Corrosion Science 46 (2004) 297312 www.elsevier.

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Chromate conversion coatings on aluminium: inuences of alloying

Y. Liu a, P. Skeldon
a

a,*

, G.E. Thompson a, H. Habazaki b, K. Shimizu c

Corrosion and Protection Centre, University of Manchester Institute of Science and Technology, P.O. Box 88, Manchester M60 1QD, UK Graduate Engineering School, Hokkaido University, N13 W8, Kita-ku, Sapporo 060-8628, Japan c University Chemical Laboratory, Keio University, 4-1-1 Hiyoshi, Yokohama 223, Japan Received 30 April 2003; accepted 19 June 2003

Abstract The growth kinetics of chromate/uoride conversion coatings are examined for 99.99% aluminium, and Al2.3at.%Cu, Al1.9at.%Au and Al20at.%Au alloys. The thickening of coatings and thinning of substrates, the latter deposited by magnetron sputtering, are determined by transmission electron microscopy. The results reveal consumption of substrates during the coating process, to the maximum immersion time of 24 min. Initial relatively rapid thinning in the period to 6 min is followed by slower, approximately constant thinning at about 9.3, 6.2, 6.0 and 5.4 nm min1 for the 99.99%Al, Al2.3at.%Cu, Al1.9at.%Au and Al 20at.%Au alloys respectively. The ratio of the number of chromium atoms in the conversion coating, determined by Rutherford backscattering spectroscopy, to the number of oxidized substrate atoms is about 3, indicating a low eciency of coating growth. Alloying decreases the coating thickness, as well as metal consumption. Alloying elements initially enrich beneath the coating, in alloy layers of a few nanometres thickness. Later, copper may be oxidized, and then enter the coating, whereas gold is occluded as nanoparticles. The gold nanoparticles act as markers to indicate formation of coating material at the metal/coating interface. Sudden loss of coating on the alloys, after about 69 min, occurs soon after entry of alloying element species into the coating. The loss may be related to the presence of nanoparticles of gold and copper near the alloy/coating interface, the latter possibly forming by reduction of copper species, that disrupt the bonding of the coating either directly though their presence or through their action as local cathodes. 2003 Elsevier Ltd. All rights reserved.

Corresponding author. Tel.: +44-161-200-4872; fax: +44-161-200-4865. E-mail address: p.skeldon@umist.ac.uk (P. Skeldon).

0010-938X/$ - see front matter 2003 Elsevier Ltd. All rights reserved. doi:10.1016/S0010-938X(03)00157-4

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Keywords: A. Aluminium; A. Alloys; Conversion coatings; Chromate

1. Introduction Chromate/uoride conversion coating is a highly eective method of pre-treatment of aluminium alloys for service in corrosive environments. The coatings combine excellence as a base for paints, simplicity of application and long-term corrosion resistance, with residual chromate ions contributing to the last [15]. A drawback is the potentially high cost of process control and euent treatment due to health hazards associated with hexavalent chromium. Consequently, there has been extensive research for replacements, although none has been proved as eective in overall performance [6,7]. The coatings have been used since the early part of the last century [8,9]. Numerous studies have been carried out of their growth, which involves formation of hydrated Cr2 O3 , typically a few hundred nanometres to a few microns in thickness, by immersion of the substrate in the chromate bath for a few minutes [5,8,10,11]. However, locally, the thickness of the coating on aluminium alloys can be greatly reduced where the second phase particles intersect the surface [1215]. Although an overall mechanism of coating formation is available for matrix regions composed mainly of aluminium [1618], understanding of local inuences of alloying elements is limited. Such inuences are investigated here, with focus on modication of the growth mechanism and the light that is shed on corrosion protection at second phase generally. There is also interest in the eects of alloying elements at the matrix regions, since the low levels of alloy element can be concentrated in the alloy layer just beneath the conversion layers [19]. Use of sputtering-deposited metastable alloys, free of signicant amounts of second phase, allows relatively precise measurement of thickness changes of the deposit due to growth of the coating, by transmission electron microscopy (TEM). Further, AlAu alloys provide opportunity to use gold as a marker to investigate sites of coating growth.

