Thin Solid Films 520 (2012) 5267–5271

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Thin Solid Films
journal homepage: www.elsevier.com/locate/tsf

Silica doped with lanthanum sol–gel thin films for corrosion protection
M. Abuín a, A. Serrano b, J. Llopis a, M.A. García b, c, N. Carmona a,⁎
a
b
c

Department of Materials Physics, Complutense University at Madrid, Avda. Complutense sn, 28004 Madrid, Spain
Glass and Ceramic Institute, CSIC, C. Kelsen 5, 28049 Madrid, Spain
IMDEA Nanoscience, Fco. Tomás y Valiente 7, 28049 Madrid, Spain

a r t i c l e

i n f o

Article history:
Received 13 September 2011
Received in revised form 13 March 2012
Accepted 16 March 2012
Available online 27 March 2012
Keywords:
Lanthanum
Corrosion protection
Sol–gel film
Scanning electron microscopy
X-ray absorption spectroscopy

a b s t r a c t
We present here anticorrosive silica coatings doped with lanthanum ions for the protection of metallic surfaces as an alternative to chromate (VI)-based conversion coatings. The coatings were synthesized by the
sol–gel method starting from silicon alkoxides and two different lanthanum precursors: La (III) acetate hydrate and La (III) isopropoxide. Artificial corrosion tests in acid and alkaline media showed their effectiveness
for the corrosion protection of AA2024 aluminum alloy sheets for coating prepared with both precursors. The
X-ray absorption Near Edge Structure and X-ray Absorption Fine Structure analysis of the coatings confirmed
the key role of lanthanum in the structural properties of the coating determining its anticorrosive properties.
© 2012 Elsevier B.V. All rights reserved.

1. Introduction
The corrosion of metallic structures has a significant impact on
countries economy and a big effort is made every year to overcome
its effects. The common use of Cr (VI) as anticorrosive pre-treatment
for metallic surfaces is becoming increasingly restrictive due to its carcinogen characteristic for the human race and substantial contribution
to environmental pollution [1]. Therefore, recent restrictive legislation
according to anticorrosive pre-treatments based on chromates has
motivated further studied on this field. In recent years, corrosion inhibitors with lower environmental impact as conventional ones are
used to delay corrosion on metallic materials forming the so-called
smart coatings [2]. In this sense, materials containing rare earth ions,
as lanthanum ions, constitute an interesting alternative because of
their good self-healing properties.
One of the most interesting and economical alternatives to obtain
thin films with improved properties is sol–gel technology [1,3]. Compared to other methods, it offers many advantages such as their transparency, good adhesion, hydrophobic character, abrasion resistance,
chemical and thermal stability, or easy cleaning [4,5]. They are environmentally friendly and waste-free. Additionally to the protective
character of the developed films, the possibility to develop them at
economically viable costs is also a critical factor to consider sol–gel
coating for the anticorrosive industry. The main drawback of this process is the limited thickness able to reach (b1 μm). To overcome this

⁎ Corresponding author.
E-mail address: n.carmona@fis.ucm.es (N. Carmona).
0040-6090/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.tsf.2012.03.046

limitation, the addition of inhibitors and the formulation of hybrid
compositions are the main strategies.
Development of additional routes for synthesis and preparation of
complex oxides with functional properties requires a better understanding of the relationship between their structure, and the physical
properties. In general, EXAFS (X-ray Absorption Fine Structure) and
XANES (X-ray absorption Near Edge Structure) have proved to be
useful techniques for structural studies of amorphous materials like
glasses and gels (coordination, chemical nature of bonding, symmetries, etc.) [6,7].
In this work we address the preparation of Lanthanum doped silica coatings by sol–gel method and the study of their anticorrosive
properties. We try to establish the relationship between the coating
structure and its properties. To this purpose, sol–gel films were prepared using different La precursors and upon different preparation
conditions. The structure of the coating was studied by X-ray Absorption Spectroscopy (XAS) measurements at the La L3-edge to determine its effect in the anticorrosive properties.
2. Experimental section
2.1. Thin films preparation
Films were prepared from solutions composed of tetraethylorthosilicate (TEOS) and methyl-triethoxysilane (MTEOS) as precursors, distilled
water to perform the hydrolysis, absolute ethanol as solvent and nitric
acid as catalyst. The respective molar ratios were 0.8:0.2:3:8:0.01. Finally,
La (III) acetate hydrate (a-) or La (III) isopropoxide (p-) were added in
1 mol% as doping agent. The solutions were stirred for at least 2 h before
deposition. Films were deposited upon microscope glass slides and

