Progress in Organic Coatings 57 (2006) 307313

Adhesion performance of an epoxy clear coat on aluminum alloy in the presence of vinyl and amino-silane primers
M. Mohseni a, , M. Mirabedini b , M. Hashemi b , G.E. Thompson c
b

Amirkabir University of Technology, Polymer Department, P.O. Box 15875-44132, Tehran, Iran Iran Polymer & Petrochemical Institute, Colour & Surface Coatings Department, P.O. Box 14965-115, Tehran, Iran c Corrosion & Protection Centre, School of Materials, The University of Manchester, M60 1QD, UK Received 26 December 2005; received in revised form 9 August 2006; accepted 4 September 2006

Abstract The inuence of amino and vinyl-silane-based treatments on the performance of an epoxy coated AA 1050 aluminum has been studied. The surface energy of the silane treated samples was determined using static contact angle measurement. Chemical interactions between the silane layer and aluminum substrates were also examined using FTIR-ATR spectroscopy. Pull-off adhesion was used under wet, dry and recovery conditions. The contact angle measurements showed a relative increase in the surface free energy of the silane treated specimens. For specimens treated with silane solutions below the IEP of aluminum, adhesion strengths were higher than those for pHs higher than IEP. This may suggest that an acidbase interaction occurs between the negatively charged silanol species and the positively charged AA surface. FTIR revealed two modes of interaction, one between silane and Al3+ (SiOAl), and the other indicative of a siloxane network (SiOSi). Thickness measurement showed that the silane layer is 100200 nm thick indicating that the silane formed at the surface is not a monomolecular layer. Direct pull-off adhesion measurements of silane treated samples showed a signicant improvement in initial bond strength compared with degreased aluminum substrates. However, those silane solutions having pHs higher than 8.4 showed inferior adhesion in comparison to those having lower pHs. The adhesion improvement was maintained, to some extent, after exposure to salt spray cabinet. In spite of good dry, wet and recovery adhesion, silane treated surfaces are not comparable with chromated AA aluminum in terms corrosion resistance. 2006 Elsevier B.V. All rights reserved.
Keywords: Silane treatment; Adhesion strength; Aluminum; Surface free energy; Wettability

1. Introduction Adhesion is one of the key phenomena in obtaining good mechanical and other physico-chemical properties of coating materials. It is generally believed that there are six mechanisms involved in adhesion process [1], with the most important adsorption theory stating that for good adhesion, intimate contact must present at the interface between the coating and the substrate. To achieve this, the secondary forces, such as Van der Waals or other types of interatomic or intermolecular interactions, e.g. hydrogen bonding and acidbase interactions, represent the major driving forces. The rst law of adhesion explained by the adsorption theory, state that the surface free energy of the substrate compared with that of the coating material should be sufciently high for the contact angle of the

two phases to tend to the lowest possible value. This leads to spontaneous wetting, rendering the work of adhesion positive. This may be mathematically expressed by the Young equation [2]: WA = 1 + 2 12 = (1 + cos )1 where is the contact angle, 1 the surface free energy of the liquid coating, 2 the surface free energy of the substrate and 12 is the interfacial surface tension. This equation is generally applicable to cases where two bodies are brought into contact. In cases where a third material, such as a liquid (e.g. water), is involved, the work of adhesion can be expressed as [3]:
e d d = 2[l (1 l ) WA 1/2

(1 l )
p p 1/2

p p 1/2

d d ( 2 l ) 1/2

1/2

(2 l )

p p 1/2

+ (1 2 )

d d + (1 2 )

Corresponding author. Tel.: +98 21 64542441; fax: +98 21 66468243. E-mail address: mmohseni@cic.aut.ac.ir (M. Mohseni).

d and where l is the surface free energy of the third phase; ld , 1 d 2 are the dispersive part of the surface free energy of phases

0300-9440/$ see front matter 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.porgcoat.2006.09.007

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Fig. 1. Simplied schematic of bonding mechanism between silane molecules and metal surface hydroxide layer: (a) before condensation: hydrogen-bonded interface and (b) after condensation: covalent-bonded interface [15].

