Anodization of Different Aluminum Samples

Dela Merced, M.S.E.

Department of Mining, Metallurgical, and Materials Engineering
University of the Philippines Diliman

Quezon City, Philippines

Introduction
Anodization, from the Greek word anodos which means a way up (American Heritage Dictionary, n.d.), is a
process that involves metals which are treated electrochemically resulting to the formation of stable films or
coatings for the surface protection. (Ebnesajjad 2011) The film formed is either an oxide or oxyhydroxide which
protect the aluminum or titanium metal. (Silveston P. L. 2013) Most anodization procedures form a thick porous
film typically of amorphous oxide. (Silveston P. L. 2013) Anodization is done to aluminum to enhance other
properties aside from corrosion protection such as durability and wear resistance, heat dissipation, electrical
insulation, adhesion and surface lubrication. It is also done to create a base or primer for secondary coatings.
(McKeen 2006) Meanwhile, titanium anodization is done to apply color to titanium, aid on looking for stress
cracks in base material, and to also enhance adhesion and corrosion resistance. (Anoplate.com 2015) There are
many advantages of anodizing over other protection techniques for aluminum. These advantages are as follows:
a) comparing anodizing and painting, anodizing is less expensive (with the exception of coil painted products);
b) anodizing produces harder coating which makes it better for aluminums that are subjected to highly abusive
(physical) and abrasive environments; c) film produced is part of the metal (cannot be peeled off); d) aesthetic
advantages such as richer metallic appearance and control of color variation amount; and e) coating produced by
anodizing dos not fail due to exposure to UV light. (SAF - Southern Aluminum Finishing Co, Inc. 2015) Typical
applications for anodized aluminum include aircraft and or automotive parts, architectural and construction
materials for structural purposes, industrial electronics, satellites, and decorative purposes.
(Spectraaluminum.com 2015) To illustrate the anodization process, Figure 1 shows the outline of the
anodization set-up and the actual set-up to be used in the experiment.

Figure 1. Anodization Set-ups (L- outline of set-up, R- actual set-up to be used)

Results and Discussion

The samples that were dyed using the anodization of aluminum were a Coca Cola can aluminum sheet, an
Aluminum plate, and a Coca Cola can cap opener. Shown in Table 1 is the summary of the images taken before
and after application of dye (except for the coke can cap opener) and the corresponding microstructures.
Table 1. Summary of images
Coke Can Aluminum Sheet

Aluminum Metal Plate

Coke Can Cap

Opener

Alumin
um
Metal
After Dyeing
Before Dyeing

After Dyeing
Before Dyeing

After Dyeing

Microst
ructure

It can be seen from the table that the dye was most evident on the aluminum metal plate while the samples from
the coke can (aluminum sheet and cap opener) showed only a light application of the dye. This is because the
samples from the coke can have an epoxy coating that is only microns thick making it invisible to the naked eye.
This prevents contaminants such as corrosion products, and colorants to affect the inside surface of the cans.
(Waldman 2015). A change in the microstructures of the aluminum sheet and plate can be seen after being
subjected to dyeing.
During the anodization process, a series of reactions occur in the electrochemical cell. Once the current is
flowing in the cell, sulfuric acid decomposes thus resulting to the movement of the hydrogen ions to the cathode
which are then reduced to hydrogen gas. (Groves 2010) This reaction is shown in Equation 1.

H 2(g )

++2 e
2 H

(Equation 1)

The negatively charged ions then simultaneously move to the anode. Positively charged aluminum ions (Al 3+)
are then generated in the anode and move towards the anode due to the electrical charge from the power source.
Aluminum oxide is then formed in the surface of the anode due to the reaction of the aluminum ions with the
oxide/hydroxide ions. (Groves 2010) These reactions are shown in the Figure 2.

Figure 2. Reaction of Aluminum with oxide/hyrdroxide to form aluminum oxide(Groves 2010)

Over-all reaction that occurs in the electrochemical cell is shown in the following equation.


++ 6 e
2 Al +3 H 2 O Al2 O 3 +6 H

(Equation 2)

Different steps may then be associated to the growth of the layer formed during anodization. Initial stages of
anodizing produce an oxide layer that is uniform and dense which makes it resistant to corrosion and wear. This
layer is known as the barrier layer. Once the high electrical resistance of the oxide reduces the potential of the
applied voltage in the electrolytic cell, growth of the layer stops. The subsequent growth of the layer occurs in
low growth rate and competes with the acid reaction shown in Equation 3.

