Intelligent self-healing corrosion resistant vanadia coating for AA2024

Abdel Salam Hamdy

a, b,
, I. Doench
b
, H. Mhwald
b
a
Central Metallurgical Research and Development Institute, CMRDI, P.O. Box: 87, Helwan, Cairo, Egypt
b
Max Planck Institute of Colloids and Interfaces, Am Mhlenberg 1, 14476 Potsdam, Germany
a b s t r a c t a r t i c l e i n f o
Available online 14 June 2011
Keywords:
Chemical conversion coatings
Vanadia
EIS
AA2024
Surface treatment
Self-healing
Protective lms
Cyclic voltammetry
Marine corrosion
This paper is a continuation of our investigation into the designing of chromate-free anti-corrosion coatings
for aluminum and magnesium based materials for marine, automotive and aerospace applications. In this
paper, a simple vanadia based chemical conversion coating was applied for improving the corrosion resistance
of high strength AA2024 alloy. The effect of vanadia solution concentrations (10, 30 and 50 g/l) on the
corrosion behavior was investigated. EIS, linear polarization and cyclic voltammetry techniques were used to
evaluate the electrochemical behavior in 3.5% NaCl. Vanadia coatings prepared by dissolving 10 g of vanadate
salt per liter showed the best localized corrosion resistance as measured by EIS and polarization techniques.
The optimum conditions to obtain corrosion protective coatings for AA2024 were determined. Surface
examination of the samples was investigated using AFM, SEM-EDS and macroscopic images.
2011 Elsevier B.V. All rights reserved.
1. Introduction
The typical aluminumsurface is covered by a 37 nm thick natural
oxide lm. However, this thin layer is not sufcient to protect against
corrosion agents and does not yield good adhesion to subsequent
layers of the coating. Moreover, the presence of some alloying
elements such as copper in AA2024 alloy particularly increases pitting
corrosion attack by forming galvanic couples.
Coating systems used for military aircraft typically employ a
hexavalent chromium (Cr(VI)) conversion coating in direct contact
with the metallic substrate, a strontium chromate primer over the
conversion coating, and a topcoat over the primer (see Fig. 1).
However, chromium has been identied as a human carcinogen that
can signicantly increase the risk of lung cancer. As a result, Cr(VI)-
based coatings are being phased out but nding a suitable
replacement has proved challenging.
Extensive research has been invested for designing alternative
eco-friendly technologies such as anodization [1], solgel treatment
[26], pigmented coatings [7], conductive pigments/polymers, pig-
ment-based cathodic protection [8,9], green chemical conversion
coatings [1018], and aluminum nitride thin lms [1925].
This paper addresses part of our research activities at Max Planck
Institute (MPI), focuses on a two-layer coating system, including a
non-chromate conversion coating layer and a commercially available,
self-priming top coating containing nontoxic corrosion inhibiting
materials for high-strength aluminum alloys (Fig. 1).
Previous efforts to replace the chromate-based coatings in
particular chromate primers with more benign materials have had
some success. For example, a chromate-free primer developed for
several magnesium and aluminum alloys and composites [118].
However, non-chromate primers based on cerium salts, for example,
are relatively expensive and a long treatment time is needed.
Introducing environmentally benign such as vanadia based
conversion coatings prior to a commercially available top coatings
(such as epoxy, uoropolymer,etc.) is an attractive alternative to
the existing systems, as it would reduce the complexity of the coating
system into two layers while at the same time reducing volatile
organic compounds. When used with a non-chromate conversion
coating, an environmentally acceptable anti-corrosion coating system
would be obtained.
Conversion coatings are aqueous chemical surface treatments
that provide metallic surfaces with increased corrosion resistance
and enhanced paint adhesion. Work done at MPI, together with
other previous research work [17,18,2629]; have identied
vanadium oxide-based conversion coatings (VCC) as potentially
viable corrosion inhibitors and replacements for chromate conver-
sion coatings on magnesium and aluminum alloys and composites.
The VCCs show promise for corrosion protection to high-strength
aluminum alloys, such as the 2024-T3 used in military and
commercial aircraft.
