Journal of The Electrochemical Society, 153 8 B325-B329 2006

0013-4651/2006/153 8 /B325/5/$20.00 The Electrochemical Society

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Corrosion Resistant High-Silica-Zeolite MFI Coating

One General Solution Formulation for Aluminum Alloy AA-2024-T3, AA-5052-H32, AA-6061-T4, and AA-7075-T6
Derek E. Beving,a Andrew M. P. McDonnell,a Weishen Yang,b and Yushan Yana,*,z
a

Department of Chemical and Environmental Engineering, University of California, Riverside, California 92521, USA b State Key Laboratory of Catalysis, Dalian Institue of Chemical Physics, Chinese Academy of Sciences, Dalian, China Corrosion resistant high-silica-zeolite HSZ MFI coatings have been synthesized by in situ crystallization using a single solution formulation on a series of aluminum alloys with rather different chemical compositions including AA-2024-T3, AA-5052-H32, AA-6061-T4, and AA-7075-T6. The coatings are continuous, compact, and of uniform thickness 10 m . The coatings are demonstrated by using ASTM D 3359B-02 method to have excellent adhesion to all metal substrates tested. The cross-sectional composition analysis shows a gradual and continuous change of Si/Al ratio from pure aluminum at the substrate surface to almost innity at the free coating surface, and this is suggested to be the origin of excellent of adhesion observed. In addition, a simple detergent solution pretreatment is shown to be adequate for the reproducible formation of high quality coatings. 2006 The Electrochemical Society. DOI: 10.1149/1.2207845 All rights reserved. Manuscript submitted January 11, 2006; revised manuscript received February 6, 2006. Available electronically June 15, 2006.

Chromate conversion coatings have long been the accepted standard for corrosion protection of aerospace aluminum alloys e.g., AA-2024-T3 . They are remarkably effective and durable, but their application processes release hexavalent chromium, which is a known human carcinogen. The possible human exposures during the coating application and subsequent waste disposal have generated serious worker health and safety and environmental concerns.1,2 As a result, the chromium based technology is becoming increasingly costly to use, and much effort has been dedicated to identifying and developing environmentally friendly, chromium-free coatings with equivalent or superior corrosion performance as a viable replacement. Zeolites are microporous crystalline aluminosilicates. They have been commercially used in powder or powder composite form as shape-selective catalysts, molecular sieving separation media, and ion exchangers. Zeolites are nontoxic and have been actively investigated as carriers, controlled release agents, and adjuvants for certain drugs3-5 Thus a zeolite coating, if proved to be corrosion resistant, has the potential to become an environmentally benign alternative for chromate conversion coatings. We have previously demonstrated that as-synthesized structuredirecting agent SDA containing high-silica-zeolite HSZ MFI coatings on aluminum alloy 2024-T3 AA-2024-T3 have superior corrosion resistance to chromate conversion coatings and chromic acid anodization coatings in strong acids, bases, and pitting aggressive media.6 Because of the presence of the SDA molecules i.e., tetrapropylammonium hydroxide in their zeolitic pores, the assynthesized MFI coatings are nonporous, and thus can serve as a barrier to corrosive species. There are many zeolites available today with different topology and each topology is designated with a three-letter code e.g., MFI www.iza-online.org . We have also demonstrated that the in situ crystallization coating deposition process can coat surfaces of complex shape and in conned spaces.6 Preliminary work has shown that the HSZ-MFI coating is thermally stable when tested at 240C, and its mechanical properties is also satisfactory.7,8 We have also shown that in addition to HSZ MFI, SDA containing pure-silica-zeolites PSZs such as MFI, MTW and BEA coatings can provide good corrosion resistance on both AA2024-T3 and stainless steel 304-2b despite their differences in pore dimensionality, microporosity, and framework density.9 HSZ and PSZ MFI coatings have been formed by in situ crystallization or its modied form on numerous substrate types including

* Electrochemical Society Active Member.

