Corrosion Science 45 (2003) 25412562 www.elsevier.

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Alteration of wettability and inhibition of corrosion in narrow aluminium 7075 gaps by thin polymer lms
O.M. Matarredona, K. Mach, M.M. Rieger, E.A. ORear
*
School of Chemical Engineering and Materials Science and Institute of Applied Surfactant Research, University of Oklahoma, Norman, OK 73019, USA Received 5 November 2002; accepted 4 March 2003

Abstract The admicellar polymerization process was adapted to deposit polystyrene (PS) and poly(methyl methacrylate) (PMMA) onto aluminium 7075 surfaces. Characterization of the lms was performed using FTIR spectroscopy, scanning electron microscopy and atomic force microscopy. Dynamic contact angles conrmed the hydrophobic nature of modied aluminium substrates. Articial crevices made from coated aluminium 7075 coupons were developed to simulate the crevices formed on aircraft. Water uptake measurements showed that PS delayed water penetration in the crevices for almost 4 h. Accelerated corrosion tests revealed the protective characteristics of PMMA. Image analysis was used to quantify the extent of corrosion in the crevice. 2003 Elsevier Ltd. All rights reserved.
Keywords: A. Aluminium; C. Crevice corrosion; C. Polymer coatings

1. Introduction Corrosion of aluminium alloys, particularly 7075 or 2024, is a critical issue for many of the United States Air Forces aging aircraft. These alloys are primarily used for their mechanical properties. However, they contain signicant amounts of copper, which makes them more susceptible to corrosion than pure aluminium. Due to political circumstances and scal constraints, the US Air Force is being forced to

Corresponding author. Tel.: +1-405-325-5811; fax: +1-405-325-5813. E-mail address: eorear@ou.edu (E.A. ORear).

0010-938X/$ - see front matter 2003 Elsevier Ltd. All rights reserved. doi:10.1016/S0010-938X(03)00084-2

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extend the working life of some of their aging aircraft eet by as much as 40 years in some cases. This could represent a serious risk if no maintenance and reconditioning processes are applied, which in many cases is a major economic eort. To guarantee full operability, these aircraft are frequently inspected for possible failure spots throughout the entire structure. After inspection, the damaged pieces need to be repaired or replaced. If minor deterioration due to corrosion is found, the usual procedure is to polish or sand the corroded area. However, this can only be done down to a certain thickness to avoid weak spots and thus further stress failure. For more severe corrosion, the entire part must be replaced. This maintenance process can take as long as an entire year. Having an aircraft inoperative for a year is a large inconvenience, and works against defence readiness, or having the aircraft ready for duty at any critical time. These issues make the traditional approach to the problem of corrosion costly and time consuming. For years, researchers have concentrated on nding the answer to the corrosion problem, although most of the work has focused on corrosion on the outer skin of the aircraft. As a result, a wide variety of protective surface treatments have been developed, mainly based on the application of primers, topcoats and conversion coatings [16]. Among these treatments, chromate-based conversion primers are considered the most popular corrosion inhibitors in spite of growing environmental concerns. However, the most problematic areas on these older aircraft often occur around the faying surfaces and the crevices between aluminium and steel layers. These locations are dicult to reach, and traditional coatings cannot protect them from corrosion. The original protection to the interfaces between steel fasteners, the aluminium wing skin and lap joints was aorded by the application of cadmium plating and/or chromate-based primers. But, paint removal and repainting procedures, performed during the maintenance overhauls that the plane endures throughout its life, can cause the removal of these corrosion barriers that once covered fastener joints and other critical interfaces, leaving them exposed to the elements of the atmosphere and thus susceptible to a new localized corrosion attack. Inside a crack or a crevice, localized corrosion can take place in the presence of water, oxygen and electrolytes [7]. In a humid environment, such as a rainy day, and under depletion of oxygen on one side of the crevice, an electrochemical local cell can be formed (anodic region). This generates a corrosion potential such that the region richer in oxygen acts as the cathodic species [8]. In contrast, no corrosion processes occur in the absence of water. Thus, the easiest way to avoid corrosion would be to create a barrier to block the entrance of water into the crevices. This barrier could be applied in the form of a hydrophobic coating on the inner surfaces of the crevice, in order to prevent water uptake into these locations before damage has occurred. In contrast to the mechanisms in which traditional organic coatings function [9], the idea presented here is to prevent water transport in the direction parallel to non-exposed surfaces. Fig. 1 illustrates a steel fastener joint before and after application of a lm by admicellar polymerization. The hypothesis is that modication of the hydrophilic nature of the aluminium surface, by forming a thin hydrophobic polymer lm inside the crevice, should help block the capillary forces that pull the water into the gaps. This change

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Fig. 1. Fastener joint: (a) before admicellar polymerization and (b) after admicellar polymerization.