The coatings are deposited from aqueous solutions containing
sodium vanadate using a very simple spontaneous free immersion
processing technology that is very similar to that currently used for
Thin Solid Films 520 (2011) 16681678
Corresponding author. Max Planck Institute of Colloids and Interfaces, Am
Mhlenberg 1, 14476 Potsdam, Germany. Tel.: +202 25010640; fax: +202 25010639.
E-mail address: asalam85@yahoo.com (A.S. Hamdy).
0040-6090/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.tsf.2011.05.080
Contents lists available at ScienceDirect
Thin Solid Films
j our nal homepage: www. el sevi er. com/ l ocat e/ t sf
the toxic chromate system. A thin layer of vanadiumoxide conversion
coatings is deposited on the aluminum alloy surface by a chemically
driven deposition process. Typically, uniformly distributed compact
coatings of thickness about 1 to 1.2 m were deposited. Depositions
are achieved in 10 min and use commercially available chemical,
materials and equipment, making the overall process compatible with
industrial operations such as those employed by current automotive
and aircraft manufacturers.
The adhesion performance can be improved simply by cleaning
the substrate surface prior to vanadia coatings, but these solvents
usually remove only oils and greases, leaving more tenacious
materials such as surface oxides, which may prevent inter-diffusion
and thus adhesion. For thin lms formed from the gas phase, the
adhesion is generally promoted by including plasma pre-sputtering,
which removes the surface oxide, before forming the new layer. In
case of solid-phase-formed lms, surface properties such as
roughness are important and, therefore, the substrate is commonly
polished before the next layer is formed. In case of liquid-phase lm
formation, as concerned in this project, chemical surface modiers
using alkaline etching in 1 M NaOH solution at 60 C followed by
acidic pickling in 20% HNO
3
at room temperature are applied prior
to the new vanadia lm being formed.
Coatings that result from these processes are composed mostly
of vanadium oxide phases. The operating parameters and condi-
tions used to deposit the coating signicantly inuence the quality
and performance of the deposited lms. Three critical steps in
producing the vanadium oxide conversion coatings are surface
preparation, vanadia coating concentration and pH, and post-
deposition treatment using hot air drying. This paper will focus
on investigating the effect of vanadia coating concentration on the
corrosion protection performance of AA2024 T3.
Fig. 1. A schematic representation (not to scale) showing (a) the three layers of a conventional toxic chromate-containing corrosion protection system and (b) the two layer
vanadium oxide coating technology in the system being developed by the MPI team.
Table 1
Chemical composition (wt.%) of AA2024 T3.
Element Cu Si Fe Mg Mn Al
wt.% 4.46 0.18 0.28 1.35 0.64 Balance
a b
Uncoated
Surface defects
Uncoated
Pitting corrosion
Counts Counts
80000
30000
20000
10000
0
60000
40000
20000
0
0 2 4 6 0 2 4 6
Energy (keV) Energy (keV)
Fig. 2. SEM-EDS for the blank samples before (a) and after (b) corrosion in 3.5% NaCl solution for one week. The images focus into the surface defects and localized corrosion zones.
1669 A.S. Hamdy et al. / Thin Solid Films 520 (2011) 16681678
Studies to improve and optimize these critical steps were
conducted thoroughly during this project for some magnesium and
aluminum alloys. The corrosion behavior was studied in 3.5% NaCl
solution by means of EIS and cyclic voltammetry techniques. Surface
examination was performed by AFM, SEM-EDS and visual inspection.
2. Experimental
2.1. Materials and surface preparation
Specimens of AA2024 alloy in the form 3060 mm taken from
sheet of 3 mmthick were abraded to 800 # nish with SiC grit papers,
degreased in acetone, washed with distilled water, and dried in dry
air. The chemical composition (wt.%) is given in Table 1.