2. Experimental Chromate conversion coatings were grown on several sputtering-deposited materials, including 99.99% aluminium, Al2.3at.%Cu, Al1.9at.%Au and Al 20at.%Au alloys. Superimposed layers were also prepared from 99.99% aluminium and Al20at.%Au alloy. The various materials were deposited using an Atom Tech Ltd magnetron sputtering system, with 99.99% Al, 99.99% Cu and 99.9% Au targets. The chamber was rst evacuated to 2 107 mbar, with sputtering then carried out at 5 103 mbar in 99.998% argon. Materials were deposited at 0.1 nm s1 on to electropolished 99.99% aluminium substrates that were attached to a rotating copper table, the temperature of which remained below 308 K. Superimposed layers were deposited without interruption of sputtering. The working areas of specimens were

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dened by lacquer. Conversion coatings were then produced by immersion of specimens for selected times in a solution consisting of 3.5 g Na2 Cr2 O7 , 4 g CrO3 , and 0.8 g NaF in 1 l of deionized water at 293 K. Coated specimens were rinsed in deionized water, dried in cool air and stored in a desiccator. Electron-transparent sections of specimens were prepared by ultramicrotomy, with nominal thickness 10 nm, and examined by TEM in a JEOL 2000 FX II instrument. Coatings were analysed by Rutherford backscattering spectroscopy (RBS), using either 1.55 or 2.00 MeV He ions, supplied by the Van de Graa accelerator of the University of Paris. Data were interpreted by the RUMP program. 3. Results 3.1. 99.99% aluminium Transmission electron micrographs reveal thinning of the sputtering-deposited 99.99% aluminium and growth of the coating with increasing time of conversion treatment (Fig. 1(a)(c)). The initial metal layer, of thickness 475 25 nm, comprises columnar grains of width 100 25 nm (Fig. 1(a)). Roughness, up to 50 nm, at the layer surface is typical for the conditions of sputtering. Fine voids and oxide lm, the latter remaining from electropolishing, mark the interface between the deposit and the underlying aluminium. The coating thickens and the aluminium thins with increasing time of treatment, as disclosed by specimens treated for 1 and 24 min (Fig. 1(b) and (c)). The coating material is of amorphous appearance, with crack-like features that may arise from drying of the coating and damage during sectioning. Thinning of the aluminium is relatively rapid in the rst 3 min of treatment, during which about 100 nm of metal are consumed (Fig. 2(a)). The rate then reduces to an approximately constant value of 9.3 nm min1 between 6 and 24 min, the longest immersion time employed. The coating correspondingly thickens rapidly in the rst 3 min, forming a layer of thickness about 200 nm (Fig. 2(b)) at an average rate of 67 nm min1 . Thereafter, growth slows substantially, with a thickness of about 280 nm achieved at 24 min, at an average rate of about 4.4 nm min1 . The apparent eciency of conversion of aluminium was determined by measurements of the chromium contents of coatings by RBS, which were compared with the thinning of the aluminium, from TEM. Examples of RBS spectra are shown later for the alloys (see Fig. 5); spectra for aluminium were similar, though obviously without signals for alloying elements. A high eciency would correspond to reduction of one Cr(VI) species, with incorporation of the product Cr(III) species into the coating, for each aluminium atom that is oxidized. The results reveal that the number of aluminium atoms in the consumed aluminium exceeds the number of chromium atoms in the coating material. The ratio varies with time of coating, being in the approximate range 34 following treatments for between 1 and 24 min (Fig. 3). Thus, only 2533% of oxidized aluminium atoms lead to chromium species in the nal coating.

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Fig. 1. Transmission electron micrographs of high purity aluminium sputtering deposited onto a high purity aluminium substrate following deposition (a), and later chromate conversion treatments for 1 min (b) and 24 min (c).