in behavior was rst shown by Wu et al. on aluminium oxide powder in 1988 [10], and can be achieved using a process called admicellar polymerization [10,11]. The overall goal of this work was to adapt the admicellar polymerization process for aluminium alloy substrates in order to mitigate corrosion by preventing water uptake into crevices of aluminium-based aircraft. The work presented is geared towards understanding how process conditions such as pH, temperature and concentration aect the thin lm properties, the hydrophobic behavior of the crevices, and ultimately, the corrosion inhibition inside the aluminium crevices. To understand how the admicellar polymerized lm functions as a corrosion coating, a fundamental investigation of the polymer, metal and aqueous interfaces has also been performed. 2. Experimental 2.1. Materials Aluminium alloy 7075 plates were cut from commercial grating sheets provided by Kaiser Aluminum Corp. Sodium dodecyl sulfate (98% pure), ethyl alcohol (HPLC grade), tetrahydrofuran (99.9% pure), sulfuric acid (concentrated), styrene monomer (99% pure) and the initiator, 2,20 -azobisisobutyronitrile (AIBN), were provided by Aldrich. Methyl methacrylate (PMMA) (99% pure) was supplied by Johnson Matthey Electronics. Chromerge was purchased from Fisher Scientic. Sodium chloride (99% pure) was supplied by Spectrum Chemicals. Both styrene and methyl methacrylate were ltered prior to use with chromatographic alumina powder (Aldrich), to remove the inhibitor. The silanation agent (Glassclad 6C) was purchased from United Chemical Technologies. Except as noted above, all materials were used as received. 2.2. Surface modication Admicellar polymerization is based on the formation of an ultrathin polymeric lm conned inside a surfactant bilayer called an admicelle, which occurs under

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suitable adsorption conditions on an inorganic surface. This phenomenon has been widely investigated on many types of substrates (e.g. alumina, titanium oxide, silica, mica, glass bers and cotton) and with a variety of polymerizing monomers (tetrauorethylene, styrene, pyrrole, isoprene and butadiene) inside either cationic or anionic surfactant admicelles [1021]. The process can be photochemically and thermally activated with either water soluble or virtually water-insoluble initiators. There are three basic steps to admicellar polymerization [10]: (i) Admicelle formation: a bilayer of surfactant molecules is adsorbed on the solid surface, driven typically by the electrical charges generated on the substrate above or below the point of zero charge (PZC). For the adsorption of anionic surfactants, the substrate must exhibit a positive charge. This can be achieved by lowering the pH below the PZC. For aluminium oxide the PZC is close to 9. (ii) Monomer adsolubilization: at equilibrium, the monomer in aqueous solution partitions into the hydrophobic interior of the admicelle [2225]. Thus, the surfactant layer acts as a two-dimensional solvent at the substratesolution interface to concentrate the insoluble monomer. (iii) Polymer formation: in the last step, free-radical initiators, such as inorganic salts or organic azo-compounds, start the polymerization. After the polymerization is completed, the outer layer of the surfactant can be rinsed o, to leave the polymer lm exposed. The advantages of this process with respect to other conventional corrosion prevention techniques are the following: (1) small amounts of chemicals are needed; (2) there are no organic solvents involved, which makes the process economical and almost free of waste; (3) the process is robust as can be applied on a variety of substrates and geometries with very good adhesion and (4) many dierent monomers can be polymerized by admicellar polymerization. In the present study, the admicellar polymerization process was adapted from previous work [10,11] to deposit lms of polystyrene (PS) and PMMA onto aluminium alloy surfaces to act as the hydrophobic water barrier. This project employed the common anionic surfactant sodium dodecylsulfate (SDS) to form admicelles. The polymerization was thermally initiated with the water-insoluble initiator 2,20 -azobisisobutyronitrile. Flat (i.e. open) and crevice-like models made of AA7075 were used as described below to evaluate lm characteristics and performance. The admicellar polymerization process was applied on 7075 aluminium alloy (i) 2.54 cm 2.54 cm, and (ii) 3.81 cm 2.54 cm, 1 mm thick coupons. To guarantee the surfactant adsorption onto the substrate, several surface preparation steps were performed. The samples were rst brushed with commercial soap and water, followed by rinsing with tetrahydrofuran (99.9% pure) to remove the ink stamp on the alloys as supplied by the manufacturer. A chromicsulphuric acid mixture (Chromerge ) was used as an acid wash, to remove the previous existing protective coating on the aluminium specimens and to form a thin oxide layer on the substrate. Finally, the plates were rinsed liberally with deionized water. The clean surfaces were analyzed by energy dispersive X-ray analysis (EDXA) to ensure that chromium from the acid wash was not present on the surface prior to the admicellar process. The experimental conditions for the admicellar polymerization were varied as follows: the feed concentration of SDS was xed at 6000 lM, below but close to the

