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Corrosion Science
journal homepage: www.elsevier.com/locate/corsci
Polymer Engineering Department, Amirkabir University of Technology, P.O. Box 15875-413, Tehran, Iran
Colour, Resin & Surface Coatings Department, Iran Polymer and Petrochemical Institute, P.O. Box 14965-115, Tehran, Iran
a r t i c l e
i n f o
Article history:
Received 11 August 2009
Accepted 6 February 2010
Available online 14 February 2010
Keywords:
A. Aluminium
B. EIS
B. IR spectroscopy
B. SEM
C. Polymer coatings
a b s t r a c t
The inuence of various blends of hexauorozirconic-acid (Zr), polyacrylic-acid (PAA) and polyacrylamide (PAM) pretreatment on the performance of an epoxy coated aluminium substrate was investigated
and compared to that of a so-called chromate/phosphate conversion coating (CPCC).
Adhesive-strength of epoxy coated substrates was evaluated using pull-off and tape tests. Salt spray,
humidity chambers and EIS were employed to characterize corrosion performance of coated substrates
with different initial surface pretreatments. Among the Zr-based formulations, PAA/Zr and PAA/PAM/Zr
showed the best adhesion strength, while the later revealed a good corrosion performance as well. However, CPCC pretreated sample was still superior in these aspects.
2010 Elsevier Ltd. All rights reserved.
1. Introduction
Aluminium and its alloys are widely used because of their some
what unique properties, such as lightweight, relative low toxicity
and a fair corrosion resistance [1,2] and the surface pretreatments
play an important role in the protection of aluminium and aluminium alloys [3]. Although the aluminium surface naturally covers
with an air-formed oxide lm, about 23 nm, it is an insufcient
barrier for moderately long-term corrosion prevention of the
underlying substrate. The mentioned oxide-lm covered aluminium is attacked in certain environments, even after being further
coated by an organic protective coating [4].
Consequently, chemical conversion coatings are applied to aluminium to improve corrosion resistance and/or to establish a base
for subsequent application of organic coatings. Conversion coatings
on aluminium and its alloys are generally performed in solutions
containing chromate and uoride ions [1]. The coating usually
develops in the presence of uoride ions, which involves a cathodic
reduction of Cr(VI) to Cr(III) together with the evolution of hydrogen. Chromium-based treatments have been used widely with
good anti-corrosive performance, but the toxicity and carcinogenic
nature of hexavalent chromium are well documented [5]. Thus,
several alternative treatments, including zirconium- or titaniumcontaining processes, or thin layers of polymeric materials, have
been introduced [1,613].
* Corresponding author. Tel.: +98 21 4458 0040; fax: +98 21 4458 0023.
E-mail address: m.mirabedini@ippi.ac.ir (S.M. Mirabedini).
0010-938X/$ - see front matter 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2010.02.014
1949
that hot water treated, PAA and CPCC pretreated samples provide
the highest surface free energies. Comparison of these results with
adhesion strength measurements showed that good wettability is
an essential factor in achieving relatively good dry adhesive joints,
however; this cannot be considered to be a sufcient reason for
high bond strengths achieved in practice.
In a further study [20], Zr and PAA were selected to provide a
chrome-equivalent corrosion protection as well as to facilitate
the adhesion of a polyester/epoxy powder coating. Experimental
results revealed that adhesion of an aluminium substrate in the
presence of a polyester/epoxy coating had indeed improved by a
PAA/Zr based pretreatment and a chromate-based equivalent corrosion performance was achieved [20].
The main purpose of the present study was to evaluate the
interaction between PAA, PAM and Zr on an 1050 aluminium alloy
surface. Additionally, the effect of different composition of PAA/
PAM/Zr pretreatments on the adhesion strength and corrosion protection performance of a clear epoxy coating on the aluminium alloy were also studied.
2. Experimental
2.1. Materials
Aluminium alloy (1050) was supplied by Arak Al Company as
0.5 mm thick sheets in H18 temper. PAA (average molecular
weight: 104,000) as a 63% solution in distilled water, and carboxyl
modied PAM (average molecular weight: 200,000) were both
supplied by ACROC Organic (Fisher Chemicals). Hexauorozirconic
acid was obtained from Aldrich Chemicals Company as a 45% solution in distilled water.