z

E-mail: yushan.yan@ucr.edu

metals, ceramics, and others e.g., stainless steels 304, 316L, AA2024-T3, silicon wafer, -Al2O3, zirconia, fused-quartz, copper, copper alloy, 08KP steel, pig iron, brass, silver, and nickel .6,9-17 Except for our previous works on corrosion protection of aluminum alloys, however, all of these studies have focused on applications such as separation membranes, catalytic membrane reactors, and coatings for adsorption and catalysis. Thus corrosion resistance of these MFI coatings has not been examined. These MFI coatings appeared to be uniform in thickness and showed no signs of delamination after calcination or high temperature treatment,11-17 suggesting excellent adhesion to the various metal substrates. However, the adhesion has not been quantitatively examined by a standard test, the passing of which is essential for the qualication of corrosion resistant coatings. AA-2024-T3, AA-5052-H32, AA-6061-T4, and AA-7075-T6 are all relevant for military applications. Although their corrosion susceptibility varies, they in general all require corrosion protection. Since the chemical compositions of these alloys vary signicantly especially in terms of major alloying element Table I , they have usually required different pretreatment or coating formulation. Thus it has long been desired that a simple substrate pretreatment and a single coating formulation capable of providing corrosion resistance to all these alloys are developed to achieve tremendous cost savings. Research on chromate conversion coatings CCCs on AAs by Leggat et al. clearly demonstrates this need.19 They applied CCCs to three different aluminum alloys AA-2024-T3, AA6061-T6 and AA7075-T6 using a single chemical formulation permitted by military specication: MIL-C-81706. Prior to CCC application all alloys were pretreated in a deoxidizing solution by two methods. In the rst method, the samples were in contact with the deoxidizing solution for 5 min and then rinsed in tap water. In the second pretreatment method the samples were manually abraded with nonmetallic scouring pads while in contact with the deoxidizing solution for 12 min and then rinsed in tap water. Salt spray testing was carried out according to ASTM B-117, only the abraded AA-6061 coatings passed the 168 h salt spray exposure required for quality conformance by Mil-C-81706. CCC coated AA-2024 samples for both pretreatments failed to pass the salt spray test by the earliest check point time at 24 h. All CCC coated AA-7075 samples that had the second pretreatment had failed by 24 h of exposure, whereas with the rst pretreatment, failure of all coated AA-7075 and AA-6061 samples did not occur until 66 h of exposure. The disparate salt spray performance based on aluminum alloy type and surface pretreatment observed by Leggat et al.19 shows that one CCC chemical formulation does not universally provide adequate corrosion protection to aluminum alloys.

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Journal of The Electrochemical Society, 153 8 B325-B329 2006

Table I. Chemical compositions (wt %) for AAs.18 Alloy 2024 5052 6061 7075 Si 0.50 0.25 0.400.80 0.400.50 Fe 0.50 0.40 0.70 Cu 3.804.90 0.10 0.150.40 1.202.00 Mn 0.300.90 0.10 0.15 0.30 Mg 1.201.80 2.202.80 0.801.20 2.102.90 Cr 0.10 0.150.35 0.040.35 0.180.28 Zn 0.25 0.10 0.25 5.106.40 Ti 0.15 0.15 0.20