whereas l , 1 and 2 being the polar part of the surface free energy phases. Calculating the theoretical work of adhesion in the presence of water, for metallic surfaces coated by organic coatings, gives rise to negative values of the work of adhesion, indicating that the adhesive strength does not appear to be stable and that the secondary forces may not be sufciently strong when the coated substrate is exposed to water. This implies that the bonding between the coating and substrate at the interface should be reinforced through chemical interactions. Pretreatment of aluminum through different procedures, such as chromating, phosphating, use of polymeric materials or other processes in which chemical interactions may occur at the interface is one of the obvious reasons why such pretreatments have commercial interest. Currently, environmental concerns impose new regulations on the use of carcinogenic compounds such as hexavalent chromium, the toxicity of which is well documented [46]. Many alternative treatments, such as silane-based adhesion promoters, have been introduced as potential replacements for chromium-based pretreatments [712]. The variability of adhesion promoters in terms of their chemistry, together with their potential to react with both aluminum and coating materials, have led to the wide use of these compounds today. Organo-functional silanes, which are known as adhesion promoters, can be employed to improve the adhesion of organic coatings to the aluminum surface. These adhesion promoters contain various functional groups, including amino, epoxy, vinyl and alkyl groups [1315]. Due to their bifunctionality, the silane bonding agents are capable of forming chemical bonds with active sites on the substrate and with the corresponding reactive groups of the binder molecules [16,17]. In this way, stable, high-energy coupling takes place between the substrate and the coating. Silanes are therefore classed as chemically active bonding agents. A proposed bonding mechanism of silanes to metal surfaces is shown schematically in Fig. 1 [18]. When a metal is immersed into a dilute silane solution (e.g. 25 vol.%) for a few seconds,

silanols (SiOH) in the silane solution adsorb spontaneously onto the surface through hydrogen bonds (Fig. 1(a)). Upon drying, two key condensation reactions occur at the silane/metal interfacial region. SiOH groups from the silane solution and the metal hydroxyls (HOSub ) from the metal surface hydroxide form covalent metallo-siloxane bonds (3). Excess SiOH groups, adsorbed on the surface, also condense to form a siloxane, SiOSi, lm (2). The as-formed SiOSub and SiOSi covalent bonds are assumed to be responsible for the excellent bonding of the silane lm to the metal substrate. The mechanism of adhesion is based on siloxane formation over the substrate surface, which is anchored by chemical bonding. In this study, the inuence of two types of silane-based treatments, namely amino and vinyl-silane on the adhesion properties and corrosion performance of an epoxy coated 1050 aluminum substrate is examined. 2. Experimental 2.1. Materials AA 1050 aluminum alloy sheets, 0.5 mm thickness, were supplied by Arak Al Co. Amino-propyl trimethoxy silane and vinyl trimethoxy silane were obtained from Degussa. A 100% solid epoxy clear coat, cured with polyamine hardener, was supplied by Saman Chemical Co. All other common chemicals were of analytical grade purity. 2.2. Solgel coating system Before application, the OR groups of the silane were transformed to active SiOH groups for the subsequent condensation reactions. The transformation is usually realized by hydrolyzing the silane in a dilute aqueous solution. Thus, a 2 wt.% silane solution was prepared by adding the silane to a mixture of 4:1 ethanol and distilled water. The solutions were stirred for 10 min.