2.2. Solutions and surface treatment
Solutions used in this work were prepared using sodium vanadate
salt with different vanadia solution concentrations. The AA2024
substrates were treated by simple free immersion in vanadia solutions
under the following conditions:
1. As polished (as a blank) without vanadia coatings
2. Treatment in 10 g/l NaVO
3
solutions for 10 min
3. Treatment in 30 g/l NaVO
3
solutions for 10 min
4. Treatment in 50 g/l NaVO
3
solutions for 10 min
After coatings, the samples of each group were washed with
nano-pure water and dried with hot air. A comparison will be made
a
b
10 g/l
Self-healing
Self-healing
Nucleation of vanadia
over a pitting zone
(Self-healing)
10 g/l
10 g/l
Compact coating
Flower like morphology
Counts
15000
10000
5000
0
Counts
15000
20000
10000
5000
0
0 2 4 6 8 10
0 2 4 6
Energy (keV)
Energy (keV)
Fig. 3. SEM-EDS for the vanadia coated (10 g/l) samples before (a) and after (b) one week in 3.5% NaCl solution. The images focus into the nucleation of vanadium oxide over the
corroded zones and the self-healing tendency due to vanadia.
1670 A.S. Hamdy et al. / Thin Solid Films 520 (2011) 16681678
between the corrosion resistances during seven days of immersion
in 3.5% NaCl solution.
2.3. Testing
2.3.1. Electrochemical impedance spectroscopy (EIS)
EIS technique was used to evaluate the electrochemical behavior
of the uncoated (as-polished) and coated AA2024 samples in 3.5%
NaCl solution open to air and at room temperature for up to seven
days. A three-electrode set-up was used with impedance spectra
being recorded at the corrosion potential E
corr
. A saturated calomel
electrode (SCE) was used as the reference electrode. It was coupled
capacitively to a Platinum wire to reduce the phase shift at high
frequencies. EIS was performed between 0.01 Hz and 65 kHz
frequency range using a frequency response analyzer (Electro-
chemical analyzer instrument: CompactStat Ivium Soft 1.805
Release IVIUM Technologies Netherlands). The amplitude of the
sinusoidal voltage signal was 10 mV. The exposed surface area was
4 cm
2
. All curves were normalized to 1 cm
2
.
2.3.2. Cyclic voltammetry measurements
Cyclic voltammetry measurements of the samples previously
immersed for seven days in 3.5% NaCl solution were made at a scan
rate of 0.07 mV/s using CompactStat Ivium Soft 1.805 Release IVIUM
Technologies Netherlands. The potential was recorded starting from
a cathodic potential (100 mV) and allowed to sweep to anodic
potential direction till a sudden shift in the current to the active
direction was observed. At that point the sample was enforced to
sweep again in the cathodic direction. The exposed surface area was
4 cm
2
. All curves were normalized to 1 cm
2
.
a
b
30 g/l 30 g/l
30 g/l
Surface defects
Counts
Energy (keV)
Energy (keV)
80000
Counts
40000
30000
20000
10000
0
0 2 4 6
60000
40000
20000
0
0 2 4 6
Fig. 4. SEM-EDS for the vanadia coated (30 g/l) samples before (a) and after (b) one week in 3.5% NaCl solution. The images focus into the healing behavior with increasing the
vanadia concentration.
1671 A.S. Hamdy et al. / Thin Solid Films 520 (2011) 16681678
2.3.3. Surface characterization
SEM and EDS were used to examine the surface morphology of the
coated samples before and after the immersion in 3.5% NaCl solution.
SEMimages of the samples that immersed in 3.5% NaCl for seven days,
washed with deionized water and then dried were obtained using a
Gemini LEO 1550, 3 kV operating voltage, Zeiss, Germany. Microprobe
analysis was performed using DSM 940, Thungsten Kathod, Zeiss,
Germany, Coupled EDX ISIS, SiLi-Detector, Energy resolution 133 eV,
Oxford. Each analysis was preformed three times at different spots
using screen analysis at very high magnication covering the whole
size of the spot.
Atomic Force Microscopy (AFM) images were taken using the
Dimension NanoScope IIIa Controller Scanning mode: tapping mode
Veeco Instruments USA, to investigate the surface morphology on the
coated and uncoated substrate surfaces before corrosion.