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CMC (CMC for SDS % 8000 lM). SDS/monomer concentration ratios were varied from 1:1, 1:2, 1:5 to 1:8 to study the eect of monomer concentration on lm performance. The initiator/monomer concentration ratios were varied from 1:20, 1:10, 1:5 to 1:2. Monomer and initiator were dissolved in ethanol rst to enhance molecular dispersion in water and to aid mass transfer. The volumes of ethanol were about 10 times and 40 times the amounts of monomer and initiator respectively. No additional electrolyte for the admicelle formation was added. The initial pH was adjusted to 5 and 6 with concentrated sulphuric acid. Flat plates were placed in clean plastic vials, 20 and 25 ml solution volumes were added for the 2.54 and the 3.81 cm samples, respectively, and the vials sealed. Adsorption time for the SDS was xed to 4 h, which preliminary work had indicated to be sucient for equilibrium to be reached. After the adsorption step, the vials were immersed in a preheated water bath. The temperature for the polymerization was xed at 75 C for reaction times of 1 and 2 h. Following the polymerization, the reaction was quenched by immersion of the vials in an iced-water bath. The plates were then pulled out and rinsed with deionized water to remove extractable surfactant and leave the polymer exposed. Next, samples were placed in an oven overnight to evaporate the remaining water on the surface as well as any residual non-polymerized monomer. 2.3. Characterization techniques In order to conrm the formation of a polymeric lm on the substrate, spectra of coated at plates for both PS and PMMA were acquired by Specular Reection FTIR on a Nicolet Nexus 670 FTIR spectrometer. To contrast the results obtained, SEM images of bare and coated aluminium single coupons were acquired with a JEOL JSM-880 with a LaB6 emitter operated at 15 kV. This technique also helped in assessing the uniformity and coverage of the lms. Since the lm thickness is very important for corrosion protection, estimations of the average lm thickness were performed with atomic force microscopy (AFM) analysis, using a NanoScope III, multimode scanning mode microscope (Digital Instruments). The samples were scanned under tapping mode. Standard silicon nitride tips were used as purchased from Digital Instruments. Measurements were based on cross-section analysis, to nd the height from the edge of the lm to the bare substrate. For this test, the substrate surface was exposed by scraping beforehand with a razor blade while being careful not to damage the surface of the aluminium. It was observed that the aluminium specimens, as supplied by the manufacturer, presented a very high initial roughness. This interfered with the measurements of the lm thickness, because the initial roughness of the substrate was in the same order of magnitude as the thickness of the polymer lms. In order to obtain reliable thickness values, samples for the AFM test were polished before the deposition of the polymer. No acid wash pretreatment was applied because the polish step removed the paint and oil from the surface. We started with 320-grid ACE sandpaper, and went down to a 1500 grid. The nal polish was provided with a 5-lm alumina powder solution.

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Because the goal was to create highly hydrophobic lms for the prevention of water uptake in crevices, contact angle measurements were performed as the main method of surface characterization. Since wetting lms and coatings involves the ow of water over the solid, dynamic contact angle analysis was chosen as an appropriate technique for wetting studies. A dynamic contact angle analyzer (Cahn Industries, Inc., DCA-322) was operated under the Wilhelmy method. This technique has been extensively used in the past for the measurement of contact angles on polymers [26], self-assembled monolayers [2729] and ultrathin lms [18,30] in contact with dierent liquids. In this work, contact angles for coated and bare aluminium at plates in deionized water were measured. Eight samples were prepared for each polymerization condition to test reproducibility and contact angles were measured three times for each sample and averaged. After having characterized the quality of the lms on individual aluminium plates, articial crevices were built from matched plates to evaluate the protective properties of the coating inside crevice-like locations. Once the process that consistently produced the highest contact angles was determined, individual coupons were coated under these conditions for fabrication of the crevices from the matched pair of coupons. Coated and bare aluminium plates were held together using 150 lm thick glass cover slides on both sides of the crevice as the spacers, to create an articial gap in between (Fig. 2). For polymer-coated samples, the spacers were previously modied by silanation to avoid water penetration in between the coated aluminium and the glass spacer. For this purpose, a 1% silanation agent solution in hexane was used according to the manufacturers instructions to pretreat the cover slip. In the case of bare aluminium crevices, the spacers remained uncoated to maintain the hydrophilic boundary conditions. The aluminium coupons were held together between two blocks of acrylic polymer attached with screws, as shown in Fig. 2. The sandwiched samples were then exposed to 3.5 wt.% NaCl deionized water, by bringing the edge of the coupon into contact with the solution so that the corrosive

Glass container

Cover glass Spacer: 150 m thick

3.5 wt.% NaCl solution

Polymer block

Fig. 2. Articial crevice model.

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media was drawn into the gap by capillary forces. The exposure times varied from 1, 2, 4, 12 to 24 h. Tests were run on PS and PMMA coated aluminium crevices, while bare aluminium crevices were also tested for comparison as controls. After each test, crevices were opened up for examination. Water uptake measurements were taken inside coated and bare aluminium articial crevices. The height of the column of salted water inside was measured with time and the percentage of wetted area was calculated on each crevice. A total of three articial crevices were tested under the same conditions and averaged. To quantify the extent of corrosion inside the crevices, we made use of image analysis software. The use of quantitative image analysis for characterization of corrosion is well known and is considered a reliable technique for evaluation of coating defects and performance against corrosion [3134]. Additionally, image analysis is a useful technique for discrimination of corrosion mechanisms and byproducts [35,36]. For corrosion evaluation purposes, an image of each crevice wall was acquired with a NIKON N90S camera and scanned under maximum resolution. Images were then processed with a Metavue software package. Changing brightness and contrast intensities, the regions of interest were thresholded and isolated from the total area. The threshold levels were adjusted based on the brightness and intensity of the sample before exposure to corrosion under the same illumination conditions, which served as the reference. It was possible to eliminate any undesired features, such as scratches or original stains on the sample, by adjusting the shape factor and the equivalent radius of the features. After these elements were subtracted, the software provided the numerical areas of highlighted regions so that results from bare aluminium, PS and PMMA crevices could be compared.