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350 300 Matrix Consumed (nm) 250 200 150 100 50 0 0 (a) 300 250 Coating Growth (nm) 200 150 100 50 0 0 (b) 5 10 15 Time (min) 20 25 Superpure Al Al-2.3Cu% Al-1.9Au% Al-20%Au Al-Au multilayer 5 10 15 Time (min) 20 25 Superpure Al Al-2.3Cu% Al-1.9Au% Al-20%Au Al-Au multilayer

301

Fig. 2. Loss of substrate thickness (a) and thickness of conversion coatings (b), determined from transmission electron micrographs, for high-purity aluminium, Al2.3at.%Cu, Al1.9at.%Au and Al20at.%Au alloys, and a superimposed high-purity aluminium/Al20at.%Au alloy/electropolished aluminium substrate, following chromate conversion treatments.

3.2. Al2.3at.%Cu alloy The Al2.3at.%Cu alloy of thickness 360 20 nm, with columnar grains of width 50 20 nm and surface roughness of about 20 nm, also reveals progressive thinning with increasing time of treatment, as revealed by comparison of the initial alloy and following treatments for 1 and 24 min (Fig. 4(a)(d)). Similar to the previous trend, the thinning is fastest in the rst 3 min of treatment, followed by a slower, roughly constant, rate of thinning, at 6.2 nm min1 . The latter rate is lower than that of 99.99% aluminium by about 33% (Fig. 2(a)). The coating thickens in the rst 6 min of treatment, but at longer times coatings are greatly reduced in thickness (Fig. 2(b)). The initial coatings resemble those formed on the high purity aluminium (Fig. 4(b)),

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10 9 8 7 6 Al/Cr 5 4 3 2 1 0 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 Time (min)

Fig. 3. Number of aluminium atoms consumed, determined from loss of substrate thickness by TEM, and number of chromium atoms in the conversion coating, determined from RBS, for high-purity aluminium following chromate conversion treatments.

Fig. 4. Transmission electron micrographs of Al2.3at.%Cu alloy sputtering deposited onto a high purity aluminium substrate following deposition (a), and later chromate conversion treatments for 1 min (b), 6 min (c), and 12 min (d).

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but those following the thickness reduction have an altered ne texture (Fig. 4(d)). Atomic number contrast indicates enrichment of copper in an alloy layer of thickness about 2 nm just beneath the coating. Accurate measurement of thicknesses of enriched layers for this and later alloys is hindered by the roughness of the alloy/ coating interfaces. Typical RBS spectra for the conversion-coated alloy reveal peaks for chromium (Fig. 5(a)), with the peak width dependent upon coating thickness. As expected, the position of the leading edge of the peak, about channel 360, indicates chromium at the surface of the specimen. The aluminium yield, at lower energies, is shifted from the position for surface aluminium, with the shift being similar to the width of the chromium peak. Thus, the main part of the coating material contains no measurable amount of aluminium, with the Al:Cr atomic ratio being less than 0.05, based on pile-up background in the region between the chromium and aluminium yields. The depth resolution is insucient to detect any alumina layer, of a few nanometres

Fig. 5. Experimental and simulated (solid line) RBS spectra for (a) Al2.3at.%Cu (inset of (a)treatment for 12 min.), (b) Al1.9at.%Au and (c) Al20at.%Au alloys with respective chromate treatments of 3, 6 and 3 min. The bars indicate energies corresponding to Al, Au and Cu at the surface.

