ECP LAB

ANODIZING OF ALUMINIUM

GROUP B5

Electro chemical processes Laboratory

Anodizing of Aluminium
Department of Process Engineering and Energy
Technology

Group B5
Soroush Azarian Moghadam

32339

Vignesh Thiyagarajan

32337

Supervisor
Prof. Dr.-Ing. Brigitte Haase
WS 2014-15

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ANODIZING OF ALUMINIUM

GROUP B5

Contents
List of Figures .......................................................................................................................................... 2
List of Tables ........................................................................................................................................... 3
1 Introduction ......................................................................................................................................... 4
2 Theoretical Background ....................................................................................................................... 4
2.1 The Anodizing Process .................................................................................................................. 4
2.2 Electrochemistry of anodizing ...................................................................................................... 5
2.3 Metal analysis using EIS ................................................................................................................ 6
3 Experimental procedure ...................................................................................................................... 7
3.1 Apparatus ...................................................................................................................................... 7
3.2 Procedure ...................................................................................................................................... 7
3.3 Analyzing Aluminum Strip ............................................................................................................. 8
4 Discussions and Results........................................................................................................................ 9
4.2 Anodized and Sealed Aluminium ................................................................................................ 10
4.3 Anodized Aluminium ................................................................................................................... 12
4.4 Nyquist plots ............................................................................................................................... 12
4 .5 Equivalent circuit analysis .......................................................................................................... 13
5 Conclusion .......................................................................................................................................... 15
References ............................................................................................................................................ 15

List of Figures
Figure 1 Apparatus for anodizing aluminum .......................................................................................... 5
Figure 2 Experimental set up .................................................................................................................. 7
Figure 3 Ground aluminum ..................................................................................................................... 8
Figure 4 Anodized aluminum .................................................................................................................. 8
Figure 5 EIS Spectrometer....................................................................................................................... 9
Figure 6 BODE Plot for Ground aluminium ............................................................................................. 9
Figure 7 BODE phase Shift-Ground Aluminum ..................................................................................... 10
Figure 8 BODE Plot- Anodzied and Sealed Aluminium ......................................................................... 10
Figure 9 BODE Phase Plot for two Trials ............................................................................................... 11
Figure 10 BODE Plot for Anodized Aluminium ...................................................................................... 12
Figure 11 Nyquist Plot-Anodized .......................................................................................................... 12
Figure 12 Nyquist Plot-anodized and sealed ........................................................................................ 13

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ANODIZING OF ALUMINIUM

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List of Tables
Table 1 Ground Aluminium collected data ........................................................................................... 14
Table 2 Anodized Aluminium collected data ........................................... Error! Bookmark not defined.
Table 3 Anodized and Sealed collected data ........................................... Error! Bookmark not defined.

ECP LAB

ANODIZING OF ALUMINIUM

GROUP B5

1 Introduction
The main goal of this experiment is to analyze the electrical and physical properties of
anodized aluminium strip and to compare with original ground aluminium strip through
Electrochemical Impedance spectroscopy.
By definition, Anodizing is a process to electrolytically coat a metallic surface with a
protective or decorative oxide. The anodic coating consists of aluminum oxide and is
considered resistant to corrosion and abrasion. Coatings are 0.1 mm to 1.0 mm thick and
are essentially transparent, although they may be colored.
Unlike most other finishes, anodizing preserves the natural luster, texture, and beauty of
the metal itself. The anodized coating is hard, durable, will never peel, and, under normal
conditions, will never wear through.
In the experiment, the electrochemical impedance spectroscopy is used to analyze the two
sides of our aluminum strip in which one side has been anodized while the other side has
not been. At the end, we discuss and conclude by

2 Theoretical Background
In this chapter, the process behind anodizing and chemical reactions involved in anodizing
are discussed.

2.1 The Anodizing Process

Anodizing is a process for producing decorative and protective films on articles made up of
aluminium and its alloys in particular. But anodizing is also also applied for zinc, titanium
alloys. The article of interest is made the anode of an electrolytic cell with aqueous sulfuric
acid as electrolyte. The following overall oxidation reaction occurs during the process,
2Al + 3H2O Al2O3 + 6H+ + 6e-

(2.1.1)

A dense even layer of oxide about 0.08 m thick is formed rapidly, followed much more
slowly with a more porous layer up to 25m thick. Before anodizing, the surface of the
article must be thoroughly cleaned, normally using a detergent based process and etched
with a solution of sodium hydroxide. After anodizing, the surface may be coloured with a
dye or by an electrolytic method using appropriate metal cations. It can be sealed by placing
in boiling water during which the pores in the oxide layer are being closed off.
Oxide formation on the surfaces of metals is a naturally occurring phenomenon that results
from exposure to oxygen and moisture in the air. Although oxidation on ferrous metals, also
known as rust, can cause the eventual destruction of the material, metals such as aluminum
alloys, zinc, titanium, magnesium and tantalum can benefit from an oxide layer. If
manipulated to be thick enough, these oxidative layers can offer corrosion and wear
resistant properties to these metals. This is the principle that underpins the anodizing
process used to impart protective and attractive finishes on many non-ferrous metal items.

