow anodizing or
alodizing operations, continuous makeup of water and active ingredients can maintain successful operation for a
period of time; however, as the acid or alkali bath solutions continually attack the metal being coated, eventually the
bath must be dumped and the process restarted with new anodizing or alodizing solution. These dumps of spent
solutions, which normally occur about once per month, represent a major waste stream.
Coloring
Coloring, if included in the process, produces wastes that are specific to the coloring process being used.
Tables 10-17 and 10-18 present typical wastewater sources with typical flows and characteristics from an
aluminum anodizingoperation, which includes acid polishing prior to the caustic etch. The process also includes a
coloring process.
Table 10-17. Wastewater from an Actual Anodizing Plant (anodizing capacity of the plant: 2,500 tons aluminum per month)
Description Alkaline Wastewater Acidic Wastewater Rinsewater
H SO (%)
2 4 — 15 —
Al (%)
3+
5.0-9.0 1.5-1.8 —
SS (mg l)
*
— — 100-200
Blow-down
Fabrication Negligible
Finishing
Miscellaneous
Total 101,000
Wastes Minimization
As discussed previously, wastes from rinsing can be minimized and sometimes eliminated by use of counter-current
rinsing and by using the most concentrated rinse wastes as makeup water for baths that precede that particular rinse.
Other waste minimizing alternatives include use of air squeegees to minimize dragout and use of either static rinses
or maintaining makeup water flow-through at as low a rate as possible. Strict adherence to the rule of turning water
off when the rinse line is not in use is an absolute requirement. Regarding the processing baths, which may include
cleaning baths, deoxidizing, caustic etching, acid etching, anodizing, alodizing, and coloring, all solutions should be
rebuilt and/or maintained at working strength according to need based on work done rather than by a regular
timetable.
In some cases usable and even marketable products have been prepared from spent acid etch solutions. When
aluminum is the metal being coated, sodium hydroxide can be recovered using the Bayer reaction. This can be
accomplished by operating the caustic soda etch tank (where applicable) so as to favor movement of the
following chemical equilibrium to the right:
(10-4)NaAlO2+2H2O→Al(OH)3+NaOH
When operation is conducted in such a manner, it is said that the etching bath is operated in a metastable range.
However, crystallization nuclei are needed for sodium aluminate to decompose to sodium hydroxide and aluminum
hydroxide. A process patented by Alcoa introduces the waste etch solution to a reactor that contains 300 to 500 g/L
aluminum hydroxide. Precipitated aluminum hydroxide is separated from the sodium hydroxide solution by
filtration, and the sodium hydroxide solution is returned to the caustic etch process. The aluminum hydroxide can be
marketed as a waste treatment chemical.
Another method that combines waste treatment (of the caustic etch wastes) with wastes minimization is
to precipitate and recover calcium aluminate from spent caustic etching solutions. High-calcium lime that contains
aluminum ions at a high pH is added to the spent etch solution. The recovered calcium aluminate can be sold or
given to a cement manufacturer to be used as an additive. Spent caustic etch solutions have been processed as shown
by the following chemical reaction:
(10-5)NaAlO2+2SiO3Na2+9H2O→4NaOH+Al2O3·Na2O·2SiO2
Question:
What change in surface finish, or roughness (Ra/Rz), can be expected when parts are anodized? S.D.
Answer:
Anodizing does affect the surface finish of the aluminum substrate. The extent of change in the surface
roughness depends largely on the type of anodic process performed. Usually anodizing causes increased
roughness. In preparation for anodizing, caustic etching, for example, roughens the surface to a degree
depending on the etch bath conditions and time of etching. Chemical and electrolytic brightening
smooth the surface. Generally speaking, the higher the anodizing voltage, the more roughening that
occurs. For example, a hardcoated part anodized to a 1-2 mil anodic coating thickness and with little, or
no, etching prior to anodizing will result in a Ra of 2-3 times that of the original bare metal finish. This
means 2-3 times rougher after anodizing than before. In lower voltage processes such as Type II anodize
with 0.3-0.4 mil coatings, the surface may be roughened by about one-third to one-half again of the
original Ra value. A little used process of anodizing in oxalic acid produces parts that are much
smoother than if they were anodized in sulfuric acid.
If surface roughness after anodizing is a primary concern for the parts being manufactured, you may
want to design some testing to see what gives the best results for your product. The type and amount of
mechanical finishing, the type of chemical cleanup prior to anodizing and the anodizing itself can be
varied to give you what is most acceptable