With all of the aforementioned encouraging data we have obtained so far on HSZ MFI coating on AA-2024-T3, the key question we attempt to answer in this study is whether we can use the simple pretreatment method and the coating HSZ MFI formulation we have developed for AA-2024-T3 for other aluminum alloys e.g., 5052H32, 6061-T4, and 7075-T6. The ability to use one common pretreatment and one coating formulation on different aluminum alloys means tremendous cost savings. Another goal of this study is to apply a commonly used standard adhesion test method to demonstrate that the coatings not only have excellent corrosion resistance but also remarkable adhesion. We also show that the excellent adhesion likely originates from the innitely graded chemical composition across the lm thickness. Experimental Coating solution formulation. High-silica-zeolite HSZ MFI coating was prepared by in situ hydrothermal crystallization method. First, a clear synthesis solution with molar composition 0.16TPAOH:0.64NaOH:TEOS:92H2O:0.0018Al gram composition 17.03 g TPAOH, 5.36 g NaOH, 43.60 g TEOS, 336.00 g H2O, 0.0105 g Al was prepared by dissolving aluminum powder 200 mesh, 99.95+ wt %, Aldrich in sodium hydroxide 99.99 wt %, Aldrich and double de-ionized DDI water followed by drop-wise addition of tetraproylammonium hydroxide TPAOH, 40 wt %, aqueous solution, SACHEM and tetraethylorthosilicate TEOS, 98 wt %, Aldrich under stirring. The clear solution was aged at room temperature for 4 h under stirring before use. Substrate pretreatment. All aluminum alloys were commercially purchased. AA-7075-T6 and 5052-H32 were purchased from American Aerospace Materials, Monterey Park, CA. AA-2024-T3 and AA-6061-T4 were purchased from Advanced Alloys, Inc., Rancho Cucamonga, CA. The substrates were sized to 2 3.5 cm and cleaned at four different temperatures ambient, 45, 60, and 80C for 1 h in an Alconox detergent solution prepared with 3.0 grams Alconox in 400 mL deionized DI H2O to determine whether there was a correlation between cleaning temperature and reproducible HSZ coatings on all AAs. The substrates were then rinsed under DI water with mild rubbing. Substrates were dried with compressed air and kept at ambient conditions for less than 1 h before immersion in zeolite synthesis solution. Coating deposition. A 45 mL Teon-lined Parr autoclave was used as the synthesis vessel and the substrate was xed vertically inside the synthesis solution using a Teon holder. Crystallization was carried out in a convection oven at 175C for 16 h. The autoclave was then removed and quenched with tap water. The coated sample was water rinsed and dried in ambient room air for at least 12 h before characterization. Characterization. The X-ray diffraction XRD patterns were obtained on Siemens D-500 diffractometer using Cu K radiation. HSZ-AA coating samples were directly used for XRD analysis and were xed and aligned in the sample holder carefully to minimize shifts in 2-theta angles. Scanning electron microscope SEM micrographs were obtained on a Philips XL30-FEG scanning electron microscope operated at 20 kV. An Au/Pd coating was applied to MFI-AA samples by sputtering for 45 s for both surface and crosssectional SEM imaging. Samples were etched for cross-sectional SEM imaging by dipping the MFI-AA samples in 49 wt % HF for