. Samples were immersed into an acid solution (HCl 0. The coatings resulted homogeneous. 2. Sample name La content (mol%) La (III) precursor Densification temperature (°C) La-a-20 La-a-100 La-a-500 La-p-20 La-p-100 La-p-500 1 1 1 1 1 1 Acetate hydrate Acetate hydrate Acetate hydrate Isopropoxide Isopropoxide Isopropoxide 20 100 500 20 100 500 10 µm Fig. They presented high transparency with transmittance over 90% in the VIS range (400–700 nm) while the cut-off at 50% transmittance was 301 nm (see Table 2).0 kV. n1.2 eV.3 eV and 5861. 10 µm La-p-10 d Table 1 Samples compositions and characteristics. Calculations were made following the expression: t ¼ M· 10 µm Basic attack La-a-100 c λ1 ·λ2 2⋅ðλ1 ·n2  λ2 ⋅n1 Þ where M corresponds to 1 for two consecutive minimums or maximums and ½ for a consecutive minimum and maximum. Films resistance against corrosion was checked by weathering tests according to modified ISO 1776 and 695 Standard [8. Table 1 summarizes compositions and densification temperatures used during the synthesis.1 eV at a step increment of 0. 1 displays the Scanning Electron Microscope (SEM) images of the La-a-100 and La-p-100 films after acid and basic attack.2 92.0 mm s− 1).1 N at 25 °C) or into a basic one (NaOH 0. c) La-a-100 after basic attack and d) La-p-100 film after basic attack. Fig. Films thickness was obtained from interference of transmittance spectra in the ultraviolet–visible-near infrared regions (UV–VIS-NIR) according to [10]. Optical property La-a-100 La-p-100 Average transmittance (%) (400–700 nm) Wavelength cut-off at 50% T (nm) Coating thickness without weathering (nm) Coating thickness after acid attack (nm) Coating thickness after basic attack (nm) 93. Spectra were recorded from 200 to 800 nm with 0. b) La-p-100 after acid attack. 100 and 500 °C. After coating. Superficial features of the La thin films later on were observed with a JEOL Scanning Microscope 6335 F working at 10. n2 are refractive indices corresponding to wavelengths λ1 and λ2 respectively.2. / Thin Solid Films 520 (2012) 5267–5271 aluminium alloy AA2024-T3 sheets by dip coating at a constant drawing speed (2.2). Abuín et al.5 nm spectral resolution. XANES spectra were collected at room temperature in fluorescence mode at the La L3-edge (p-d transitions) between 5406. colourless. without cracks.07 301 233 ± 16 295 ± 5 271 ± 7 301 205 ± 13 278 ± 5 90 ± 50 Coatings effectiveness to corrosion resistance was confirmed by means of accelerated ageing tests by immersion in acid and basic solutions (as explained in 2. crack-free and showed well adhesion. room temperature (25 °C) and relative humidity (35%). Structural study of the La environment XANES and EXAFS spectroscopy were performed in the beam line BM25 (Spanish-SPLine CRG) at the European Synchrotron Radiation Facility (ESRF). As it can be seen. Samples were placed behind a 1 mm width slit mask. monoliths of 20 mm diameter were also prepared.3. Films characterization Transmission spectra of films just prepared were measured with a UV–VIS-NIR Shimadzu 3100 double-beam spectrophotometer equipped with an integrating sphere.5268 M.6 ± 0. Four to seven scans of all samples were collected for signal averaging. surfaces are stable. Results and discussions Coatings containing 1 mol% of La2O3 were prepared on both.1 N at 25 °C) for 1 h. 1. The appearance of these surfaces is similar to Acid attack La-a-100 a 2. glass and aluminium alloy AA2024-T3 substrates. Table 2 Optical properties of the sol–gel films. SEM images of the surface morphology of the sol–gel films: a) La-a-100 after acid attack. pores or detachments. All spectra were calibrated by measuring standard La2O3 compounds as references. monoliths and films were dried and annealed in air at 20. The spectra were treated and normalized using the IEFFIT code. For convenience.43 ± 0. Film thicknesses determined in this way are shown in Table 2. 10 µm La-p-100 b 3. Samples for analysis (both films and monoliths) and reference compounds were placed at 45º from the incident X-rays and fluorescence signal was collected using a multi-element solid state detector.9].