3++3 H 2 O
+ 2 Al
Al2 O 3 +6 H
Aluminum ions are then released into the solution. For low voltages applied, only the barrier layer forms.
However since aluminum ions are produced gradually, smoothening of the underlying metal surface occurs. At
higher voltages, oxide layer grows beyond the barrier layer. The secondary layer formed has a pore-like
structure. This is the result of the competing acid reaction with the anodization process. (Groves 2010)
A great factor in the anodization process is the bath used. The most common acidic bath used is the sulfuric acid
bath. This medium produces an oxide layer that is thick and only slightly porous containing substantial amount
of sulfate ions. (Wood, 1983) This anodization media is used for architectural aluminum. (Pocius 2012) Other
anodization media that can be used for aluminum are phosphoric and chromic acid. The oxide layer produced
using chromic acid is marginally thinner and with greater porosity compared to that of sulfuric acid. Also the
oxide produced using chromic acid is pure

Al 2 O 3 . (Pocius 2012) Phosphoric acid anodization produces the

thinnest and most porous oxide layer among the three acidic media. Substantial amount of phosphate ion is
present in the oxide layer. For aluminums used in the aerospace industry, chromic and phosphoric acid media
may be used. Concentration of the bath also affects the thickness and texture of the layer. For high sulfuric acid
concentration, the oxide layer is thin and porous while low sulfuric acid concentration produces a hard and
dense layer.
Since anodization leads to the production of an oxide layer with a porous structure, the anodized aluminum
becomes amenable for dyeing. Shown in Figure 3 is the structure of the anode layer.

Figure 3. Structure of Anode Layer (Groves 2010)

To complete the dyeing procedure, boiling should be done to the aluminum piece in order to close-off the pores
wherein the dyes seeped in. This method is known as the sealing process. (Groves 2010). After the sealing

process, the theoretical thickness of the anodized aluminum may then be computed. Table 2 shows the summary
of pertinent values including the calculated theoretical thickness of anodization.
Table 2. Summary of Values

Average current
Time for current
Coulombs
Moles of electrons
Moles of Al reacted
Moles of Al2O3
Grams of Al2O3
Volume of Al2O3 (cubic

Aluminum Sheet
0.01 A
30 mins
18
1.865284974 x 10-4
6.21761658 x 10-5
3.10880829 x 10-5
0.003170984456
0.0007987366388

Aluminum Plate
0.11A
20 mins
132
1.367875648 x 10-3
4.559585492 x 10-4
2.279792746 x 10-4
0.02325388601
0.005857404018

Can Cap Opener

0.02A
10 mins
12
1.243523316 x 10-4
4.14507772 x 10-5
2.07253886 x 10-5
0.0023989637
0.0005324910925

1cm by 0.5cm

1cm by 0.5cm

1cm by 0.5cm

0.001597473278

0.01171480404

0.001064982185

cm)

Area anodized
(assume square area)
Thickness of
anodization (cm)

Based from the calculated theoretical thickness of anodization, it can be observed that the aluminum metal plate
subjected to high current and moderate anodization time produced the thickest anodization layer. This is in line
with the literature that dictates that as voltage or current is increased, the oxide layer grows beyond the barrier
layer and produces a porous structure that adsorbs the dye. (Groves 2010)

REFERENCES:
Anoplate.com. 2015. Anodizing: Hard, Hardcoat, Sulfuric, Chromic, Aluminum and Titanium Anodize.
http://www.anoplate.com/finishes/anodizing.html.
Ebnesajjad, Sina. 2011. 6.2.4 Anodization. Handbook of Adhesives and Surface Preparation - Technology,
Applications and Manufacturing. Elsevier. http://app.knovel.com/hotlink/pdf/id:kt008TY6OF/handbookadhesives-surface/anodization.
Groves, Geoff. 2010. Anodising of Aluminium. New Zeland Insitute of Chemistry, no. 1: 7.
http://nzic.org.nz/ChemProcesses/metals/8E.pdf.
McKeen, Laurence W. 2006. 8.3.5 Anodization. Fluorinated Coatings and Finishes Handbook -The Definitive
Users Guide and Databook. William Andrew Publishing/Plastics Design Library.
http://app.knovel.com/hotlink/pdf/id:kt003WSMJ7/fluorinated-coatings/anodization.
Pocius, Alphonsus V. 2012. 7.4.1 Mechanism of Anodization. Adhesion and Adhesives Technology - An
Introduction (3rd Edition). Hanser Publishers.
http://app.knovel.com/hotlink/pdf/id:kt00ARO9T3/adhesion-adhesives-technology/mechanismanodization.
Silveston P. L., Hudgins R R. 2013. 9.4 Anodization. Periodic Operation of Reactors. Elsevier.
http://app.knovel.com/hotlink/pdf/id:kt00BIXMR1/periodic-operation-reactors/anodization.
Spectraaluminum.com. 2015. Aluminum Extrusion. http://www.spectraaluminum.com/benefits-of-aluminumanodizing.
Waldman, Jonathan. 2015. The Secret Life of the Aluminum Can, a Feat of Engineering. WIRED.
http://www.wired.com/2015/03/secret-life-aluminum-can-true-modern-marvel/.

American Heritage Dictionary of the English Language, 4th edition,

"anodize," http://www.yourdictionary.com/anode (accessed November 29, 2015).
SAF - Southern Aluminum Finishing Co, Inc.,. 2015. 'To Anodize, Paint, Powder Coat Your Aluminum?
Specification Help.'. https://www.saf.com/how-to-specify/how-to-decide-between-anodizing-painting-andpowder-coating/.
Wood, G. C., Thompson, G. E., in Corrosion: Aqueous Processes and Passive Films,
Vol. 23, Treatise on Materials Science and Technology. Scully, J. C.(Ed.) (1983)
Academic Press, London

APPENDIX