5 s. For coating cross-sectional elemental analysis, MFI coated AA2024-T3 was imbedded in epoxy and cross-sectional wafers were cut using a diamond saw. Surfaces of wafers were sanded using 400 grit sandpaper followed by 600 grit sandpaper and polished on a Buehler, Ecomet 3 grinder-polisher using a 0.3 m slurry particle size. The silicon to aluminum ratio of the MFI coating at different points from the substrate/zeolite interface was determined by semiquantitative energy dispersive X-ray microanalysis EDAX , performed on a Philips XL-30 scanning electron microscope equipped with an EDAX EDS analytical system. X-ray photoelectron spectroscopy XPS was performed on the HSZ-AA surface by using a VG electron spectroscopy for chemical analysis, ESCALAB MK-2X spectrometer, equipped with a single channel detector with Al K radiation. The Al2p peak at 74.7 eV was used as an internal standard. Adhesion. Adhesion of the zeolite coatings to the AA substrates was measured according to American Society for Testing and Materials ASTM ASTM D 3359B-02. The adhesion test kit was purchased from Paul N. Gardner Company, Inc. The cutting tool was tted with a blade containing 11 teeth spaced 1.0 mm apart. Coated substrates were secured to the lab bench by a C-clamp and the cutting tool was used to make the cross-cut pattern at 90 angles through the coating. The coating was brushed lightly with a soft brush after each cut to remove excess debris from the surface. Permacel 99 tape was applied to the cut surface and rubbed with the eraser end of a pencil to ensure good contact with the coating and then removed after 90 s. Samples were evaluated under a lighted magnifying glass 7 times magnication and rated according to the ASTM rating scheme. DC polarization. Polarization testing was carried out with a Solartron potentiostat SI 1287 in a three-electrode conguration with the zeolite coated substrate as the working electrode, a platinum foil as the counter electrode, and a saturated calomel electrode SCE as the reference electrode. The corrosive medium was either 0.5 M H2SO4, 0.5 M NaCl/HCl pH 3.0 , or 0.5 M NaOH aqueous solution. The edges of the coated substrate were sealed with epoxy while keeping exposed the coating surface on which corrosionresistance was to be measured. Zeolite coated samples were immersed in the corrosive medium for 30 min 2 min for NaOH solution prior to the polarization test. The temperature of the solution during polarization tests was at ambient temperature. A sweep rate of 1 mV/s was applied and all potentials were referred to the SCE. Results and Discussion Out of the four temperatures studied, consistently reproducible HSZ coatings on all AAs were produced when the substrate cleaning solution was at 60C Table II . At this temperature greater than 99% of all substrates were successfully coated with a continuous, compact and corrosion resistant HSZ MFI coating. Excellent HSZ MFI coatings could also form on the AAs at the other tested cleaning solution temperatures ambient, 45, and 80C but with reduced frequency of successful coating falling between 80 and 90%. The concentration of 3.0 g Alconox in 400 mL DI H2O was the initial concentration tested for cleaning the AAs. Cleaning efcacy of different concentrations of the detergent were not tested, other than 30.0 g Alconox in 400 mL DI H2O, a tenfold increase, showing no observable difference in HSZ MFI coating quality. Based on these ndings, all of our subsequent samples were pretreated according to

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Table II. Substrate cleaning solution temperature and consistent HSZ MFI coatings, indicating greater than 99% successfully coated. Cleaning temperature C Ambient 45 60 80 Alluminum Alloy 2024-T4 5052-H32 6061-T6 7075-T6

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the protocol of cleaning in Alconox detergent solution 3.0 g Alconox in 400 mL DI H2O at 60C for 1 h. At the time of this manuscript submission over one thousand aluminum alloy substrates have been coated with HSZ MFI. The XRD patterns of all of the coatings are consistent with MFI framework structure Fig. 1 . The similarity between XRD patterns among all the coatings suggests similar crystallographic random orientation. The surface SEM images Fig. 2a-d of the coatings on all AAs conrm the random orientation suggested by XRD. The surface images also show that the coatings are polycrystalline, compact, and continuous, which are conrmed by the cross-sectional images Fig. 2e-h . A vertical scale bar is provided in each of the cross-sectional images for better estimation of the coating thickness. The coatings on AA-6061-T4 and AA-7075-T6 are about 9 m thick Fig. 2f and h whereas the ones on AA-2024-T3 and AA-5052-H32 are around 12 m Fig. 2b and d . Because the zeolitic micropores are plugged by the SDA molecules, pinholes become the most crucial parameter in determining corrosion resistance of a polycrystalline zeolite barrier coating. It is expected that higher intergrowth leads to higher corrosion resistance. Surface Fig. 2a-d and cross-sectional Fig. 2e-h SEM images conrm the formation of HSZ MFI coatings with excellent intergrowth, suggesting possible good corrosion resistance. Corrosion resistance of the HSZ MFI coatings was examined by dc polarization, a commonly used technique for corrosion studies.20 In a typical polarization curve, lower polarization current means high corrosion resistance or vice versa. Corrosion resistance of HSZ MFI on AAs was tested in three corrosive media Fig. 3 . Resistance to general corrosion was tested in both acidic 0.5 M H2SO4 aqueous solution, Fig. 3a and basic 0.5 M NaOH aqueous solution, Fig. 3b media. General corrosion is characterized as non-localized corrosion over the entire surface. Resistance to localized corrosion was tested in an aggressive pitting corrosive medium 0.5 M NaCl adjusted to pH 3.0 with HCl Fig. 3c .