Macroscopic images were taken using a digital optical metallo-
graphic microscope VHX-100K, KEYENCE, Japan, to investigate the
types of corrosion produced on the substrate surfaces after seven days
of immersion in 3.5% NaCl solution.
3. Results and discussion
3.1. Coatings characterization and surface examination
3.1.1. SEM-EDS micrographs and visual inspection
SEM micrograph of the uncoated aluminum samples before
immersion in 3.5% NaCl solution revealed presence of some surface
defects which stimulate pitting corrosion on AA2024 alloys
(Fig. 2a). After vanadia treatment, a relatively thick layer of
vanadium oxide depends on the vanadia concentration (about
40000
a
b
Micro-cracks
50 g/l 50 g/l
50 g/l
Surface defects
Counts
Energy (keV)
Energy (keV)
80000
Counts
40000
30000
20000
10000
0
0 2 4 6
60000
20000
0
0 2 4 6
Fig. 5. SEM-EDS for the vanadia coated (50 g/l) samples before (a) and after (b) one week in 3.5% NaCl solution. The images focus into the healing behavior with increasing the
vanadia concentration.
1672 A.S. Hamdy et al. / Thin Solid Films 520 (2011) 16681678
1.01.2 m) was formed. However, increasing the thickness due to
increasing the vanadia concentration affects negatively the coating
distribution over aluminum substrate where many coating defects
were observed for the samples coated with 30 and 50 g/l vanadia
(Figs. 3a, 4a and 5a).
After seven days of immersion in 3.5% NaCl solution, visual
inspection and microscopic examination of the uncoated samples
showed severe pitting as well as crevice corrosion (Fig. 6). The average
number of pits on the surface of the uncoated samples was 10 pits/cm
2
.
A marked decrease in the crevice corrosion areas was observed for the
vanadia coatedsamples (Figs. 3b, 4band5b). Moreover, the number and
the size of pitting attack decreased sharply for the samples coated with
vanadia. The number of pits was calculatedtobeless than2, 4and8 pits/
cm
2
for the samples treated in 10, 30 and 50 g/l vanadia solution
respectively (Fig. 6). The sample treated in 50 g/l solution showed a
dramatic decrease in the pitting and crevice corrosion resistance where
severe corroded surface full of pits with a vanadia layer loosely adhered
to the substrate. This indicates that increasing vanadia concentration
(N10 g/l) adversely affected the coating efciency (Fig. 6). The chemical
reaction behind formation of loosely adhered coating in that case is not
so clear and may be due to changing the vanadia-solution pH. The best
localized corrosion resistance was obtained from the samples that
treated with 10 g/l vanadia solution with a surface free of pitting and
limited zones of crevice (Figs. 3b, 4b 5b and Fig. 6).
3.1.2. Atomic Force Microscopy (AFM) examinations
The surface topography and roughness of the aluminum
substrate before and after applying the vanadia coatings were
examined by AFM. Uncoated aluminum substrates revealed a
naturally occurring aluminum oxide of high roughness distributed
over the substrate (Fig. 7a). The phase image of uncoated substrate
showed aluminum oxide phase with some small areas of different
phases which can be explained by the different oxides formed due
to different alloying elements in the AA2024 alloy under
investigation.
In general, vanadia coated samples (especially those treated at
lower vanadia solution concentrations 10 and 30 g/l) revealed a
more compact surface due to formation of vanadium rich oxide
lms (Fig. 7b and c). Such lms are characterized by lower
roughness and hence, better and uniform surface distribution of
the vanadia rich oxides over the Al substrate compared with
uncoated and coated ones at higher (50 g/l) vanadia concentration
(Fig. 7a, b, c and d). The phase images of vanadia coated substrates
showed two phases which can be explained by the formation of
vanadium-rich oxide incorporated in the aluminum oxide layer.