Aluminium oxide powder with an average particle diameter of
0.1 lm was purchased from Merck Company. Epikote 1001, epoxy
clear coat, and its hardener, Ardur115 polyamide were supplied by
Shell Company. All chemicals used in this study, were of analytical
grade having high percentages of purity.
2.2. Sample preparation
Preliminary surface cleaning was carried out in acetone using a
soft brush. For chemical etching, the specimens were immersed in
a 5 wt.% solution of NaOH for 3 min at 50 C followed by washing
with distilled water. For desmutting of etched aluminium surfaces,
the specimens were then placed for 1 min in a 50% v/v solution of
nitric acid in water were then subsequently washed with distilled
water, and dried for 1 h at 50 C. The samples were then treated by
immersion in a solution of different combined weight percentages
of PAA, PAM and Zr at 20 1 C for 3 min.
Taguchi statistical analysis method was employed to optimize
the number of pretreatment solutions shown in Table 1. The specimens were then allowed to dry under ambient temperature. Postheating treatment was carried out in an oven at 145 C for 20 min.
For comparison purposes, a chromate/phosphate conversion coating (CPCC) solution was also used; the treatment involved the Alodine procedure [1], with a specic immersion time of 5 min.
Table 1
Pretreated samples with different combinations of PAA, PAM and Zr.
Treatment no.
PAA
PAM
Zr
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
0.0
0.0
0.0
0.0
0.5
0.5
0.5
0.5
1.0
1.0
1.0
1.0
2.0
2.0
2.0
2.0
0.0
0.5
1.0
2.0
0.0
0.5
1.0
2.0
0.0
0.5
1.0
2.0
0.0
0.5
1.0
2.0
0.0
0.05
0.1
0.2
0.5
0.0
0.2
0.1
0.1
0.2
0.0
0.05
0.2
0.1
0.05
0.0
The number of pretreatment solutions were used are emphasized (bold) in Table 1.
Table 2
Mixture compounds for FTIR analysis.
No.
Combination
1
2
3
4
5
PAA + Al2O3
PAM + Al2O3
PAM + Zr
PAA + Zr + Al2O3
PAA + PAM
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ACOOH H2 O $ ACOO H3 O
In the FTIR spectrum of mixture of PAM and H2ZrF6, Fig. 1C, due
to the dipole moment in the carbonyl group and the resonance effect of nitrogen, an absorption band in the region 16001700 cm1
was observed. Additionally the CO stretch band at 1270 cm1 has
disappeared from the spectrum of mixture compounds with
H2ZrF6. The disappearance of this band and the presence of an
adsorption band at 830 cm1 occur when acrylic acid reacts with
a ourozirconate compound. Applying polymers in combination
with a zirconium compound has been claimed to cause cross-linking at the aluminium surface [1].
1951
Table 3
FTIR assignments.
No.
Functionality
1
2
3
4
5
6
7
8
9
10
11
33002200
17251700
1557
1456
1417
1275
1106
35002500
16001700
14161457
1262
OH (acid)
COO (acid)
Acid salt. Ionized form
CH2
CHCO
OCOH (dimmer)
OCOH (dimmer)
NH2 (two peaks)
CNH2
NH2
CN
1952
Table 4
Visual observations of samples during 1000 h humidity test.
Table 5
Visual observation of samples during 1000 h salt spray test.
Treatment
no.
Treatment
no.
4
10 and 13
16
CPCC
4
10 and 13
16
CPCC
attacks the polymer at the interface between the polymer and the
substrate.
With increased immersion time, the radius of the high frequency semi-circle (Fig. 4C and F) is rapidly decreased, suggesting
that the barrier properties of the coating is progressively decreased, and the corrosion rate continues to increase to the end
of the test.
Fig. 4 reveals that PAA-based treated samples exhibit more tendencies to negative direction. When an aluminium surface treated
with PAA is immersed in the test solution, as mentioned previously, un-reacted functional groups on the PAA polymeric chain
1953
the coating capacitance, Cc, the coating resistance, Rpf, the charge
transfer resistance, Rct, and the double layer capacitance, Cdl.
3.4. Adhesion strength measurements
The adhesion of coatings may be inuenced by and are many
factors surface pretreatments play an important role in the corrosion protection of aluminium alloys [35]. The adhesion strength of
differently treated Al samples is shown in Fig. 6. As shown in Fig. 6
the pull-off adhesion test revealed that samples Nos. 10 and 13 had
higher dry adhesion values compared with samples Nos. 4 and 16.