Figure 2. Surface a,b,c,d and cross-sectional e,f,g,h SEM images of HSZ MFI coating on Al-alloys: AA-2024-T3 a,e , AA-5052-H32 b,f , AA6061-T4 c,g , AA-7075-T6 d,h .

Figure 1. XRD patterns of HSZ MFI coatings on aluminum alloys. Asterisk indicates reections due to aluminum alloy.

Overall, the corrosion currents of the coated AAs are 47 orders of magnitude smaller than the corresponding non-coated bare Alalloys, indicating good barrier properties of zeolite coatings in both general and pitting corrosive media. Samples shown in Fig. 3a and c were immersed in the corrosive medium for 30 min prior to dc polarization testing. Samples tested in 0.5 M NaOH medium were immersed in the corrosive solution for 2 min prior to dc polarization testing. The shortened immersion time for the NaOH solution was necessary in order to start the corrosion testing before a protective oxide layer formed on the bare Al-alloys. The data clearly shows that MFI coatings can signicantly reduce corrosion on AAs. Coating delamination was not observed after polarization tests under optical microscope or SEM. Corrosion testing under similar and more harsh corrosion environments by Cheng et al. demonstrated that both anodized and chromate conversion coatings did not protect the underlying Al-alloy from serious general and pitting corrosion, whereas HSZ MFI coatings completely protected the underlying AAs from corrosion.6 Strong adhesion of the zeolite coating to the metal surface is of critical importance. Void space at the coating-metal interface is responsible for the accumulation of water and ions at the interface, and believed to be a primary failure mechanism for corrosion resistant coatings.21 It is known that the chemical nature22 and the structural properties23-25 of the substrate surface inuences nucleation, growth and adhesion of zeolite crystals. It appears that AAs can induce a strong gel-substrate interaction during coating formation leading to strongly adhered coatings. Strong interaction between the coating and AAs was indicated from the cross-sectional images of the coatings Fig. 2e-h . No delamination of the coating occurred during MFI removal in 49 wt % hydrouoric acid. To quantify the adhesion of the MFI coatings to the AAs, ASTM Standard D 3359-02 cross cut tape test was used. MFI coatings on all AAs received the highest rating, 5B, for strength of adhesion. Although not required by the ASTM D3359, the tested samples were analyzed under a high resolution polarized light microscope to provide a more

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Figure 4. Polarized light microscope image of high-silica-zeolite MFI coating on a AA-2024-T3, b AA-5052-H32, c AA-6061-T4, d AA7075-T6 tested for adhesion by ASTM standard D 3359-02 Method B.

Figure 3. DC polarization curves for bare and HSZ MFI coated aluminum alloys 1: 2024-T3; 2: 5052-H32; 3: 6061-T4; 4: 7075-T6 preincubated in corrosive media. a 0.5 M H2SO4 30 min preincubation ; b 0.5 M NaOH 2 min preincubation ; c 0.5 M NaCl/HCl pH 3.0 30 min preincubation .

critical look at the adhesion of MFI coating on each AA Fig. 4 . Note that the gap between the blades is very small 1.0 mm , and there was no signicant peeling off of coatings after the cross cutting through the zeolite coating for all alloy types. Similar to corrosion resistance, despite the chemical composition differences Table I , strong adhesion has been achieved for HSZ MFI coating on all AAs. One possible explanation for the excellent adhesion observed between the coating and AA is the incorporation of substrate aluminum into the ZSM-5 coating. It is well known that when MFI membranes are prepared on alumina supports, aluminum can be leached from the support and incorporated into the MFI framework, due to the highly alkaline conditions prevailing during synthesis.26 Support materials have been shown to contribute both aluminum11,26-28 and silicon29 to zeolite membranes synthesized by in situ hydrothermal methods on different substrates. To investigate this, a MFI coated AA-2024-T3 was embedded in epoxy, cut into cross-sectional wafers with a diamond saw, polished Fig. 5a , and subjected to EDAX