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Preliminary room temperature surface cleaning of the aluminum samples (Q-panel size) involved immersion in a nonionic detergent at 4045 C for 5 min, followed by immersion in acetone for 10 min at room temperature. The third step involved etching in 5 wt.% NaOH solution with low agitation at 5055 C. The nal step was an immersion in 20% HNO3 solution for 3 min at room temperature (desmutting) [12]. The samples were then pretreated in 2 wt.% silane solution for 2 min. The pH of amino-silane solution was adjusted at 7.5 and 9 and that of vinyl-silane to 5 and 10. The initial pH values of amino and vinyl-silane were 10.5 and 6, respectively. The silane treated samples were then cured for 24 h at room temperature in a dust free chamber. In order to compare protection afforded by the solgel surface treatments and chromate conversion coatings, the panels were coated with Alodine 1200 chromate conversion coating [12]. A clear epoxy coating was used throughout this study for evaluation of corrosion protection performance. The clear coating was applied using a lm applicator at ambient temperature and 50% relative humidity. Panels were allowed to cure for 14 days prior to examination. The thicknesses of the cured coated samples were measured using an Elcometer 345 instrument to an accuracy of 0.1 m, with measurements carried out on a set of ve replicate samples. The coating thicknesses varied from 28.8 to 31.4 m. 2.3. Static contact angle measurements For determination of the surface energy of the treated AA 1050 alloy substrates, selected test liquids, with different values of sl for a common solid, depending upon the dispersion and dipolar interactions of the liquids, were utilized. For reliable determination of the surface energy, different test liquids as indicated in Table 1 are usually preferred. A KRUSS G2/G40 contact angle measuring system was employed. The treated alloys were located on the sample holder and each test liquid (0.05 ml) was then placed on the sample using a syringe. The angle between the baseline of the drop and the tangent at the drop boundary was measured, using a direct reading goniometer telescope, with a magnied image of the droplet displayed on a screen. The measurement was accomplished after a period of about 60 s. 2.4. FTIR spectroscopy A BRUKER FTIR-ATR spectrophotometer was employed. The alloys, treated with a 20% silane solution at two different pH
Table 1 Surface free energies of the test liquids Liquid Water Formamide Ethylene glycol 1,5-Pentanediol Benzyl alcohol
d lv

values, were analyzed in a reection-absorbance spectroscopy attachment; this included four scans, with a resolution of 8 cm1 . 2.5. Adhesion measurements Pull-off adhesion testing of the coating was performed according to the procedure described in ASTM D 4541. The dollies of 20 mm diameter were glued to the surface of the coated panels with a cyano-acrylate adhesive. After curing, the xture was loaded and the joint strained a constant rate of 5 mm/min with a pull-off tester (Erickson Model 525) until a plug of the coating material had detached from the alloy surface. For each test, ve replicate samples were employed, with the average value quoted. The adhesion strength of the coated specimens in the presence of water (wet adhesion) was measured after 1000 h exposure of the specimens in a humidity cabinet. 2.6. Accelerated tests Corrosion resistance of the coating was accomplished using the procedures described in ASTM B 117, salt spray, and ASTM D 2247, humidity exposure. A 5 wt.% NaCl solution was used for the salt spray. Treated samples (with and without coatings) were placed in a standard salt spray chamber for 1000 h at 35 1.5 C. Visual assessment of the macroscopic surface and the scribed regions were made for the presence of any corrosion, blistering, softening and other lm defects. 3. Results and discussion Adhesion promoters can be employed in adhesive joint by different methods including: (i) substrate surface treatment prior to applying the coating, (ii) reactive intermediates for modication of base polymer and (iii) additives that are integrally blended in the coating formulation. In here the rst approach has been selected. It is believed that the chemisorption of silane compounds is provided the mechanism by which the adhesive performance of coatings to its substrate can be explained [19]. One of the factors inuencing the performance of the silane compounds as primer is the pH of the solution applied to the substrate [19,20]. The surfaces of metal and metal oxides are made up of hydrated hydroxyl groups in equilibrium with atmospheric moisture. An electro-kinetic surface potential is imposed on these surfaces in aqueous environment as a function of H+ and OH ion concentrations. This potential is called zeta potential. The pH at which the zeta potential of a surface is zero is known as the isoelectric point of the surface (IEP). In an aqueous medium of pH higher than the IEP, the surface will be anionic while, at lower pH, it will be cationic. Table 2 shows the result of contact angle measurement of differently applied silane solutions on aluminum alloy using different test liquids. Based on the contact angle measurements, the corresponding free energy of the surface has been calculated by means of the OwenWendt method [21], in which the polar and dispersive parts of the surface free d )1/2 verenergy are obtained by plotting the (1 + cos )l /2(1 sus (1 )
p 1/2 d) /(1 1/2