A comparison between images in Fig. 7b, c and d indicates that
increasing the vanadia solution concentration from 10 g/l to 50 g/l
increases the surface roughness of the lm formed and hence,
increase the chance for localized corrosion to occur. This observation
can be considered as another evidence for decreasing the corrosion
resistance with increasing the vanadia concentration.
3.2. Electrochemical impedance spectroscopy
The corrosion resistance of AA2024 samples uncoated and
coated with vanadia solutions of different concentrations ranging
from 0 to 50 g/l was investigated in 3.5% NaCl solution. According to
Nyquist plots (Fig. 8a), the surface resistance increases in presence
Pitting corrosion
Crevice corrosion
Uncoated
Crevice corrosion
10 g/l
50 g/l
Pitting corrosion
30 g/l
Crevice corrosion
Fig. 6. Macroscopic images for AA2024 samples treated in different vanadia concentration solutions after seven days of free immersion in 3.5% NaCl solution.
1673 A.S. Hamdy et al. / Thin Solid Films 520 (2011) 16681678
1674 A.S. Hamdy et al. / Thin Solid Films 520 (2011) 16681678
Fig. 7. AFM of AA2024 substrate before corrosion. a. uncoated. b. 10 g/l vanadia coated c. 30 g/l vanadia coated d. 50 g/l vanadia coated.
1
6
7
5
A
.
S
.
H
a
m
d
y
e
t
a
l
.
/
T
h
i
n
S
o
l
i
d
F
i
l
m
s
5
2
0
(
2
0
1
1
)
1
6
6
8

1
6
7
8
of vanadia coatings. However, increasing the concentration of
vanadia solution from 10 g/l up to 50 g/l seems to have an adverse
effect on the localized corrosion resistances. Generally, localized
corrosion attack due to the presence of silicon as an alloying
element in an aluminum matrix is the most common form of
corrosion in AA2024 alloys. It is known that localized corrosion
(pitting and crevice corrosion) is more dangerous than general
(uniform) corrosion. Visual inspection (Fig. 6) revealed that
localized corrosion is the most predominant corrosion form in the
uncoated samples. Conversely, the most predominant corrosion
form in the vanadia coated samples is the general corrosion
especially for the samples coated with low vanadia concentration,
i.e. 10 and 30 g/l (Fig. 6). The surface resistance measured by mean
of electrochemical impedance spectroscopy is the summation of
localized (pitting+crevice) and general corrosion resistances. This
can explain why the value of surface resistance seems to be higher
in case of the uncoated samples (Fig. 8a) although severe localized
corrosion occurred and the values measured for some vanadia
coated samples were relatively low although the localized corrosion
attack decreased.
This result conrms the observation of SEM and visual inspection
where the number of pits was deceased to be less than 2 pits/cm
2
for
the samples coated with 10 g/l vanadia solution (Fig. 6) which can be
attributed to formation of a compact vanadium-rich oxide lm
distributed uniformly over the aluminum substrate (Fig. 7b).
The impedance spectra after one week of immersion in NaCl
solution of bare AA2024 alloy and all vanadia treated samples show
the presence of two time constants (Fig. 8b). The time constant with
the maximum at around 110
2
Hz in the phase angle plot attributed
to the charge transfer resistance of corrosion process. However, the
phase angle () of the sample coated with 10 g/l vanadia is 60 degree
and the other phase angles are 80 degree. The second additional time
constant at low frequencies attributed to relaxation of mass transport
in the solid phase due to the growth of the corrosion product layer.
The time constant related to the corrosion process for all vanadia
coated samples (except 10 g/l vanadia) moves to higher frequencies,
approaching to the bare Al substrate.
The presence of vanadia coating prepared in 10 g/l vanadia
solution promotes the increasing of the low frequency impedance
by almost 1.4 orders of magnitude compared to the bare Al alloy and
other vanadia coating conditions. The reduction of impedance reveals
the deterioration of the protection system. The shift of phase angle
towards zero at very lowfrequency (Fig. 8b) for the uncoated samples
and the samples coated with 30 g/l indicating the occurrence of the
localized corrosion. Conversely, the samples coated with 10 g/l
vanadia showed a stable phase angle at low frequency conrming
the resistance to localized corrosion. The resistance and capacitance
values associated with the vanadia-coating prepared in 10 g/l vanadia
solution reect good barrier properties, associated with the imped-
iment of the electrolyte to reach the metallic substrate.