3. Results and discussion PS and PMMA ultrathin lms were deposited on aluminium 7075 coupons using the admicellar polymerization process described above. This was conrmed by Specular Reection FTIR obtained from PS and PMMA coated at plates after preparation under various experimental conditions. Specular Reection provided a quick and non-destructive method for detecting the presence of surface coatings. The single beam spectrum of bare aluminium plates served as the background. After acquiring 120 scans of PS and PMMA coated samples at a resolution of 4 cm1 , the background was subtracted to yield the nal IR spectra obtained. The results are presented in %transmittance arbitrary units. At the initial stages of the investigation, for reaction times of less than 1 h and for low monomer/initiator ratios, no peaks had been observed. For reaction times of 2 h and a monomer/SDS ratio of 5:1 characteristic peaks of PS and PMMA started to appear. The IR spectrum of PS on aluminium is presented in Fig. 3. Characteristic C@C peaks for PS started to show in the region of 1600 cm1 (characteristic of aromatics) at styrene:SDS ratios in solution equal or above 5:1. In addition, the C@CH bond emerged at 3025 cm1 . Two characteristic peaks for the CCH bonds appeared at 2853 and 2994 cm1 . The spectrum obtained was compared with a PS lm standard from Aldrich. For PMMA

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Fig. 3. Specular reection FTIR spectrum of PS coated aluminium 7075: (a) PS on aluminium 7075 and (b) standard PS lm.

polymerized in the same conditions as PS, a very intense characteristic peak appeared at 1740 cm1 , which corresponded to the C@O bond of the ester group, as shown in Fig. 4. Additionally, when compared with a PMMA standard, there was a very good match on the nger print region. Thus, the FTIR spectra obtained after the adjustment of the experimental conditions indicated a that a larger amount of

Fig. 4. Specular reection FTIR spectrum of PMMA coated aluminium 7075: (a) standard PMMA and (b) PMMA on aluminium 7075.

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Fig. 5. SEM images of (a) bare aluminium 7075, (b) PS coated aluminium 7075 and (c) PMMA coated aluminium 7075 (50 000).

polymer had deposited on the surface and that the thickness of these lms had increased generating an IR signal of sucient intensity to be detectable. FTIR results did not provide any information regarding the coverage and uniformity of the lms. Representative SEM images of untreated and coated aluminium are presented in Fig. 5. The porous structure of the aluminium oxide (Fig. 5(a)) is probably a consequence of the acid wash pretreatment applied to bare aluminium for removal of the organic coating as supplied by the manufacturer. However, at such a small scale, that does not seem to interfere with the polymer deposition. Fig. 5(b) and (c) show the presence of both PS and PMMA on the aluminium surface. As observed, typical polymer globular aggregates formed on top of the metal oxide. PS appeared more porous whereas PMMA seemed to be more compact, with clusters spanning or lling the holes left by the acid attack. The SEM images revealed that there was a good coverage and that the lms were uniform although not at. These observations were in agreement with the FTIR results and conrmed that PS and PMMA lms had been deposited on aluminium 7075 by admicellar polymerization. Once the FTIR and SEM results veried the presence of the coatings, we made use of an AFM technique to estimate the thickness of the lms, a very important parameter in corrosion control coatings. Results from the AFM cross-section analysis for PS and PMMA under optimum admicellar polymerization conditions are presented in Fig. 6. In the present work, lms in the range of 150269 nm were measured for PS and PMMA lms on aluminium coupons, respectively. In previous work, thin lms obtained on aluminium oxide and mica by admicellar polymerization have been reported to reach from several to tens of nanometers in thickness [10,17,37]. It has been proved that the growth of some polymers can actually be limited by the admicelles. This phenomenon was shown by Yuan et al. [17] who obtained polypyrrole lms on mica thicker than 150 nm in the absence of surfactants, whereas those obtained by admicellar polymerization were in the range of 30 60 nm. The increase in the thickness achieved in our study could be related to a higher concentration of monomer in the admicelle during the polymerization reaction. Since the surface area of at aluminium coupons is signicantly less than that for porous materials (e.g. alumina powder or silica), monomer in the bulk acts as a

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Fig. 6. AFM cross-section analysis on (a) PS coated aluminium 7075 and (b) on PMMA coated aluminium 7075. Monomer/SDS ratio is 5:1, AIBN/styrene ratio is 1:20, pH 6, reaction time is 2 h. Vertical thickness: 163 and 269 nm respectively.

reservoir available for adsolubilization and reaction in this system. Additionally, a higher monomer/surfactant ratio and a longer reaction time could have contributed to this eect. Because the objective of this study was to deposit a hydrophobic lm that acted as a water barrier inside aluminium narrow gaps, contact angle measurements were performed to test the wettability of PS and PMMA lms deposited on aluminium coupons. Before the polymer lms were deposited onto the aluminium surface, the average advancing contact angles in deionized water ranged between 30 and 50, indicating that the uncoated coupons were moderately hydrophilic in nature. Tables 1 and 2 show average dynamic contact angles obtained from PS and PMMA coated samples after a 2-h reaction at an initial pH of 6 for a SDS/monomer ratio of 1:5 and an AIBN/Monomer ratio of 1:20. Admicellar polymerization of PS yielded a hydrophobic material evident from drops of water beading up on the surface when rinsed with deionized water. For these polymerization conditions, PS coated coupons exhibited advancing contact angles greater than 100 in 90% of the cases, somewhat higher than those reported in the literature measured either with the Wilhelmy technique or with other methods [18,26,3840]. Receding contact angles for PS samples, however, presented a large standard deviation, with values of 0 for many samples. These low receding angles were probably related to the presence of water molecules in the lm, accumulated on the surface during contact angle ex-