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thickness, immediately adjacent to the metal. Dips in the aluminium yield, from regions of buried metal layers, indicate the back of the deposited metal. The oxygen yield from the coating is superimposed on the yield from aluminium. Chromium and oxygen signals were consistent with coating material composed of Cr2 O3 nH2 O (n % 2). Notably, the initial coating was free of copper species, which was evident from the shift in the copper yield from the position corresponding to near surface concentrations, by amounts correlating with the coating thickness. The background signal indicated Cu:Cr ratios of less than 0.005 in the main coating material. Yields due to enrichment of copper in the alloy were usually obscured due to coincidence of the enrichment peaks with the much greater peaks of the chromium in the coatings. The peak at channel numbers immediately to the left of the chromium peak is due to an enhanced concentration of copper in the rst few atomic layers of the deposited alloy, which arises as the targets settle to the steady sputtering condition. For more protracted treatment times of the alloy, when the coatings are signicantly thinner than previously, indicating detachment of the coating, copper enrichment at the near surface is revealed (see arrow in inset of Fig. 5(a)). The enrichment level, of about 9 1015 Cu atoms cm2 , is about 50% higher than that required beneath amorphous alumina lms in order that copper can be oxidized [19], suggesting there may be additional contributions, for instance from re-located copper. The ratio of the numbers of aluminium atoms oxidized, determined from thickness reductions of alloy layers from TEM, and the numbers of chromium atoms in the coating, from RBS, is about 2 at immersion times just before loss of coating thickness. The result is apparently lower than that found for high purity aluminium, which may relate to overestimate of the amount of chromium in the coating due to overlap of signals of copper and chromium in RBS spectra and variability in the initial thickness of the alloy layers between specimens. 3.3. Al1.9at.%Au alloy The behaviour of the Al1.9at.%Au alloy, which comprised grains of size about 4060 nm and surface roughness of about 30 nm, was similar to that of the previous alloy, with respective rates of thinning of about 6.0 and 6.2 nm min1 in the approximately linear region following the relatively rapid initial coating development (Fig. 6(a)(d), Fig. 2(a)). The coating also reduced in thickness for treatments times above 6 min (Fig. 2(b)). The alloy layer, of original thickness 160 15 nm, was consumed between immersion times of 16 and 24 min. The coating formed for up to 6 min was similar in appearance to that on aluminium. Enrichment of gold occurred in the alloy in a layer of thickness about 2 nm (Fig. 6(b)). For treatment times up to 6 min, there was no evidence of gold in the coating. However, at longer times, particles of gold, of size about 5 nm, were incorporated into coating material of altered texture. The RBS spectra prior to coating loss were similar to those for the Al2.3at.%Cu alloy, revealing absence of gold in the initial coatings composed of Cr2 O3 nH2 O (Fig. 5(b)). Enrichment of gold in the alloy was readily evident, with levels reaching about 6 1015 Au atoms cm2 at 6 min immersion. The ratio of the numbers of

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Fig. 6. Transmission electron micrographs of Al1.9at.%Au alloy sputtering deposited onto a high purity aluminium substrate following deposition (a), and later chromate conversion treatments for 1 min (b), 6 min (c), and 16 min (d).

aluminium atoms oxidized, from TEM, and the numbers of chromium atoms in the coating, from RBS, is about 3 at an immersion time of 6 min, just prior to loss of coating thickness. The result is close to that obtained for the high-purity aluminium. 3.4. Al20at.%Au alloy The relatively thin layer of Al20at.%Au alloy, of thickness 80 15 nm, was of indistinct structure, possibly consisting of amorphous and crystalline regions, with surface roughness of about 30 nm (Fig. 7(a)). The alloy enriches in gold, in a layer of thickness about 10 nm, during the initial formation of the conversion coating, with gold particles already being incorporated in to the coating following treatment for 3 min (Fig. 7(b)). By 14 min, the alloy layer is consumed, and gold particles are present throughout the coating (Fig. 7(c)). Coating then develops at a greatly increased rate beneath the gold-containing coating by conversion of the electropolished aluminium. (Fig. 7(d)). The average rate of thinning of the alloy was about 30% of that of high purity aluminium (Fig. 2(a)). The coating thickened on the alloy at a

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Fig. 7. Transmission electron micrographs of Al20at.%Au alloy sputtering deposited onto a high purity aluminium substrate following deposition (a), and later chromate conversion treatments for 3 min (b) 14 min (c), and 16 min (d).

correspondingly low rate, with a rate in the linear region of about 4.5 nm min1 , until the alloy was fully converted (Fig. 2(b)). RBS spectra revealed peaks for chromium in the coating and gold in the relatively thin alloy layer and in the coating material (Fig. 5(c)). The thinness of the alloy and coatings prevented resolution of detailed distributions of species in the specimens in the stages prior to consumption of the alloy. However, signicant loss of chromium was evident with increasing the time of coating from 1 to 6 min. Thus, the initial coating, at 1 min, contained about 7 1016 Cr atoms cm2 . This amount reduced by factors of 2.0 and 4.0 at 3 and 6 min respectively. In contrast, the level of gold diminished by very small amounts, corresponding to respective factors of 1.01 and 1.03. Thus, coating material, but little gold, is lost from the alloy during immersion. Following consumption of the alloy, new coating material clearly formed beneath the gold-containing material, consistent with TEM observations. 3.5. High-purity aluminium/Al20at.%Au alloy The initial specimen comprised 45 10 nm of Al20at.%Au alloy deposited onto electropolished aluminium, with a nal layer of 99.99% aluminium, of thickness 85 15 nm, deposited on the alloy (Fig. 8(a)). Consistent with previous kinetics (Fig. 2(a)), the aluminium layer was consumed within 3 min of treatment (Fig. 8(b)). Conversion of the Al20at.%Au alloy then proceeded at an approximately constant