lv 51.0 18.7 21.3 15.7 8.7

lv 72.8 58.2 47.7 43.3 38.9

21.8 39.5 26.4 27.6 30.3

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M. Mohseni et al. / Progress in Organic Coatings 57 (2006) 307313 Table 3 Dry, wet and recovery adhesion strengths (kPa) of silane treated AA 1050 alloy Pretreatment (mJ/m2 ) Etched and desmutted Chromated 0.5% Amino-silane 1.0% Amino-silane 2.0% Amino-silane 0.5% Vinyl-silane 1.0% Vinyl-silane 2.0% Vinyl-silane STD: standard deviation. Adhesion strength (kPa) (STD) Dry 652.8 (88.4) 1400.6 (78.0) 1373.6 (102.0) 1506.9 (109.2) 1792.2 (57.2) 1379.3 (88.0) 2413.2 (119.0) 2758.9 (158.0) Wet 453.2 (97.2) 1142.0 (77.2) 816.0 (66.4) 1378.0 (81.0) 1509.6 (58.4) 689.5 (77.0) 1550 (75.0) 1369.4 (112.0) Recovery 612.0 (68.0) 1210.1 (147.2) 965.0 (142.8) 1400.6 (61.2) 1536.9 (90.4) 1241.2 (126.0) 1327.0 (116.0) 2068.5 (102.0)

Table 2 Surface energy values and critical surface free energies of treated AA 1050 alloy Pretreatment Owens surface free energy p Untreated Acetone degreased Etched and desmutted Chromate treated Amino-silane treated (pH 7.5) Amino-silane treated (pH 9.0) Vinyl-silane treated (pH 5.0) Vinyl-silane treated (pH 9.0) 1.5 12.6 23.9 31.0 44.85 28.15 28.99 10.99 d 21.3 20.0 12.1 19.6 7.83 19 27.83 27.86

22.8 32.6 36.0 50.6 52.68 47.15 56.82 38.85

The slope of the tted line and the intercept give (s ) d )1/2 respectively. Table 2 shows that the polar and disand (s persive components of the surface free energy of amino and vinyl-silane treated surfaces are different. The isoelectric point of aluminum is about 8.7. The natural pH of amino-silane is 10.5, while that of vinyl-silane is 6.5. As revealed in Table 2, the surface treatment of the AA 1050 alloy using silane primers has considerably increased the surface free energy of substrate compared with that of desmutted surface. The results in Table 2 reveal that there are differences in surface free energy of silane treated surface above or below the IEP. The silane compound is more likely to contain negative SiO species upon hydrolysis. For the amino-silane at pH 7.5 (which is lower than the pH of IEP), the tendency of negatively charged silanol groups to react with the positively charged surface appears more probable. This leads to an orientation of silane compound through silanol groups at the interface. As the pH of the treatment bath is adjusted towards 7.5, the aluminum becomes less negative while the amine functionality of amino-silane becomes more positive. Below the IEP of the AA 1050 alloy also becomes more positive and repels the amino, causing right-side up orientation [19,20]. A similar observation is made for vinyl-silane solutions in which the surface free energy of treated surface at pH 9 is lower than that of those adjusted at pH 5. On the other hand, with increase of the pH of the silane compound to alkaline region, the rate of condensation of silanols tends to increase while the rate of hydrolysis is more probable at acidic pH. It appears that the IEP can be regarded as an important factor by which the orientation of silane is made. The results in Table 2 also show that the dispersive component of surface free energy of amino-silane treated surface has increased from 7.83 to 19 mJ/m2 , while that of polar component has decreased from 44.85 to 28.15 mJ/m2 . This has led to a lower total free energy of surface at pH 9 at which the dominant charge of the surface is negative, therefore giving rise to less adsorption of silanol at the interface and a more ready condition for the formation of a siloxane bond at the surface. For vinyl-silane the dispersive part of the surface free energy has not changed considerably compared with the polar part at the two studied pH values employed, suggesting that adsorption on the surface has occurred through the silanol groups. The higher pH values, as indicated above, prevent the adsorption due to the surface being more negatively charged. The surface free energy of aluminum treated with vinyl-silane is slightly higher