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Table 1 Average dynamic contact angles of at plates polymerized with styrene at pH 6 after 2 h reaction process Sample # 1 2 3 4 5 6 7 8 Average hA (deg) 105.3 103.4 105.1 108.3 106.5 105.2 95.9 103.1 104.1 5.35 (95% condence interval) hR (deg) 0.0 0.0 41.0 37.7 37.0 12.7 45.8 0.0 21.8 14.19

SDS concentration is 6000 M. Styrene/SDS ratio is 5:1, AIBN/styrene concentration ratio is 1:20. Table 2 Average dynamic contact angles of at plates polymerized with methyl methacrylate at pH 6 after 2 h reaction process Sample # 1 2 3 4 5 6 7 8 Average hA (deg) 94.9 100.0 96.6 94.3 94.3 92.3 98.0 95.3 95.7 1.66 (95% condence interval) hR (deg) 45.2 48.8 48.7 53.6 41.3 34.2 53.2 41.3 45.8 4.59

SDS concentration is 6000 lM. MMA/SDS ratio is 5:1, AIBN/MMA concentration ratio is 1:20.

periments. PMMA advancing contact angles were not as high as those for PS but still very hydrophobic, ranging from 78 to 95 on average, slightly higher than those reported previously in the literature [26,39,40]. It is well known that dynamic contact angles are dependent on the analytical method, in which factors such as the rate of motion of the three-phase contact line are crucial. The Wilhelmy technique is extremely sensitive to geometry changes with respect to the ideal at plate, and the aluminium coupons employed in this study were far from ideal. In particular, it has been demonstrated that the advancing contact angle is inuenced by the surface roughness. Various studies discuss the eect of surface roughness on contact angle hysteresis [41,42]. As observed in Fig. 5, PS and PMMA lms presented a high degree of roughness that probably contributed to an increase in the advancing contact angles with respect to the contact angles of perfectly at PS and PMMA. To contrast these observations, the SEM images of thin at pieces of commercial grade PS and PMMA were analyzed (data not shown). Processed commercial polymers turned out to be smooth and at when compared to admicellar polymerized lms. For further comparison, the dynamic contact angles of eight at

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PS and PMMA coupons of commercial grade were measured. The average values of advancing contact angles for commercial PS were slightly above 90, whereas the average for Plexiglass was around 90. Receding contact angles for commercial PS and PMMA showed average values close to 44 and 20, respectively. In both cases the results were closer to what has been reported in the literature [18,26,3840]. Clearly, the low receding contact angles obtained on PS coated aluminium samples were due to the inherent roughness of the substrate and admicellar-polymerized samples. This indicated the importance of the eect of surface roughness on dynamic contact angle measurements. Because the lm quality and contact angle seemed to vary depending on the lm polymerization conditions, several process conditions were analyzed. Values of pH below 5 led to less hydrophobic modied surfaces because the native aluminium oxide dissolves at pH values below 4. It is possible that competition between the adsorption of the surfactant onto the surface and the dissolution of the aluminium oxide layer led to incomplete coverage of the surface. Advancing contact angles obtained at pH values below 5 were smaller than 90 in most cases. At pH values above 6 however, the positive charge density on the aluminium oxide surface was diminished and conditions favorable to surfactant adsorption reduced. For these reasons, subsequent lm depositions were carried out at pH values between 5 and 6 to guarantee a positive charge on the aluminium oxide substrate. The eect of the SDS/monomer ratio was also studied. Excess monomer above a 1:5 ratio resulted in unsolubilized monomer that formed drops in solution that ultimately deposited on the surface producing a non-uniform lm. Also, at these high monomer ratios, emulsion polymerization was also believed to have taken place from micelles formed in solution and not on the aluminium surface. The same eect was observed by Wu et al. [10] after lm formation on alumina powder with excess monomer, in which spherical polymer particles that formed in solution deposited onto the alumina powder surface. For ratios of 1:1 and 1:2 the coatings were uniform but not thick enough to be observed under the FTIR. However, no dierences in the contact angles measurements were observed and the advancing contact angles ranged from 90 to 100. Therefore, a 1:5 SDS/monomer ratio was chosen for the admicellar polymerization before the corrosion tests. In addition, the initiator/monomer ratio seemed to play an important role on the morphology of the coatings, and thus, on the contact angles obtained. Average dynamic contact angles under dierent AIBN/monomer ratios are presented in Fig. 7(a) and (b). The initiator/monomer concentration ratios were varied from 1:20, 1:10, and 1:5 to 1:2, while the SDS/monomer of 1:5 and other polymerization conditions were xed. The highest initiator/monomer ratio studied, which was 1:2, resulted in the lowest contact angles obtained for both PS and PMMA coatings. However, when this ratio was reduced to 1:20, the highest contact angles were obtained and the surface presented smaller roughness values as measured by AFM [43]. As observed in Fig. 7(b), for PMMA coated coupons there is a greater than 20 dierence in the advancing contact angles between an AIBN/MMA ratio of 1:20 compared to 1:2. The variation in both the advancing and the receding contact angles follows the same trend. Lesser AIBN/monomer ratios led to higher contact