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Fig. 8. Transmission electron micrographs of a superimposed high-purity aluminium/Al20at.%Au alloy/ electropolished aluminium substrate following deposition (a), and later chromate conversion treatments for 3 min (b), 12 min (c), and 14 min (d).

rate, almost 10 times slower than that for 99.99% aluminium and similar to that in the nal stages of the previous specimens. Following 12 min immersion, gold was enriched in a residual alloy layer of thickness about 18 nm, located immediately beneath the coating (Fig. 8(c)). By 14 min, the alloy was consumed, and gold particles formed a marker layer within the coating, with coating material developing beneath the marker by conversion of the electropolished aluminium (Fig. 8(d)). At this stage, the coating was of greatly reduced thickness.

4. Discussion 4.1. Coating growth on aluminium Previous work has shown that in the early stages of conversion treatment of electropolished aluminium hydrated chromium oxide develops preferentially at local cathodic sites coinciding with ridges of the textured surface, where impurities may segregate [16]. With increased time of treatment, a more uniform coating forms and inuences of the substrate are less noticeable. In the present work, such coatings of

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relatively uniform thickness had been established at the shortest treatment times employed of 1 min. The coating on high-purity aluminium thickens rapidly to about 200 nm in 3 min, with the rate then reducing by a factor of roughly 15 between 6 and 24 min. The rate of thinning of the aluminium also reduces at about 3 min, but only by a factor of about 3. The overall reaction for coating formation, including the parallel processes of oxidation of the aluminium to form alumina and reduction of chromate ions, is given by: 2Al Cr2 O2 2H n 1H2 O ! Cr2 O3 nH2 O Al2 O3 7 Accordingly, one Cr(VI) ion is reduced with oxidation of one aluminium atom. Fluoride ions dissolve the alumina at the base of the coating, forming soluble aluminium uoride, by the reaction Al2 O3 6HF ! 2AlF3 3H2 O that allows oxidation of aluminium to proceed relatively rapidly. Dissolved aluminium species are presumed to diuse through the coating to the solution, since amounts of aluminium in the nal coating are low. According to RBS and TEM, approximately three aluminium atoms are oxidized for each chromium atom that is incorporated into the coating. The low apparent eciency can be explained by one, or a combination, of dissolution of coating material, mechanical loss of coating material, or side reactions that consume aluminium or that form soluble chromium species. Considering the rst possibility, the 99.99% aluminium/Al20at.%Au alloy results in a coating of relatively constant thickness for treatment times between 3 and 12 min. In this period, growth of the coating is retarded by the underlying alloy, which is reached by about 3 min. In order to explain the low eciency on high-purity aluminium, the equivalent of about 400 nm of coating material should dissolve during 9 min immersion. This would require practically total loss of the coating on the superimposed-layer specimen, which clearly does not occur. Further, there is no evidence of mechanical loss of such a thickness of material, until later times of immersion. Thus, it appears that side reactions are important, such as reduction of oxygen, evolution of hydrogen or reduction of chromate ions with formation of soluble chromium uoride. The thinning of aluminium during coating formation is equivalent to an average corrosion current density in the rst 3 min of about 1.6 mA cm2 , thereafter reducing to a steady value of about 0.5 mA cm2 . These values greatly exceed the levels for diusion-controlled reduction of oxygen, which can only make a minor contribution to the total cathodic current. Hydrogen evolution is potentially a greater contributor due to the abundance of H ions. However, evidence of gas generation appeared only for the alloys, with isolated bubbles forming on the surface of the specimen during treatment. Concerning the formation of soluble chromium uoride, no experimental support for its presence appears to have been published.