Based on EIS results and microscopic examination, the treatment
of AA2024 with vanadia at low concentration (10 g/l) improves the
resistance to localized corrosion due to the formation of the protective
vanadia rich oxide lm which acts as a barrier to prevent the oxygen
diffusion to the metal surface and therefore, impede corrosion but not
prevent it as conrmed by microscopic examination. Because the lm
formed is relatively thin about 1 to 1.5 m (Fig. 9), general corrosion
(but not the dangerous localized corrosion) increased due to diffusion
of chloride ions through these lms (Figs. 26). Moreover, treatment
with 10 g/l vanadia solution plays an important role in inhibiting the
active surface sites by blocking and repairing the micro-cracks and
pits (Figs. 25).
3.3. Cyclic voltammetry
Cyclic voltammetry (Fig. 10) was used to evaluate the pitting
corrosion resistance of the AA2024 samples treated with vanadia after
immersion in 3.5% NaCl solution. Generally, the results of cyclic
voltammetry of the vanadia treated samples conrmed the previous
results of EIS and microscopic examination. The samples coated with
10 g/l vanadia solution showed the smallest loop area which means
that such treatment offered the best resistance to pitting corrosion. On
the other hand, the other vanadia treated samples showed also
acceptable localized corrosion resistances compared with the
uncoated samples but still less than the resistance obtained from
10 g/l vanadia solution. This can be explained by the fact that the
surface resistance obtained from EIS data is the summation of pitting
and general corrosion resistance and conrms why the samples
treated with 10 g/l vanadia solution showed a marked corrosion
resistance compared with the other pretreatment conditions.
4. Conclusion
1. Surface treatment of AA2024 with vanadia at lowconcentration is a
promising method for improving localized corrosion resistance.
2. Based on the surface examination, EIS and polarization measure-
ments, treatment of Al substrate with 10 g/l vanadia solution plays
an important role in inhibiting the active surface sites by blocking
and repairing the pits.
3. Improving the localized corrosion resistance through a simple
technique that based on surface treatment in a very diluted vanadia
solution seems to have a very promising industrial approach in
many strategic applications such as automotive and aerospace
industries taking into account that these vanadia coatings would be
only a pre-treatment trying to provide a self-healing functionality,
and a nal top coat will be crucial to reach an adequate corrosion
protection.
0 40000
0
10000
20000
30000
40000
50000
a
b
-
Z
'

[
o
h
m
]
Z' [ohm]
as polished
V 10 @ pH 7
V 30 @ pH 7
V 50 @ pH 7
-2
-10
0
10
20
30
40
50
60
70
80
90
log (frequency) [Hz]
-

p
h
a
s
e

[
d
e
g
r
e
e
s
]
as polished
V 10 @ pH 7
V 30 @ pH 7
V 50 @ pH 7
10000 20000 30000 50000 60000
-1 0 1 2 3 4 5
Fig. 8. a. Nyquist plots and b. Bode plots for uncoated and vanadia coated AA2024
samples after seven days of immersion in 3.5% NaCl solution.
1676 A.S. Hamdy et al. / Thin Solid Films 520 (2011) 16681678
Acknowledgments
This project was funded through an Alexander von Humboldt
Research Award for Experienced Researchers granted to Dr. Abdel
Salam Hamdy. The authors would like to thank Dr. Hartmann, Max
Planck Institute of Colloids and Interfaces, Germany, for his guidance
with the SEM-EDS surface examination.
The authors would also like to thank Center of Research Excellence
in Corrosion, King Fahd University of Petroleum & Minerals, Dhahran
31261, Saudi Arabia, for funding the participation of Dr. Abdel Salam
Hamdy in the 38th International Conference on Metallurgical Coatings
and Thin Films, May 2010, San Diego, CA, USA.
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Energy (keV)
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counts
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