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Contact Angles (deg)

(a)

100 80 60 40 20 0 0.00

Advancing Receding

0.10

0.20

0.30

0.40

0.50

0.60

AIBN/Sty
120

Contact Angles (deg)

(b)
100 80 60 40 20 0 0.00

Advancing Receding

0.10

0.20 0.30 0.40 AIBN/MMA

0.50

0.60

Fig. 7. Dynamic contact angles obtained for (a) PS coated aluminium 7075 and (b) PMMA coated aluminium 7075 at plates after 2 h of reaction at pH 6. SDS concentration is 6000 lM. Monomer/SDS ratio is 5:1; AIBN/styrene ratio is 1:20 (the bars indicate 95% condence interval).

angles. In contrast, PS coated samples followed this trend only for the advancing contact angles. Receding contact angles for PS showed considerable uctuation, with no signicant trend being evident. Apparently, higher concentrations of initiator led to lower molecular weights in the polymer with shorter polymer chains forming a patchwise morphology on top of the aluminium substrate, as observed by AFM measurements [43]. Therefore, the highest contact angles were achieved with the lowest AIBN/monomer ratio, possibly due to a better distribution and coverage of longer and more entangled polymer chains of a higher molecular weight. The hysteresis between the advancing and the receding contact angles can again also be explained from the surface heterogeneity and roughness of the coupons [41,42]. The sensitivity of the receding angles to small changes in the surface composition is also well described in the literature [44]. In support of this, we note SEM images (Fig. 5) showed higher porosity of PS lms compared to PMMA lms. This suggested that PS might have been trapping greater amounts of water inside pores during the contact angle measurements, which could explain why PS lms showed very low receding contact angles in comparison to PMMA lms. Pease [45] suggested that advancing contact angles were associated

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with low-energy surfaces, whereas receding contact angles were with high-energy regions. Water trapped in the polymer after exposure during advancing contact angle measurements could have contributed to an increase in the percentage of high-energy surface (hydrophilic surface), leading to values of 0 in some of the receding contact angles. Similar experiments were done shortening the reaction time to 1 h. The contact angles measured did not show a large dierence, and were in the same range as those described above. However, the FTIR signal was aected by the length of the reaction time, since characteristic peaks for both PS and PMMA were not detectable at reaction times of less than 2 h. This suggested that longer reaction times would have little eect on the contact angle but a large eect on the thickness of the lm. As the polymerization reaction took place, more monomer could have partitioned into the admicelle and reacted to form additional polymer. This contributed to increased thickness of the lm, which was of sucient dimension as to generate detectable FTIR signals. However, this increase in the thickness did not seem to aect the contact angles. To evaluate the potential benet of high advancing contact angles, articial crevices were built from coated coupons for water uptake measurements and ultimately for corrosion prevention testing. The information provided by the wettability test was combined with the results from the image analysis of the exposed crevices. Results for the water uptake measurements are presented in Fig. 8. Bare aluminium was completely wetted by the corrosive solution at very short times, which corroborated the hydrophilic nature of the substrate observed from the contact angle measurements. PMMA coated aluminium did not appear to be very hydrophobic in this test, despite the high advancing contact angles obtained. Water penetration rose to about 70% by 12 h and slowly increased to 90% after 24 h. In contrast, the PS coating delayed the water uptake signicantly. For the rst 2 h, salt-water did not penetrate into the crevice and after 4 h, not even 50% of the surface was wetted. The

120 100
% Wetted Area

80 60 40 20 0 0 4 8 12 16 20 24 28
Exposure time (h)
Bare Aluminium PMMA PS

Fig. 8. Water uptake measurements inside bare, PMMA and PS coated aluminium 7075 crevices.