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4.2. Inuence of alloying The addition of copper and gold to aluminium reduces the kinetics of growth of the coating. In the case of gold, increased addition further slows coating development. The steady current densities following the more rapid initial coating formation for the Al2.3at.%Cu, Al1.9at.%Au and Al20at.%Au alloys are about 0.3 mA cm2 respectively. The initial rates of growth of coating material on the highpurity aluminium and the Al2.3at.%Cu and Al1.9at.%Au alloys are similar, such that the thicknesses after treatment for 1 min, about 6070 nm, agree within experimental accuracy. Enrichments of copper and of gold are developing in the alloy beneath the coating, which is typical of oxidation of dilute AlCu and AlAu alloys in the presence of an amorphous alumina-based lm, as in anodizing and electropolishing [19,20]. From previous studies of anodizing, only aluminium atoms are expected to oxidize until about 43 and about 52 nm of the present Al2.3at.%Cu and Al1.9at.%Au alloys have been consumed, with generation of enrichments of about 6 1015 Cu atoms cm2 and about 6 1015 Au atoms cm2 [19,21]. The latter value is estimated from measurements on an Al3.8at.%Au alloy for which the enrichment was 8.5 1015 Au atoms cm2 , with the study indicating that the enrichment reduces with gold level in the bulk alloy [21]. The behaviour revealed follows reasonably expectations for the Al1.9at.%Au alloy, since gold particles have been incorporated into the coating following treatment for more than above 6 min, with thinning of the alloy by about 75 nm, according to results of Fig. 2(a), compared with predicted occlusion of gold particles with thinning of 52 nm. For copper, the maximum enrichment, usually required for its oxidation is predicted with thinning of the alloy by about 43 nm, at a treatment time of about 2 min indicated by Fig. 2(a). However, the precise time of commencement of incorporation of copper into the coating was not determined in the present experiments. Enrichment of the Al20at.%Au alloy is more rapid than for the dilute alloy, due to the increased availability of gold; thinning of <8 nm should develop the maximum enrichment within about 1 min of chromate treatment, neglecting pre-existing enrichment beneath the air-formed lm on the alloy. Thus, for the shortest treatment employed, namely 3 min, coatings contain gold particles, with gold-free coating material, of thickness 510 nm, at the coating surface. Loss of coating material, but negligible loss of gold, occurs with increased immersion time in the coating bath, probably due to mechanical detachment. The reduced rate of growth of conversion coatings on the alloys may be due to thermodynamic and kinetic factors. The enrichment of the copper in the alloy leads to a positive shift in the corrosion potential of AlCu alloys [22], which may indicate a shift in the equilibrium potential of the anodic reaction. Such a shift, expected also for AlAu alloys, during conversion treatment will reduce the thermodynamic driving force for coating formation that may reduce the kinetics of growth. In the case of the Al2.3at.%Cu alloy, the copper is oxidized, after prior enrichment in the alloy, at about 6 min, and hence, copper species, presumed to be units of CuO, or possibly Cu2 O, are incorporated into the alumina lm at the base of the coating. Copper ions then presumably enter the solution, along with aluminium ions, as the