p 1/2

than that of amino-silane treated surface at pH 5 (56.82 mJ/m2 versus 52.68 mJ/m2 ). As the treating bath pH is adjusted to values above the IEP, the orientation of silanol groups at the surface is more probable. Amino-silane may also exist in water as internal zwitterions [19]. Thus the interaction of positively charged protonated amine with negatively charged silanols is a plausible case. Film of amino-silane at the natural pH is composed of highly hydrolyzed oligomers. Results in Table 2 also show that the surface free energy of vinyl-silane solution at pH 9, which is higher than the IEP of aluminum, is close to the surface free energy of desmutted surface. This can be explained by the orientation of negative silane groups at the surface being enhanced at this pH value, and that the difference between this pH and the natural pH of the starting silane solution is sufciently high to drive the condensation process to completion. These observations reveal that the interaction of silane adhesion primers can be regarded as an acidbase interaction in which a more acidic surface is reacted with the more basic species of silanol at pHs below the IEP. The increased surface free energy of silane treated substrates has been examined through the adhesive behavior of the epoxy coated AA 1050 alloy. The results of pull-off adhesion testing are summarized in Table 3 and shown graphically in Fig. 2. The adhesion strength of etched and desmutted substrates, as well as chromated surfaces, is also given in Table 3 and Fig. 2. The adhesion strength of the differently prepared surfaces reects the conditions at which silane was applied to the alloy, i.e. with different concentrations of treating bath (0.5, 1 and 2 wt.%) and pH values above and below IEP. As the adhesive joint may be inuenced by the presence of water and humid conditions, adhesion was also measured at three conditions, namely dry, wet and recovered. The dry adhesion corresponds to the samples examined 2 weeks after the epoxy clear coat was applied, while the wet and recovery adhesion were performed immediately after 1000 h exposure to salt spray cabinet and 24 h after the panels were removed from the cabinet respectively. From Fig. 2, the adhesion strength of epoxy coated samples show an increase in the presence of silane pretreatment at all concentrations used and for both silane compounds. The increase in adhesion can be explained by the relative increase in surface free energy of the substrates compared with the blank sample without any chromating or silane treatment. There are interesting points to be discussed for the data presented in Table 3 and Fig. 3.

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Fig. 2. Dry, wet and recovery pull-off adhesion of differently prepared AA 1050 alloy.

The rst is the inferior adhesion of epoxy to chromated samples compared with silane treated substrates. Although chromating has proved to be a major industrially acceptable treatment, both in terms of corrosion inhibition behavior and also on the formation of an anchor pattern through which mechanical interlocking takes place. The present data show that silane adhesion promoters outperform the chromating treatment as far as adhesion is concerned. The difference in adhesion can be attributed to the higher surface free energy of the specimens after silanization. This is considered to be the main criterion of the adsorption theory of adhesion. The higher the surface free energy of substrate the lower the contact angle of liquid coating in contact with it, therefore the higher the wetting of the substrate. Improved wetting leads to greater adhesion strength. The second point is the ability of hydrolyzed bonds at the interface to recover after exposure to wet conditions. 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 humid atmosphere. This is the reason chemisorption

Fig. 3. FTIR-ATR spectra of amino-silane treated sample. (a) Desmutted sample, and treated samples at (b) pH 7.5 and (c) pH 9.

may be preferred at the interface. With stronger bonding, such a covalent bonds between the adhesive and adherend, compared to weaker bonds, such as hydrogen or Van der Waals bonds, probably act to increase the strength of the interface. The observations from Fig. 3 reveal that the interaction of epoxy to silane treated samples cannot be considered as a simple physic-sorption on the surface, rather a stronger chemical interaction through corresponding functional groups and also the bonded interface can be recovered after its exposure to humid condition. The third point is that the concentration of silane solution may also affect the adhesion strength. All specimens reported in Fig. 2 are associated with pH regions below the IEP of the AA 1050 alloy (pH 5 for vinyl-silane and pH 7.5 for amino-silane). The difference in adhesion may be attributed to the condensation of neighboring silanols present in the solution as the concentrations change. Concentrations less than 0.5 wt.% were difcult to analyze by FTIR-ATR spectroscopy. Increased concentrations, however, gave rise to microscopic cracks upon drying. This may correspond to the inability of the lms to relax due to stress concentration. The lms were 200350 nm thick, as revealed from cross-sectioned specimens. Therefore, the 0.52 wt.% concentrations were suitable for further study. However, the lower the percentage of silane in the solutions, the lower the impact on adhesive strength of epoxy to the substrate, probably due to the weaker boundary layer low molecular weight siloxane network formed at the interface. The greater surface free energy of the vinyl-silane treated specimens also showed higher adhesive (Fig. 2). This probably corresponds to improved wetting of this silane compared to amino-silane. Hydrolysis of silane solutions prior to application on the surface and subsequent reaction at the interface are the main role of these adhesion promoters. To conrm the data presented above, FTIR-ATR spectroscopy was used to study the functional groups present at the surface of silane lms as well as at the interface. Low concentrations of silane solution (less than 0.5 wt.%) did not give rise to distinct FTIR spectra due to the very thin layer of silane. Increased concentrations, on the other hand, were found