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wetting performance of PS corresponded to the expected result, since for the process conditions chosen, the advancing contact angles for this material had exceeded 100 (Table 1). However, PS seemed to lose its hydrophobic properties gradually, until after 24 h, more than 80% of the crevice surface was wet. For corrosion evaluation inside the crevices, a digital image of each sample was acquired for further analysis after exposure to a corrosive environment. As observed in Fig. 9, there were two characteristic colorations on the bare aluminium surface after exposure to salt-water. Dark brownish areas were believed to correspond to surface roughening or pitting caused by the attack of chloride ions. From the observations made under the microscope, early pitting corrosion seemed to be dominant in these areas. It is very possible that these pits started to form at the metal inclusions present in the aluminium matrix, as described in the past by Suter and Alkire [46]. The formation of galvanic couples between aluminium and copper, more noble than aluminium, was probably responsible for the rapid corrosion of aluminium, accelerated by the presence of chloride ions in the electrolyte. Following the pit formation, characteristic white depositions started to grow after longer exposure times, presumably from precipitation of insoluble aluminium hydroxides and insoluble oxides of the alloying elements. In Fig. 10, we compare thresholded regions for bare, PMMA and PS coated aluminium crevices after 1 h in 3.5 wt.% NaCl. Similarly, results for a 24-h test are shown in Fig. 11, in which surface roughening and corrosion depositions are differentiated. Bare aluminium presented evidence of corrosion from the rst hour of exposure, the time at which the hydrophilic surface appeared completely wet by the corrosive solution (Fig. 8). These corrosion eects became worse in the course of time until after the 24th hour almost the entire surface appeared covered in surface roughness and oxide depositions (Fig. 11). According to Fig. 10, PS coated crevices did not show any evidence of corrosion attack after 1 h of exposure. This was due to the absence of salt-water inside the crevice, as indicated in Fig. 8, which shows that the PS crevice had not even been wetted after the rst couple of hours. These results conrm the hypothesis that the deposition of a hydrophobic lm with good coverage and high initial advancing contact angles (as high as 100) could block temporarily the transport of water into the crevices, and thus, stop the corrosion processes that occur inside. After 24 h however, PS presents signicant amounts of surface roughening and corrosion depositions, which followed a full wetting process reported in Fig. 8. The PS sample became signicantly wet after the 12 h, the duration at which the hydrophobic properties of the lm had been reduced signicantly. After 24 h, the state of degradation of the lm is such that PS is not capable of protecting from water uptake any more. In contrast, PMMA did not prevent water penetration into the crevice. Surprisingly, the high advancing contact angles obtained for PMMA did not lead to the water uptake results expected, and PMMA became almost completely wet at exposure times as short as 1 h. This might be due the high roughness observed from the SEM images (Fig. 5). The advancing contact angles obtained were only apparent, due to high roughness, and the actual values were probably closer to 90, similar to those obtained for at PMMA.

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Fig. 9. Bare aluminium 7075 corrosion products inside an articial crevice after 24 h in contact with 3.5 wt.% NaCl.

Fig. 10. Comparison of corrosion evaluation inside bare, PMMA and PS coated aluminium 7075 crevices after 1 h in contact with 3.5 wt.% NaCl.

However, presenting a water uptake of 70% in the rst 12 h and of 90% after 24 h (Fig. 8), PMMA seemed to act as a chemical barrier against corrosion, evident from the results shown in Figs. 10 and 11. When comparing to bare aluminium, the percentage of pitting for PMMA is insignicant after the rst hour, and after the 24th hour, surface roughening and oxide depositions are considerably reduced with respect to bare aluminium. This suggested that PMMA delayed the diusion of water normal to the surface, and thus, the corrosion reactions at the metalwater interface. These observations are in good agreement with the data obtained by Linossier et al. [47], who studied the adhesion loss of PS and PMMA coatings induced

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Fig. 11. Comparison of corrosion evaluation inside bare, PMMA and PS coated aluminium 7075 crevices after 24 h in contact with 3.5 wt.% NaCl. Row (a) corresponds to surface roughening areas and row (b) to corrosion depositions.

by water diusion in the direction normal to the lms. They observed that the water penetration through the lm was much faster in the case of PS, whereas PMMA seemed quite protective. In a dierent study, Linossier et al. [48] measured the diusion coecients of water in PS and PMMA lms applied on a at ZnS crystal.

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The values obtained were $6.0 108 cm2 /s for PS of any molecular weight and values that ranged from 0.98 108 to 1.49 108 cm2 /s for PMMA of various molecular weights at ambient temperature. Clearly the diusion coecient for PS was larger than that for PMMA, meaning that water transport was faster in the case of PS lms, and it was attributed to defects present in the PS lm. Because of these defects, swelling eects were believed to be the cause of the degeneration of PS. As observed in Fig. 5, the PS lm seemed to be more porous than PMMA, which presumably enhanced the transport of water in the direction normal to the surface. This could have caused the swelling of the PS lm, and corrosion underneath could have been much more dramatic on the wetted surface. The eect of polymer swelling after exposure to water and electrolytes is well described in the literature [49,50]. In the case of polyacrylates, such as PMMA, it has been suggested that strong interactions between the COO groups and water molecules lower the diusion coecient with respect to other less polar polymers by the creation of hydrogen bonds between two polar groups and a water molecule [51,52]. This would explain why the electrolyte seems to need more time to reach the aluminium surface and begin the corrosion attack. In order to verify in what extent PS and PMMA had protected aluminium crevices from corrosion, quantitative evaluation of surface roughening, corrosion depositions and total corrosion for bare, PMMA and PS coated aluminium was performed in triplicate, and the results are presented in Fig. 12. The analysis of variance for bare aluminium, PS and PMMA corrosion results indicated that the averages for the area percentages were signicantly dierent in all cases except for the 12 h experiment. For short exposure times, PS exhibited the lowest corrosion rate, due to the absence of salt-water inside the crevice. Although PMMA presented almost full water uptake after the rst hour, it showed a very reduced corroded area. This can also be observed in Fig. 10, where PS does not present highlighted areas from the image analysis and where the highlighted spots for PMMA are not important. As expected, the largest corroded area corresponded to the bare aluminium crevices. For long exposure times, PMMA seemed to maintain its protective properties, evident from the reduced surface roughening in Fig. 11. Such was not the case for PS, which deteriorated dramatically after the 12th hour. Although the percentage of surface roughening in PS is not as large as in the control, the amount of white depositions is similar to that of bare aluminium. This indicated that aluminium oxide dissolved more rapidly underneath the PS lm once it became wet. Fig. 13 compares average total corroded areas evaluated over the crevice total area and time dependent wetted area. In Fig. 13(a), bare aluminium exhibited the largest total corroded area in all cases except for the 12 h case. Interestingly, PMMA did not corrode above 30% in any case, whereas bare aluminium exceeded 73% of corrosion. As mentioned above, PS protected from water uptake up to about 4 h, with little corrosion present on this time frame. After that time however, rapid corrosion takes place because of the fast diusion of water through the lm. When comparing the extent of corrosion per wetted surface to that based on total area, the relative corrosion percentage for PMMA and bare aluminium remained practically the same, because their wetted areas represented a large percentage of the total area.