microanalysis to determine the silicon to aluminum ratio of the HSZ MF1 coating at different points from the substrate/MFI interface Fig. 5b . The MFI coating near the substrate/MFI interface has a very low Si:Al ratio, but the ratio increases as measurements are taken at points on the MFI coating distal to the interface to a maximum at the surface approaching innity surface Si/Al ratio measured by XPS , suggesting that aluminum from the substrate is in close association with the zeolite coating near the interface. The coatings appeared to be rooted into the AA surface despite the fact that the sample was subjected to severe mechanical shock from the diamond saw and from polishing. The strong adhesion also enabled successful polishing of the surface of the MFI coating without cracking or delamination Fig. 5a . Similar results were obtained by Dong et al., Yan et al., and Lai et al. They showed elemental analysis proles of aluminum content across MFI coatings synthesized on alumina supports decreases in the direction towards the zeolite coating surface.11,27,30 Dong et al. and Yan et al. observed no well-dened zeolite layer, distinct from the substrate, from cross-sectional SEM micrographs, and attributed the membranes good stability after calcination to strong adherence between the coating and substrate surface. Strong adhesion of the MFI coating to AA substrates is controlled, in part, by the physiochemical properties of the substrate. High mechanical strength zeolite coatings have been achieved on substrates with a large number of surface hydroxyl groups.31 When aluminum containing substrates are placed in zeolite synthesis solutions of high pH, the surface is partially dissolved during synthesis,32 generating surface aluminum oxides. Harvey and Glasser reported that aluminum acts as a cross-linking agent in the condensation of aluminosilicates.33 The strong adhesion observed between the MFI coatings and AA substrates is most likely the result of substrate aluminum leaching and incorporation into the zeolite framework, as well as, substrate surface oxides participating in condensation reactions with silanols on zeolite surfaces. Chromium-based coatings provide excellent corrosion resistance to aluminum, its alloys and other metals; however, different chemical formulations and substrate pretreatments are required to generate these protective coatings on the various metals and their alloys.34-38 In addition, intermetallic particles and inclusions present within metal alloys often pose serious problems for chromate conversion coatings. Frequently, the thickness of the protective coating is signicantly thinner over these inclusions and thus severely compromise their corrosion performance.34-38 In comparison, zeolite coatings are of a uniform thickness over the entire substrate surface, including the intermetallic particles and inclusions. The intermetallic particles and inclusions also present problems for the substrate cleaning and preparation for chromate based coatings. During substrate cleaning and preparation, the intermetallic particles and inclu-

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Figure 5. a SEM of polished MFI coating on AA-2024-T3 after being imbedded in epoxy and cut with a diamond saw and b Si/Al ratio determined by EDAX at specic distances from AA/MFI interface.

sions can be exposed, thus potentially compromising the corrosion resistance of the chromium based coatings. In contrast, zeolite coating synthesis uses a substrate cleaning and preparation on all metals and alloys that is extremely mild and only required a simple immersion in cleaning solution using a commercially available detergent. Conclusions In summary, we have shown that a single chemical formulation is able to generate excellent corrosion-resistant HSZ MFI coatings on all of the aluminum alloys studied. This same formulation has also produced excellent corrosion-resistant HSZ MFI coatings on stainless and carbon steels6,9 and thus is highly likely to provide excellent corrosion resistant coatings on many other metal types. The metal cleaning and pretreatment required for MFI coating deposition is extremely mild and one simple cleaning method can lead to effective coatings on all of the aluminum alloys. The coatings are of uniform thickness across the entire metal surface, including intermetallic particles and inclusions. The HSZ MFI coatings possess excellent adhesion to the substrates. All of the useful features demonstrated in this study plus the fact that the in situ crystallization method is intrinsically simple, clean, and environmentally friendly suggest that zeolite coatings can be viable replacements for chromium based corrosion-resistant coatings. Acknowledgments We acknowledge the nancial support from the Strategic Environmental Research and Development Program of the Department of Defense DoD/SERDP .
The University of California, Riverside, assisted in meeting the publication costs of this article.

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