ECP LAB

ANODIZING OF ALUMINIUM

GROUP B5

The anodizing process involves passing an electric current through an electrolyte solution
between a positively charged anode (in this case the anodized item) and a negatively
charged cathode. This resultant reaction changes the crystal structure of the anode surface
and causes a layer of oxide to be deposited on it in. This is known as an electrolytic
passivation process. The characteristics of this oxide film can be manipulated during this
process, thereby allowing for a high degree of control over the end result. Generally the
synthesized layers are more robust than those occurring naturally. As a matter of interest,
the anode role played by the product is the source of the name- anodizing.
Anodized oxide layers are generally fairly porous by nature and require the application of
sealant to ensure maximum corrosion and wear resistance. The film's adhesion to the metal
is far stronger than conventional plating or painting films though, thus making anodized
finishes particularly durable. This durability offers an excellent base for the post-treatment
application of paints and dyes, with coloured anodized finishes exhibiting outstanding
longevity even with continuous use. Anodizing also helps prevent galling, or adhesive wear,
of threaded or sliding parts at their points of friction.

2.2 Electrochemistry of anodizing

The anodizing process makes use of electrolysis. The cathode (negative Terminal)
decomposes the oxonium contained in the acid (H3O+) in hydrogen and water and
hydrogen is released.
6H3O+ + 6e- 3H2 + 6H2O (2.2.1)

Figure 1 Apparatus for anodizing aluminum

As can be seen in above figure1, the scheme for anodizing is explained. It shows an
aluminium strip dipped in sulfuric acid and a desired amount of voltage is supplied. There
are two kind of reactions happening in anodizing of aluminum oxidation and aluminium
oxide formation. First reaction (oxidation) happens at anode during which oxidation of
aluminum to aluminum ions will take place [equation 2.2.2].
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ECP LAB

ANODIZING OF ALUMINIUM

2Al Al3+ + 6e-

GROUP B5

(2.2.2)

And then further reaction occurs, leading to the formation of aluminum oxide. Equation
(2.2.3)
2Al3+ + 9H2O Al2O3 + 6H3O+ (2.2.3)
And after this the overall reaction takes place which can be seen in equation (2.1.1). For
electrolyzing, we need a power supply -a DC power supply in specific which will give us a
constant voltage and current.

2.3 Metal analysis using EIS

After conducting the aluminum anodizing, the anodized surface needs to be analyzed and
the value is measured with respect to the ground surface. With help of EIS (electrochemical
impedance spectroscopy), the aluminum surface is analyzed. This will be done by
connecting the metal to an alternative current and with low amplitude and measuring the
resulting current. By variation of the frequency f (approx. 101 to 105 Hz), the impedance Z is
determined. This relationship between impedance and frequency is shown in the following
equation.
Z=F()=2 f

(2.3.1)

Where f=frequency of alternating current.

The variation of impedance with respect to frequency is plotted in Bode plot. When the
impedance becomes constant with respect to change in frequency, the impedance begins to
behave as an ohmic resistance. The reason for this is explained using the formula 2.3.2
Z=

(2.3.2)

Where Ew is the frequency induced potential and Iw is the frequency induced current. So
from this equation, we know that Impedance could be only produced by alternating current
and not by a direct current. It implies that constant impedance occurs when there is no
change in applied voltage due to capacitance in the material. The material exhibits an ohmic
behavior at this stage. The Bode phase plot measures the change in the phase of output
with respect to input signal. As a matter of fact, phase shift occurs only when capacitance
region comes in to picture whereas there is no phase shift in case of resistance.
It could be deduced that peaks in Bode phase plot implies capacitance and valleys/burrows
representing resistance. The equivalent circuit could be made using this resultant curve. The
real and imaginary parts of Impedance are plotted against each other in a Nyquist plot . The
real part denotes thickness of layer (resistance) whereas the imaginary region denotes
capacitance. The impedance Z could be derived from the following formula 2.3.3 using real
and imaginary parts.