The adhesive strength of CPCC treated samples had an average value of 140 kg/cm2. This performance generally correlated with the
formation of an anchor pattern through which mechanical interlocking takes place.
There are indications [19,20] that good adhesion between a
high energy surface and the coating layer can occur through intimate contact between the substrate and the molecules of the coating. CPCC, PAA/PAM/Zr and PAA/Zr treated substrates have higher
surface energy than other treatments. Furthermore, as a result of
chemical interactions between PAA molecules and aluminium
oxide layer on the surface (as it is evident from FTIR spectra analysis), dry adhesion strength of epoxy coating increased
additionally.
1954
Fig. 4. Impedance spectra of epoxy clear coated aluminium substrates during 20 days immersion in 3% NaCl electrolyte.
In the dry state, all coated specimens indicated no failed regions, proving good adhesive strength. However, it is understood
that the adhesive strength of the coatings in the dry state does
1955
Fig. 5. Equivalent circuit for the epoxy coated aluminium alloy substrates.
200
Fig. 7. EDS spectra of A: sample No. 10 pretreated with PAA/PAM/Zr and B: CPCC
treated sample.
100
160
80
120
60
80
40
40
20
recognized for a long time as a poor predictor of coating performance in the presence of water or electrolyte [36].
Fig. 6 reveals that in the wet stage (immediately after one week
exposure in humidity condition), the adhesion strength of all specimens are decreased in comparison with dry stage. The main reason for failure of most organic coatings is the loss of bonding (if
any) between the coating and the substrate after exposure to the
humid atmosphere. When a coated aluminium surface is exposed
to an aqueous environment, water molecules penetrate through
the coating layer, after a certain initial period, water molecules
are accumulated in the coating/substrate interface, within the aluminium oxide layer. Mechanical interlocking or/and chemical
interactions throughout the interface may affected by this phenomenon and as a result, adhesion strength decreasing will be
detected.
For PAA-based treated samples, adhesion strength decreasing
may arise from the nature of the chemical interaction between
the treatments and aluminium surface. FTIR analysis has conrmed the conversion of carboxyl acid functional groups to carboxylate ions at the PAA/aluminium oxide interface. However, only
about 40% of the acidic functional groups on the polymeric chains
may convert to the salt form. It is proposed that steric and/or conformational hindrance, associated with the polymer backbone, prevent reaction of all carboxylic acid groups in PAA with surface
hydroxyl functionalities to form carboxylate complexes [12].
It is believed that un-reacted groups may act as weak sites at
the interface, therefore, when aluminium surface, on which PAA
based treatment was deposited, is exposed to aqueous environment, dissolution may proceed leaving little ionic or complex
interaction with the metal surface. The nal poor wet adhesion
at the local site is the result of the presence of un-reacted PAA molecules on the metal surface. These molecules may dissolve in
water, creating considerable osmotic pressures, with subsequent
increase in the water volume at the interface. This concludes to
0
No. 1
No. 4
No. 10
No. 13
No. 16
CPCC
Treatment
Fig. 6. Pull off adhesion strength of various pretreated epoxy coats on aluminium and percentage of adhesive remaining after humidity test.
1956
4. Conclusion
FTIR analysis showed that there are two possible chemical
interactions, one between PAA molecules and aluminium oxide
and the other between PAA and PAM. The rst is a purely ionic
3
giving an absorption band
interaction between COO and Al
1
around 1557 cm , and the second is related to the interactions between COO and NH
3 groups which appears as a doublet in the region 14081454 cm1. FTIR and EDS spectra indicate the formation
of a relatively thin and insoluble layer of the pretreatment on the
aluminium surface. EIS tests showed that the combination of
PAA/PAM/Zr as the pretreatment demonstrated a much better corrosion performance than other formulations even after the accelerated tests, ranked second after CPCC pretreatment.
Although the polyacrylamide component does not noticeably
increase dry adhesion strength, however, it markedly improves
the corrosion protection performance of the PAA/PAM/Zr pretreatment compared to the PAA/Zr treatment.
Acknowledgements
The authors wish to acknowledge support for the research work
reports in this paper from the Amirkabir University of Technology
and Iran Polymer and Petrochemical Institute.
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