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to give relatively thick layers that cracked during lm formation, as mentioned previously. Fig. 3 shows typical FTIR-ATR spectra of an amino-silane primer together with the spectra of desmutted and etched samples. The spectra of the silane primed AA 1050 alloy show two chemical interactions, one between the silane layer and the aluminum surface (SiOAl) with an absorption band located at 9001000 cm1 [11,16,17,22]. The band near 10751100 cm1 can be assigned to the SiOSi stretching mode, indicating that some of the silanols have condensed to form polysiloxane [22,23]. The bands appear at 1580 cm1 may be assigned to NH2 deformation modes in amino group that were strongly hydrogen bonded to anionic groups. The weak bands at 1600 cm1 corresponds to polysiloxane in which the amino groups form cyclic [24,25] internal zwitterions with silanol groups. These observations are in agreement with results obtained in adhesion and contact angle measurement data which suggest that silane adhesion promoters increase the surface free energy and consequently increase the adhesion strength. This has been accomplished through the formation of primary covalent bonding between silane and AA 1050 alloy. Finally, the behavior of silane treatment was studied in salt spray cabinet. Table 4 shows the visual observation made for two silane solutions at the pH values below and above the IEP of surface. From Table 4, the desmutted surface leads to corrosion. The alloy appears dark after exposure to the humid environment. Aluminum is hydrated in aqueous conditions. Exposure of Al in wet conditions will form aluminum hydroxyl species. Corrosion of Al may be due to the presence of Fe and Si impurities. Once corrosion started, Al becomes anode and Fe and Si become cathode. Results in Table 4 indicate that only specimens that survived 1000 h exposure to salt spray cabinet was chromated. This means that the corrosion resistance of silane treated samples is inferior to chromating, but better than the desmutted samples. The main reason may be the dissolution of silane from the interface when exposed to humid and aggressive atmosphere. This observation contradicts with adhesion measurement studies. It was shown that adhesion of epoxy to silane treated surface is superior to chromating samples. This discrepancy may suggest that although adhesion promoters enhance the adhesive bonding of epoxy to Al, their presence do not presumably account