(2.3.3)
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ANODIZING OF ALUMINIUM

GROUP B5

Based on the above results, an equivalent circuit could be made to evaluate the resistance
and capacitance of aluminium strip. To put it concisely, an equivalent circuit consists of
passive electrical circuit elements whose response is calculated and compared with actual
EIS response of an element. This circuit usually consists of resistance and capacitance but
may also contain an Inductance.

3 Experimental procedure
The experimental procedure is given below under the headings - Apparatus, Procedure and
Analysis.

3.1 Apparatus
For conducting this experiment an Aluminum strip (anode) is needed. Apart from that we
need sulfuric acid solution, a power supply for electrolyzing, a strip as cathode which will be
our lead strip and an alkaline solution for Cleaning.
In below figure.2, the apparatus which is needed for our experiment is shown.

Cathode
Anode

Power
supply

solution

Figure 2 Experimental set up

3.2 Procedure
In order to have maximum anodizing, cleaning our aluminum strip is necessary. In the
laboratory, alkaline solution and distilled water were used to wash and clean aluminum
surface.

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ANODIZING OF ALUMINIUM

GROUP B5

Figure 3 Ground aluminum

As can be seen in figure 3, the un-treated aluminum first will be immersed in alkaline
solution for approximately 10 minutes at a temperature of 60 C. Then the Aluminum is
taken out and submerged it into distilled water for couple of minutes and cleaned with
tissue. After this, Aluminum is submerged into the solution of 18% sulfuric acid. The area is
calculated in cm2.
Using Aluminum strip as Anode and Lead strip as Cathode, the power supply will be set for
current of 15mA per cm2 for one hour. After that one part of the strip is broken and put in
boiled water for approximately 20 minutes and after this step that broken aluminum strip
will be completely anodized and sealed.
The difference between the anodized part and non-anodized part can be seen in below
figure 4.
We have three strips now namely anodized, anodized & sealed and non-anodized.

Treated
part

Untreate
d part

Figure 4 Anodized aluminum

3.3 Analyzing Aluminum Strip

Final part of our procedure is analyzing the Aluminum strip with help of EIS Spectroscopy
the Aluminum strip will be attached to an impedance measurement device.

ECP LAB

ANODIZING OF ALUMINIUM

GROUP B5

Figure 5 EIS Spectrometer

In this device, we have negative and positive poles in which negative one will be attached to
our strip and positive part will be attached to a counter electrode. A drop of 5% sodium
chloride is used as the gap (electrolyte) between the Strip and Electrode and with help of
software we can see the behavior of Aluminum strip in different conditions-anodized ,non anodized and sealed. The data from EIS spectrometer is discussed in the next chapter.

4 Discussions and Results

Bode plots (Abs(z) and Phase Shift) and Nyquist plots for different samples of Aluminium
have been plotted and discussed below. The above plots are made for three samples of
aluminium exhibiting different conditions- anodized and sealed, anodized and Ground
(original) samples of aluminium. It should be noted that the measured values contain a far
higher range and only a short subset of measurements were used to evaluate the Bode plots
in order to have maximum accuracy and legibility.

Absolute Z(abs Z/Ohm)

20000

BODE Plot for

Ground aluminium

15000
10000

Series1

5000
0
0

50

100

150

200

Frequency (f/s-1)

Figure 6 BODE Plot for Ground aluminium

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ANODIZING OF ALUMINIUM

GROUP B5

BODE Phase shift-Ground Aluminium

Phase shift (alpha/ )

100
80
60
40

alpha/

20
0
0

100000 200000 300000 400000

Frequency(f/s-1)

Figure 7 Bode phase Shift-Ground Aluminum

As shown in the figure 6, the absolute impedance is plotted against frequency. The
impedance shows a decrease with increasing frequency and after a certain point becomes a
constant one. When the impedance does not vary with respect to frequency, the impedance
becomes purely ohmic and so the ohmic resistance can be calculated from the graph. We
find that at a frequency of 120Hz ,the impedance becomes purely ohmic and the value of
ohmic resistance is 3438 .
The Bode Phase shift diagram (fig.7) represents the change in phase between the input and
output. On maximising the diagram, one peak could be found which represents one
capacitance regions.