Absorption (a.0 3. At temperatures above 300 °C the 5269 decomposition or oxidation of acetate ions may occur.0 5460 5480 5500 5520 5540 |χ(R)| (Å-2) Norm.u.5 1.5 2.) Norm. Absorption (a.) 1.5 0.5 Norm. 2. Coatings consolidated at low temperatures exhibit a significant fraction of organic matter and their spectra resemble those corresponding to the acetate. Absorption (a.5 2 0. a slight increase in the thickness after the immersion in solutions can be noticed for all films except for the La-p100 after basic attack (Table 2). converted into k space (conversion of energy [eV] to wavelength [inverse distance] and Fourier transformed the k-space data into R-space (conversion of wavelength to actual distance). 100 or 500 °C. Effect of densification temperature The La L3-edge XANES spectra recorded from the films prepared at different densification temperatures are shown in Fig. 0 2 4 6 R (Å) Fig.0 0.5 1.5 5600 5700 5800 Norm. The XANES spectra exhibit the edge at the same position but different white line intensity.M. The EXAFS region of the spectrum beyond the L3 edge provides a simultaneous measurement of the changes in the nearest neighbour interactions of La (bond distances and coordination number). which is higher for the acetate pointing out larger electronic localization in this compound. This indicates almost no alteration of the surfaces.0 2.8 0. indicating a higher delocalization of La 4f electrons due to hybridization with the surrounding oxygen atoms [7].) 4 2. The data were fitted using the Athena program.0 5400 5500 5600 5700 5800 5900 E (eV) Fig.0 5460 5480 5500 5520 5540 E (eV) 1 La-a-20 La-a-100 La-a-500 0 5400 5500 La(CH COO)3·xH2O 3 La 2O3 2. 4 shows a a 4.0 1.u. the white line intensity diminishes as the densification temperature increases. / Thin Solid Films 520 (2012) 5267–5271 the one of non-aged samples. This suggests no change in the lanthanum valence that remains La (III).0 0.u. It is well known that increasing the densification temperature of a sol–gel silica structure favours the evaporation of free water and occluded alcohol molecules. Nevertheless.5 3 4. although the precipitation of lanthanum hydroxide has been proposed by Mu et al. . L3 XANES normalized absorption of La-films prepared from a) acetate hydrate and b) isopropoxide densified at 20.0 4 0. In our case.2 4.5 2. 3 presents the XAS spectra for the La acetate and La2O3.2 0.1.5 3.0 0. the EXAFS oscillations were isolated after background subtraction of the raw data. No experimental evidence of salts or deposits was found on the surface of these films. This weathering seems to affect especially the film prepared from the alkoxide precursor.u. Higher densification temperatures lead to a more compact material reducing the presence of organic matter and the La adopts an environment and coordination more similar to the solid La2O3 compound [12]. [11]. Absorption (a. 3.0 1. In order to understand this temperature dependence of the XAS spectra.0 2.0 1. Therefore. Spectra of lanthanum reference compounds La2O3 and La(CH3COO)3·xH2O: a) L3 XANES normalized absorption and b) L3 EXAFS |X (R)|.4 1 La-p-20 La-p-100 La-p-500 0 0.0 3.5 1.0 5400 E (eV) 5450 5500 5550 5600 5650 E (eV) b b 4. displacement of the edge or variation in the intensity of pre-edge peaks with temperature is noticed.u. Absorption (a. 5489 eV and does not change significantly with the treatment at 20. No pre-edge shoulder. Abuín et al.0 1.6 E (eV) 0.) Norm.5 2 3. the more compact is the sol–gel structure that favours the hybridization between La and O orbitals in agreement with the XAS results while the La (III) coordination state remains unchanged. 3. 100 and 500 °C. the higher the densification temperature.) 3 La(CH COO)3·xH2O 3 La2O3 3. Fig. Fig. Actually.5 5900 0. This result is in agreement with the observed temperature dependence of the spectra corresponding to the coatings. The position of the absorption edge in the films appears at ca. 2.