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alumina layer if thinned by the uoride ions. For the Al1.9at.%Au alloy, the gold is present as metal nanoparticles, rather than as ionic species, although at this stage the possibility of direct incorporation of nanoparticles of copper is not ruled out depending upon the conditions at the alloy/coating interface. The nanoparticles may provide a physical barrier to ionic transport in the coating. However, the volume of particles in the coating is low, and the population density is probably too low to aect signicantly the kinetics of coating growth. For the Al20at.%Au alloy, there is a much greater possibility of physical hindrance of ion transport in the coating, although pathways around particles still appear to be present. The coating thickness reduces on the Al1.9at.%Au alloy around the time of occlusion of gold nanoparticles. Subsequently developed coating material contains gold nanoparticles throughout its thickness. The distribution of gold nanoparticles indicates that the coating develops mainly at the coating/alloy interface. Similar behaviour is evident for the Al20at.%Au alloy and for the superimposed layer specimen. Thus, the chromate ions are transported through the coating to the sites of reduction near the metal, which may involve electron tunnelling through a residual alumina layer next to the metal. The slower coating of the alloys, compared with that of the high-purity aluminium, suggests that the enrichment of the alloying element leads to the reduction in rate. Several studies have revealed the presence of Cr(VI) species in the hydrated Cr(III) oxide of the coating material [2,23]. Their presence can be explained by transport of Cr(VI) species through the coating to sites of coating formation near the alloy. With thickening and possible ageing of the coating, the transport is expected to slow, thereby reducing the rate of coating growth. 4.3. Detachment of coating Alloying elements are also associated with major reductions in coating thickness for treatment times in excess of about 6 min. The close coincidence of thinning of the coating on the alloys, indicating its detachment from the alloy, and achievement of enrichments of copper and of gold for their incorporation into the coating, suggests that detachment is directly associated with these events. In practice the detachment of the coating appeared to occur a short time after incorporation of gold or copper into the coating. Thus, detachment of the coating for the Al1.9at.%Au and Al 2.3at.%Cu alloys occurs with thinning of the matrix by 75 and 70 nm respectively, as indicated by results of Fig. 2(a), compared with predicted initial incorporation of alloying element species with respective thinning of 52 and 43 nm. This suggests a delay between incorporation and detachment of the coating that is related to the detachment mechanism. However, there are also some uncertainties in the thinning measurements related to small dierences in thickness of the deposited substrates between individual specimens. If the origins of detachment are essentially the same for the various alloys, the presence of gold as nanoparticles in the coating, contrasting with the possible oxidation of copper, may oer a clue to the common behaviours. In particular, reduction of copper ions that are released by dissolution of the alumina lm at the base of the coating, in addition to their relatively fast migration through the alumina layer and ejection to the solution, may generate ne

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copper deposits near the alloy/coating interface. The deposits can form since the potential of the AlCu alloy in the coating bath is in the region for stability of copper metal. Alternatively, copper nanoparticles may form directly if the potential is insucient for oxidation of copper. Thus, coatings on AlCu and AlAu alloys contain increased numbers of cathodic sites following achievement of the relevant maximum enrichments of the alloys. Several possibilities may then arise: the particles may physically weaken the bonding of the coating to the substrate; enhanced reduction of chromate may generate new coating material at a relatively high rate within the existing coating, with stresses leading to detachment; hydrogen gas may be evolved with pressures mechanically disrupting the pre-existing and newly forming coating near the alloy/coating interface. Such gas generation may explain the modied appearance of coating material formed at times after the initial detachment, with channels possibly then allowing release of gas to the solution without major disruption of the coating. Increased generation of hydrogen may also slow coating growth if the rate of reaction is under anodic control.

5. Conclusions 1. Growth of chromate conversion coatings on high-purity aluminium is relatively rapid in the rst 3 min, forming a coating of thickness 200 nm. The coating rate then reduces, becoming approximately linear over the period between 6 and 24 min at 4.4 nm min1 . Signicant thinning of the substrate takes place throughout the coating process, with a consumption rate in the linear region of coating of about 9.3 nm min1 . 2. The average number of chromium atoms incorporated into the conversion coating is approximately 2533% of the number of aluminium atoms consumed during the coating process, indicating a relatively low apparent eciency of growth of the coating material. 3. Addition of alloying elements, with formation of Al2.3at.%Cu, Al1.9at.%Au and Al20at.%Au alloys, reduces the growth rate of the coating and also the consumption of the metal, with the latter proceeding in the approximately linear region at 6.2, 6.0 and 5.4 nm min1 for each of the respective alloys. The thickening rate of the coating is slightly increased initially, with increasing alloying element concentration reducing the rate. Further, the Al2.3at.%Cu and Al1.9at./%Au alloys are also associated with relatively sudden losses of thickness of the coating after several minutes of the coating treatment. 4. In the case of copper, the initial coating is mainly free of copper species as copper is enriched in the alloy, in a layer of thickness about 2 nm, located immediately beneath the coating. A thickness of coating of about 70 nm is developed in this period. Later, copper species are incorporated into the coating when copper is enriched suciently in the alloy. 5. Similar enrichment processes take place with the gold-containing alloys. Gold enriches more strongly than copper and is occluded in the coating as nanoparticles of gold metal.