4.2 Anodized and Sealed Aluminium

1.00E+05

Bode Plot-Anodized and

sealed Aluminium

9.00E+04
8.00E+04
Abs (Z)/Ohm

7.00E+04
6.00E+04
5.00E+04

Trial 1

4.00E+04

Trial 2

3.00E+04
2.00E+04
1.00E+04
0.00E+00
0

200

400

600

800

Frequency(f/s-1)

Figure 8 Bode Plot- Anodzied and Sealed Aluminium

10

1000

ECP LAB

ANODIZING OF ALUMINIUM

GROUP B5

As you can see in figure 8, Bode plot of anodized and sealed aluminium is obtained from EIS
spectroscopy. The anodized sample was dipped in boiling water for a period of 30 minutes.
Then the sample is taken out and subjected to cleaning. After that the sample has
undergone EIS spectroscopy. Two sets of readings are taken from the sample at different
spots and it is shown in the above graph. The absolute impedance for the two regions shows
a considerable difference in the ohmic region. This behaviour may be attributed to irregular
distribution of porous layers in the anodized film. The ohmic resistance for the first region
occurs at a region of 593 Hz and the corresponding ohmic resistance is 8825.7 . for the
second set of readings the impedance becomes purely ohmic at 645Hz and the
corresponding ohmic resistance is 17450 . It is very high as compared to other results .It
may be either due to measurement error or excessive pores in that particular area which
increases the capacitance.
90

Bode Phase Plot

80

Phase shift (alpha/)

70
60
50
Alpha trial 2

40

Alpha Trial 1

30
20
10
0
0.01

100

Frequency

10000

(f/s-1)-Logarithmic

1000000

scale

Figure 9 Bode Phase Plot for two Trials

The Bode phase plot for anodized aluminium is shown in fig no.9, As you see here, the graph
shows two peaks (ridges) and two low burrows (low regions).It manifests the presence of
two capacitance regions and two resistance regions. Based on this result, an equivalent
circuit could be made and the resistance, capacitance and Inductance could be calculated.

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ECP LAB

ANODIZING OF ALUMINIUM

GROUP B5

4.3 Anodized Aluminium

10000

Bode plot for

Anodized Aluminium

9000

Abs (Z)/Ohm

8000
7000
6000
5000

trial 1

4000

trial 2

3000
2000
1000
0
0

50

100

150

200

Frequency(f/s-1)

Figure 10 Bode Plot for Anodized Aluminium

The result of the EIS spectroscopy of anodized aluminium without any further treatment is
shown in figure 10. As similar to anodized and sealed aluminium sample, two set of readings
were taken at different spots. It could be vividly seen that there is very less difference
between the two sets of readings. Here the impedance becomes completely ohmic at a
frequency of 77Hz and the corresponding ohmic resistance is 1988 and 2186 for trial 1
and trial 2 respectively.
The Bode phase shift plot shows a big peak region which further reduces down with respect
to frequency. It shows a presence of one capacitance region.

4.4 Nyquist plots

8.00E+05

Nyquist Plot-anodized

7.00E+05
6.00E+05
Z(Im)

5.00E+05
4.00E+05
3.00E+05

Trial 2

2.00E+05

trial 1

1.00E+05
0.00E+00
0.00E+00

1.00E+05

2.00E+05

3.00E+05

4.00E+05

Z(Re)

Figure 11 Nyquist Plot-Anodized strip

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5.00E+05

ECP LAB

4.00E+06
3.50E+06

ANODIZING OF ALUMINIUM

GROUP B5

Nyquist Plot- anodized

and sealed

3.00E+06
Z(Im)

2.50E+06
2.00E+06

Trial 2

1.50E+06

trial 1

1.00E+06
5.00E+05
0.00E+00
0.00E+00 1.00E+05 2.00E+05 3.00E+05 4.00E+05 5.00E+05 6.00E+05
Z(Re)

Figure 12 Nyquist Plot-anodized and sealed strip

The Nyquist plots of two samples are compared here. The imaginary part represents the
porosity of anodized layer which implies capacitance whereas the real part represents
thickness of the anodized layer which implies resistance. In both the samples, real and
imaginary parts are directly proportional and linear which implies capacitance increases
with layer thickness due to subsequent increase in porosity. Only exception is trial 1 of
anodized sample which shows an exponential increase .This could be attributed to presence
of a highly porous- uneven anodized layer. But due to sealing, that effect is nullified due to
formation of Boehmite (Hydrated aluminium oxide) in the porous region which fills up that
area. The formation is explained in equation 4.4.1.
2AlOOH (Boehmite)

(4.4.1)

4 .5 Equivalent circuit analysis

An equivalent circuit is made with the available details and the behaviour of the aluminium
in ground, anodized and anodized sealed states are analysed. The equivalent circuit
actually represents the electrical properties of aluminium with R representing resistance
(layer thickness) and Q representing capacitance (porosity). The results are given below and
are presented in comparison with Ground aluminium. A number of equivalent circuits were
created in laboratory session, but only the important ones are taken for analysis. The
preference is given to the results with low chi square value which indicates very less
difference between the experimental and measured results.