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% Corroded Area/Total Area
100 90 80 70 60 50 40 30 20 10 0

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(a)

Surface Roughening Corrosion depositions Total

4 Exposure time (h)

12

24

% Corroded Area/Total Area

100 90 80 70 60 50 40 30 20 10 0

(b)
Surface Roughening Corrosion depositions Total

4 Exposure time (h)

12

24

% Corroded Area/Total Area

100 90 80 70 60 50 40 30 20 10 0

(c)
Surface Roughening Corrosion depositions Total

4 Exposure time (h)

12

24

Fig. 12. Quantitative analysis of corrosion processes over time for bare (a), PMMA (b) and PS (c) coated aluminium 7075.

PS however, suered an increase in the net corroded area. This showed that, once PS has become wet, it does not provide an eective chemical barrier against corrosion processes. These corrosion test results reveal that the mechanisms in which these two polymers protect the substrate dier. PS behaves as a hydrophobic barrier at the initial stages as it stops the water uptake in the direction parallel to the surface. Once PS has been exposed long enough it starts to lose its hydrophobic properties, water rises into the cavity and diuses across the polymer. After losing the hydrophobicity,

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% Corroded Area/ Total Area 100 90 80 70 60 50 40 30 20 10 0

O.M. Matarredona et al. / Corrosion Science 45 (2003) 25412562

(a)

PMMA PS Bare Aluminium

4 12 Exposure time (h)

24

% Corroded Area/ Wetted Area

100 90 80 70 60 50 40 30 20 10 0

(b)

PMMA PS Bare Aluminium

4 12 Exposure time (h)

24

Fig. 13. Percentage of total corroded area evaluated over (a) total crevice area and (b) wetted crevice area for bare, PMMA and PS coated aluminium 7075 crevices.

corrosion processes could have been more severe underneath the lm. PMMA gets wet easily although it seems to act as a chemical barrier against the chloride attack due to the creation of hydrogen bonds between the COO groups and the water molecules. This suggests that the design of a polymeric lm capable of using both mechanisms would be appropriate. The answer to the problem of corrosion in narrow spaces could rely on nding a polymer that presented the hydrophobic properties of PS combined with the chemical properties of PMMA.

4. Conclusions PS and PMMA thin lms were deposited onto aluminium 7075 at substrates using the admicellar polymerization process, conrmed from the FTIR and SEM results. The thickness of the deposited lms was above 100 nm, as shown by the AFM cross-section analysis. Dynamic contact angle measurements were performed to determine the wettability of bare and coated aluminium 7075. Modied aluminium alloy specimens exhibited hydrophobic behavior after admicellar polymerization, with advancing contact angles that exceeded 100 in some cases.

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An articial crevice model from coated coupons was developed to study the water uptake and ultimately the corrosion inhibition inside bare aluminium, PS and PMMA coated crevices. Water penetration was delayed up to 4 h in the case of PScoated crevices. For short exposure times there was no evidence of corrosion on PS samples due to the absence of water inside the crevices. After 12 h, PS lost its hydrophobic properties and corrosion processes occurred. Although corrosion inhibition on PS coated samples was only partially achieved, PMMA responded eectively to the corrosion attack. PMMA however, did not show any advantage as a water barrier. For longer times and after the surface had become fully wetted, corroded areas on PMMA samples were considerably reduced from those of bare aluminium. This suggested that PS and PMMA use dierent mechanisms for corrosion inhibition. Bare aluminium became wet and easily corroded after the rst hour of exposure. Overall, bare aluminium crevices were more susceptible to wetting and corrosion attack than PMMA or PS coated articial crevices. In humid environments, admicellar polymerization shows promise as a solution to the localized corrosion processes that take place in narrow spaces, such as lap joints or other types of crevices. The answer to the problem could rely on protective lms with the hydrophobic properties of PS in combination with the chemical barrier properties of PMMA.

Acknowledgements The authors would like to express their gratitude to US Air Force EPSCOR for their nancial support through grant F49620-00-1-0241. We acknowledge Oklahoma State Board of Regents and Don Neiser from Tinker Air Force Base. Bill Chissoe from the Samuel Roberts Nobel Electron Microscopy Laboratory of the University of Oklahoma is also thanked for his assistance in SEM imaging.

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