Mork Family

Department of Chemical Engineering and Materials Science

2007 Student Symposium

Evaluation of the Corrosion Resistance of Anodized Aluminum Samples Using

Electrochemical Impedance Spectroscopy (EIS)
Yuelong Huang, Esra Kus and Prof. Florian Mansfeld
Corrosion and Environmental Effects Laboratory (CEEL)
The Mork Family Department of Chemical Engineering and Materials Science
University of Southern California, Los Angeles, CA 90089-0241
I. Introduction
The purpose of this study is to evaluate the corrosion resistance of anodized layers produced by new anodizing and sealing process using electrochemical impedance spectroscopy (EIS). The
scanning electron microscope (SEM) was employed to determine the surface structure and the thickness of the anodized layers. The impedance spectra were analyzed using an appropriate
equivalent circuit (EC). There was very little change in the impedance for all test samples during exposure period. The results of these tests suggest that anodized Al 6061 treated in the new
processes was very corrosion resistant during extended exposure time periods.
Anodized Aluminum (Al 6061) Samples Anodized aluminum interface model
1. R&D Tank Mixed Acid Equivalent circuit for the analysis of the impedance spectra for anodized Al samples.
Cpo Cb
two samples tested in 3.5wt% NaCl for 14 days
Porous Layer
2. Type III ~~
Rs
Barrier Layer
two samples tested in 3.5wt% NaCl for 14 days Aluminum Alloy
Rpo Zpo Rb
Cpo: Capacitance of the outer porous layer Cb: Capacitance of the inner barrier layer
3. Production Tank Rpo: Pore resistance. Rb: Polarization resistance of the barrier layer
three samples tested in 3.5wt% NaCl for 365 days Zpo: Constant phase element (CPE) to account for the variations of properties of the pores.

II. Experimental Methods and Results

Impedance spectra were collected at the open-circuit potential (OCP) in a three-electrode cell. A stainless steel electrode was used as the counter electrode and a SCE as the reference
electrode. The impedance spectra were obtained with a BSA-Zahner IM6 unit using a frequency range between 1 MHz to 1 mHz with an ac amplitude of 10 mV. The EIS data were analyzed
using the ANODAL software of ANALEIS. The spectra for all test panels for a given treatment were almost identical and did not change much with exposure time (Fig. 1-3). The almost
identical capacitance values at the highest and lowest frequencies suggest that the thickness of the outer porous layer and the inner barrier layer, respectively, are almost the same for the all
tested samples. The SEM pictures revealed that the coating thickness was about 63 μm (Fig. 4). The capacitance of the porous layer Cpo for the all test samples was very stable during the
entire exposure period (Fig. 5 and 6). The pore resistance Rpo had very high values for all test samples (Fig. 7 and 8). These results indicate that the anodizing process was very reproducible
and that the sealing process was very effective.

8 8
EIS Results 9
Cross Section of the anodized layer
7 7 8

7
6 6
6
5 5
5
4 4
4
3 3
3

2 2 2

1 1 1
-3 -2 -1 0 1 2 3 4 5 6 -3 -2 -1 0 1 2 3 4 5 6 -4 -3 -2 -1 0 1 2 3 4 5 6

-90 -90 -90

-80 -80 -80

-70 -70 -70

-60 -60 -60

-50 -50 -50

-40 -40 -40

-30 -30 -30

-20 -20 -20

-10 -10 -10

0 0 0
-3 -2 -1 0 1 2 3 4 5 6 -3 -2 -1 0 1 2 3 4 5 6 -4 -3 -2 -1 0 1 2 3 4 5 6

Fig. 1. Bode-plots for the R&D tank mixed Fig. 2. Bode-plots for the type III Fig. 3. Bode-plots for the production tank Fig. 4. SEM image of the production tank sample
acid sample for an exposure period of 14 days sample for an exposure period of 14 days sample for an exposure period of 365 days
15 15 6 6

13 13
LogRpo (ohm)
LogRpo (ohm)

Type3 D2Lot3
0907-073 0907-107
Cpo (nF)

Cpo (nF)

11 11
TY3 D2Lot2
0907-005 0907-005
D2Lot3 TY3
9 9 0907-107 0907-073
D2Lot2 Type3
7 7

5 5 5 5.5
0 2 4 6 8 10 12 14 16 0 50 100 150 200 250 300 350 0 2 4 6 8 10 12 14 16 0 50 100 150 200 250 300 350
Time (days) Time (days) Time (day) Time (days)

Fig. 5. Time dependence of Cpo for R&D Fig. 6. Time dependence of Cpo for Fig. 7. Time dependence of Rpo for R&D Fig. 8. Time dependence of Rpo for
tank mixed acid and type III samples production tank samples tank mixed acid and type III samples production tank samples

III. Conclusions
● The impedance spectra for the samples that were anodized in the R&D tank mixed acid were very stable during 14 days exposure.
● The impedance spectra for the type III samples suggest that oxide layers are more complex than those for the other samples. The impedance spectra did not change significantly during the
14 days exposure time which suggests that these anodized surfaces were very corrosion resistant.
● The impedance spectra for the production tank samples were very stable for an exposure time of 365 days showing that these surfaces had very high corrosion resistance.
● The very high and stable values of the pore resistance Rpo for all three processes indicate that the newly developed anodizing and sealing processes were very effective.
Acknowledgements References
Funding by Lam Research Corporation and numerous helpful 1. F. Mansfeld, G. Zhang and C. Chen, Plating and Surface Finishing, 84 , 72 ( Dec. 1997).
discussions with Dr. Hong Shih are greatly appreciated. 2. F. Mansfeld, L. T. Han, C. C. Lee and G. Zhang, Electrochim. Acta 43, 2933 (1998).
3. F. Mansfeld, H. Shih, H. Greene, C.H. Tsai, ASTM STP 1188 (1993) 37.
4. Dr. Hong Shih presentation.