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ANODIZING OF ALUMINIUM

Index Fixed

Symbol

1
2
3
4
5
6
7

0
0
0
0
0
0
0

Initial

L/H
R/Ohm
Q/(S s^n)
n
R
Q
n

GROUP B5

Error
percentage

Final

5.55E-07
3.45E+00
4.03E-07
9.23E-01
2.21E+04
2.34E-06
6.25E-01

5.55E-07
3.45E+00
4.03E-07
9.23E-01
2.21E+03
2.34E-06
6.25E-01

2.01
1.18
4.36
0.39
11.4
2.2
0.77

Table 1 Ground Aluminium collected data equivalent circuit and CPE

The constant phase element (CPE) equivalent circuit data for ground aluminium is shown in table 1.
Here R and Q represents the resistance and capacitance of diffused layers. Q/(S s^n) represents a
non ideal capacitor in which the idealness is decided by the value of n. n=0 means pure resistor and
n=1 means pure capacitor where n is an empirical value. It is used to denote the lack of
homogeneity. On the other hand the table shows a low ideal capacitance. The chi square value for
this table is 0.0008244 and the equivalent circuit model is LR(Q(RQ)).
Index

Fixed
1
2
3
4
5
6
7

Symbol
0
0
0
0
0
0
0

L
R
Q
n
R
Q
n

Initial
6.32E-07
3.93E+00
1.14E-06
9.95E-01
9.33E+05
2.23E-05
7.83E-01

Final

Error Percentage

6.33E-07
3.93E+00
1.14E-06
9.95E-01
9.33E+05
2.22E-05
7.83E-01

2.96
1.66
4.74
1.46
15.6
108
8.08

Table 2 Equivalent circuit data-Anodized Aluminium

As seen in table 2 it is found that the value of equivalent capacitance value of anodized
aluminium is lower than ground aluminium. Inductance also comes in to picture in the
circuit. The Inductance gives out reactance due to back EMF when subjected to alternating
current. The chi squared value for this table is 0.001994 and the equivalent circuit model is
LR(QR)Q.
Index

Fixed
1
2
3
4
5
6

Symbol
0
0
0
0
0
0

R
Q
N
R
Q
N

Initial
6.91E+00
3.25E-08
7.10E-01
5.02E+04
1.71E-06
8.54E-01

Final

Error Percentage

6.90E+00
3.25E-07
7.10E-01
5.02E+04
1.71E-06
8.54E-01

Table 3- Anodized and Sealed Aluminium collected data-equivalent circuit

14

27.3
4.22
0.54
2.93
1.34
0.84

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ANODIZING OF ALUMINIUM

GROUP B5

The presence of two capacitances Q in the table exactly coincides with the Bode phase plot
which indicates the presence of two capacitances.Between the two capacitances, first one
denotes the inner barrier layer and the latter one denotes the outer porous layer.
Table 3 shows the equivalent circuit data for anodized and sealed aluminium. Interestingly
the capacitance value becomes even less after sealing. As mentioned earlier, it is due to the
formation of boehmite which fills up the pores. On the other hand the resistance increases
by a huge proportion. The presence of two capacitance conforms with the result from Bode
phase shift plot showing two peak resistances. On the other hand presence of high n values
on all the three tables denotes a near ideal capacitance due to porosity. The Chi square
value is 0.004999 and the equivalent circuit value is R(QR)Q.

5 Conclusion
It is concluded that the equivalent circuit data conforms with the results of Bode phase plot for all
the three samples. On the other hand, resulting resistances from the plot of anodized and sealed
aluminium is far higher than expected values. It may be attributed to machine /human errors. To
sum up, this experiment provided the base knowledge in EIS spectroscopy and also gave a good idea
about anodizing.

References
1. Ramanathan ,Huang et al, Evaluation of the corrosion resistance of anodized aluminum 6061
using electrochemical impedance spectroscopy (EIS),University of Southern California,
Journal of Corrosion Science, 50 (2008) 35693575.
2. Franco, Anoop et al, Porous Layer Characterization of Anodized and Black-Anodized
Aluminium by Electrochemical Studies, Indian Space Research Organization-Institute of
Thermal Systems,Bangalore-India, 2012,ISRN Vol.no 323676.
3. Electrochemical Impedance Spectroscopy (EIS) ,Part 3 Data Analysis,Metrom Autolab B.V,
Utercht,Netherlands, Autolab Application Note EIS03.

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