for the corrosion inhibition, mainly because the dissolution of chromating treatment is less than that of silane treatment in wet conditions. This reasoning seems to be less applicable to chromated samples. Therefore, the introduction of silane as adhesion promoter may be benecial in terms of adhesion, both in dry and wet environment, but not necessarily benecial in terms of corrosion inhibition. The lower resistance of amino-silane treatment compared to vinyl-silane may be corresponded to the formation of protonated amine salts, which are soluble in water, reducing the ionic resistance of coating system [25]. 4. Conclusions The purpose of this article was to study the behavior of two silane adhesion promoters to be applied on AA 1050 aluminum in the presence of an epoxy clear coat. The wettability of the AA 1050 alloy was found to increase using the silane-based treatment, with the surface becoming more hydrophilic. FTIR results show two chemical interactions; one is between the silane layer and the aluminum oxide surface and the other is the siloxane network. Pull-off test results showed a clear increase in the adhesion strength of epoxy-based lacquer for aluminum samples. The increase in adhesion was more profound at pHs below the IEP of surface in which the surface tends to be more positively charged. The increase of adhesion strength and surface energy measurement results conrms the effectiveness of silane treatment in improving the wettability characteristics and adhesion properties. Corrosion behavior of epoxy coated aluminum treated with silanes, however, is not as good as chromated surface. References
[1] A.V. Pocious, Adhesion and Adhesive Technology, An Introduction, Hanser Publication, New York, 1997. [2] T. Yong, Trans. R. Soc. 95 (1805) 65. [3] A.J. Kinloch, W.A. Dukes, R.A. Gledhill, in: L.H. Lee (Ed.), Adhesion Science and Technology, Plenum Press, New York, 1975. [4] N.I. Sax, Dangerous Properties of Industrial Materials, Van Nostrand Reinhold Company, New York, 1979. [5] W.J. Van Ooij, D. Zhu, Corrosion 157 (2001) 411. [6] W.J. Van Ooij, D. Zhu, G.P. Sundararajan, S.K. Jayaseelan, Y. Fu, N. Teredesai, Surf. Eng. 16 (2000) 386. [7] T. Schram, G. Goeminne, H. Terryn, W. Vanhoolst, P. Van Espen, Trans. I. M. F. 73 (1995) 91. [8] J. Comyn, Adhesion Science, RSC Adhesion Science (RSC, Paperback Series), U.K., December, 1997. [9] W. Funk, Prog. Org. Coat. 28 (1996) 3. [10] S.M. Mirabedini, J.D. Scantlebury, G.E. Thompson, S. Moradian, Prog. Org. Coat. 46 (2) (2003) 112. [11] I. Maege, E. Jaehne, A. Henke, H.J.P. Adler, C. Bram, C. Jung, M. Stratmann, Macromol. Symp. 126 (1997) 7. [12] Melzer, U.S. Patent 5,641,542 (1997). [13] D.R. Arnott, N.E. Ryan, B.R.W. Hinton, B.A. Sexton, A.E. Hughes, Appl. Surf. Sci. 22 (1985) 236. [14] M.P. Schrieever, U.S. Patent 5,551,994 (1996). [15] I. Danilids, J.M. Sykes, J.A. Hunter, G.M. Scamans, Surf. Eng. 15 (1999) 401. [16] O. Kachurina, T.L. Metroke, E. Stesikova, E.T. Knobbe, J. Coat. Technol. 74 (2002) 43.

Table 4 Appearance of epoxy coated lms in absence and the presence of silane primer after 1000 h exposure to salt spray test Sample Desmutted Chromated Vinyl-silane (pH 5) Vinyl-silane (pH 9) Amino-silane (pH 7.5) Amino-silane (pH 9) Appearance Very dark deposits rapidly formed around scribe severe blisters all over the surface No visual change Blistering around scribed area-white deposits in no-scribed area Sever blistering-delamination of lm around scribed Black and yellow depositswhite deposits all over the surface Blistering-black and white deposits after 24 h of exposure

M. Mohseni et al. / Progress in Organic Coatings 57 (2006) 307313 [17] P. Walker, in: A.D. Wilson, J.W. Nicholson, H.J. Prosser (Eds.), Surface Coating-1, Elsevier Publishers, London, 1987 (Chapter 6). [18] S. Wernick, R. Pinner, P.G. Sheasby, The Surface Treatment and Finishing of Aluminum Alloys, Finishing Publications, U.S.A., 1987. [19] E.P. Plueddemann, Silane Coupling Agents, Plenum Press, New York, 1982. [20] F.J. Boerio, J.W. Williams, Application of Surface Science, vol. 7, North Holland Publishing Company, Amsterdam, 1981.

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[21] D.K. Owens, R.C. Wendt, J. Appl. Polym. Sci. 13 (1969) 1740. [22] D. Zhu, W.J. Van Ooij, Corros. Sci. (2003) 2177. [23] F.J. Boerio, Infrared spectra of polymers and coupling agents absorbed onto oxidized aluminum, Polym. Preprint 21 (1981) 297298. [24] T. Child, W.J. Van Ooij, Coat. World (March) (1999) 4253. [25] B.G. Tilset, A. Bjorgman, F. Lapique, C.J. Simensen, Sintef Materials Technology, SIP Seminar, 2002.