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6. Gold nanoparticles, acting as inert and immobile markers in the coating, indicate that the conversion coating forms mainly at the metal/coating interface. 7. Detachment of coating material occurs shortly after gold and copper are incorporated into the coating. This behaviour may relate to formation of nanoparticles of gold and copper that disrupt bonding of the coating material and act as cathodic sites.

Acknowledgements The authors are grateful to the Engineering and Science Research Council for support of this work and to Dr. C. Ortega of the Groupe de Physique des Solides, Universits Paris 7 et 6, for assistance with RBS measurements (work partially e supported by the Centre National de la Recherche Scientique (GDR86)).

References
[1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] [12] [13] [14] [15] [16] [17] [18] [19] [20] [21] [22] [23] J. Zhao, L. Xia, A. Sehgal, D. Lu, R.L. McCreery, G. Frankel, Surf. Coat. Technol. 140 (2001) 51. L. Xia, E. Akiyama, G. Frankel, R. McCreery, J. Electrochem. Soc. 147 (2000) 2556. J. Zhao, G. Frankel, R.L. McCreery, J. Electrochem. Soc. 145 (1998) 2258. M.W. Kendig, A.J. Davenport, H.S. Isaacs, Corros. Sci. 34 (1993) 41. F.W. Lytle, R.B. Greegor, G.L. Bibbins, K.Y. Blohowiak, R.E. Smith, G.D. Tuss, Corros. Sci. 37 (1995) 349. S.M. Cohen, Corrosion 51 (1995) 71. R.L. Twite, G.P. Bierwagen, Prog. Org. Coat. 33 (1998) 91. D.B. Freeman, A.M. Triggle, Trans. Inst. Metal Finish. 37 (1960) 56. S. Wernick, R. Pinner, Surface Treatment and Finishing of Aluminium and its Alloys, vol. 1, fourth ed., Robert Draper Ltd., 1972. W. Marchand, Electroplating Metal Finish. 14 (1961) 439. J.A. Treverton, N.C. Davies, Surf. Interface Anal. 3 (1981) 194. Y. Liu, G.E. Thompson, P. Skeldon, C.J.E. Smith, K. Shimizu, Int. Symp. Aluminium Surf. Sci. Technol., Manchester, UK, May 2000, p. 479. P.L. Hagans, C.M. Haas, Surf. Interface Anal. 21 (1994) 65. L. Jus, A.E. Hughes, S. Furman, P.J.K. Paterson, Corros. Sci. 44 (2002) 1755. W.R. McGovern, P. Schmutz, R.G. Buchheit, R.L. McCreery, J. Electrochem. Soc. 147 (2000) 4494. G.M. Brown, K. Shimizu, K. Kobayashi, G.E. Thompson, G.C. Wood, Corros. Sci. 33 (1992) 1371. G.M. Brown, K. Shimizu, K. Kobayashi, G.E. Thompson, G.C. Wood, Corros. Sci. 35 (1993) 253. G.M. Brown, K. Shimizu, K. Kobayashi, G.E. Thompson, G.C. Wood, Corros. Sci. 34 (1993) 1045. H. Habazaki, K. Shimizu, P. Skeldon, G.E. Thompson, G.C. Wood, X. Zhou, Trans. Inst. Metal Finish. 75 (1997) 18. X. Zhou, H. Habazaki, K. Shimizu, P. Skeldon, G.E. Thompson, G.C. Wood, Thin Solid Films 293 (1997) 327. H. Habazaki, K. Shimizu, P. Skeldon, G.E. Thompson, G.C. Wood, X. Zhou, J. Phys. D 30 (1997) 1833. S. Garcia-Vergara, F. Colin, P. Skeldon, G.E. Thompson, P. Bailey, T.C.Q. Noakes, H. Habazaki, K. Shimizu, J. Electrochem. Soc., in press. L. Xia, R. McCreery, J. Electrochem. Soc. 145 (1998) 3083.