it is important to determine if there are differences in the material structure and properties depending on the used precursors or if it can be chosen considering just economical reasons.68 Å respectively [13].6 1.43 Å for a CN of 6 and 2. The presence of this second neighbour. [7] in K2O-SiO2-La2O3 glasses La-p-20 La-p-100 La-p-500 1. In the coatings densified at low temperature (20 °C).4 0. suffering hydrolysis and polycondensation during the synthesis of the gel. La acetate hydrate is an economically affordable soluble salt. 3b) and is absent in the spectrum of La2O3. The ionic radii of La (III) ions are found 1. 100 and 500 °C. However.0 0. this neighbour appears only in the La acetate hydrate (Fig. 2. In these conditions. 0. EXAFS spectra of the reference compounds (Fig. This bonding distance is coincident to the sol–gel coatings densified at low temperature.8 0.2 0. Thus. 3 b) show similar interatomic La–O distance for La oxide and La acetate hydrate (ca.4 1. Oxygen ions (O 2 −) in CN 6 and CN 8 have ionic radii of 1.6 0. The assumption that they locate at interstitial positions or pores of the silica network is not yet proved.0 0 1 2 3 4 5 6 R ( Å) b 1. which has been identified by Jollivet et al. between 2. 5.87.43 Å.16 Å when is 8.2 |χ(R)| ( Å ) 1. when the coordination number (CN) is 6. the coordination number of La (III) ions in the films is reduced as densification temperature increases from 20 °C to 500 °C. the La–O bond distance diminishes to ca.4 0. La-ions can be incorporated in the silica network forming La–O–Si bonds or located in silica pores. 2 a and b) show that there are no significant differences in the position of the absorption edge. 3. and have been considered as lanthanum ions incorporated in silicate sites. the EXAFS spectrum for La2O3 can a 1. / Thin Solid Films 520 (2012) 5267–5271 the experimental EXAFS spectra of the prepared sol–gel films annealed at 20. the La (III) ions are surrounded by 8 O 2 − and the La–O bond distance is higher (ca. On the other hand. 4b and 5) indicate higher CN in coatings prepared with La acetate hydrate than for those prepared from La isopropoxide. 4).8 0.58 Å) yielding a threedimensional sol–gel network more open and expanded.6 0. and 1. 4 and 5) we deduce that there is little change in the oxygen first coordination shell.2 0. [14] at 3. Moreover. 4. The covalent radii of La. According to the radial distribution functions (Fig. Inter-atomic distances slightly diminish with the densification temperature irrespective of the used La precursors. Experimental EXAFS spectra corresponding to all La-films prepared (acetate hydrate and propoxide densified at 20.0 0. These results agree with the variations in the white line intensity observed in the XANES spectra.0 -2 -2 |χ(R)| (Å ) La-a-20 La-a-100 La-a-500 La-p-20 La-p-100 La-p-500 1.2 0.42 Å respectively. the second lanthanum neighbour is around 3. the radial distribution functions (Figs. Abuín et al. which needs to be solved. H and O are 1. the CN of the La (III) is reduced to 6 O 2 − ions surrounding each La 3 + and the sol–gel structure evolves to a one more close and compact one. From the EXAFS spectra (Figs. which are attributed to the specific synthesis route followed [15].8 0.4 0.82 Å. with very different structures leading to quite dissimilar EXAFS spectra.6 not be compared with those of the coatings densified at high temperature since they correspond to crystalline and vitreous materials respectively.58 Å for a CN of 8 atoms (calculated distances). 2. Therefore.0 0 1 2 3 4 5 6 R ( Å) Fig.8 Å.0 0.2. Experimental EXAFS spectra corresponding to La-films prepared from a) acetate hydrate and b) propoxide. It is worthy noting that the addition of even 1% of La ions could bring about this considerable improvement in properties.5 Å.5270 M. densified at 20. 2. . Thus.40 and 1. Effect of the La-precursor Lanthanum isopropoxide as well as TEOS are alcoxides. 0 1 2 3 4 5 6 R ( Å) Fig. As the densification temperature increases up to 500 °C. The anticorrosive properties of the coatings depend on the incorporation of La in the silica coating. These results are coherent with the ones found by Larson et al.6 Å). However.6 1. the La–O theoretical ionic bond distances are 2. Actually. The L3-edge XANES spectra from the films prepared from both precursors (Fig.03 Å. Neither the white line intensity changes significantly depending on the precursors (for the same densification temperature). EXAFS spectra confirm the elimination of organic matter and La incorporation in the silica coating as densification temperature increases. 100 and 500 °C).4 La-a-20 La-a-100 La-a-500 1. and preferred from the chemical point of view. A unique bond distance is observed for all acetate and propoxide films. 100 and 500 °C. the position of La (III) ions in the sol–gel structure after preparation is not fully known and will have influence in the final films anticorrosive properties. decreases with the densification temperature.4 0.23 and 0.2 -2 |χ(R)| (Å ) 1.4 and 2.2 1.

[2] A. Appl. Abuín et al. Wong. ACS Nano 3 (2009) 1753.G. [9] ISO 695. D. Mater. J. Carmona. NC acknowledged the financial support of the FSE-MEC.D.W. 2008. [7] E.A. [10] M. MA and AS acknowledge the UCM Campus of International Excellence (PICATA Program) and the CSIC (JAE Program) respectively.J. Villegas. RYC-2007-01715.P. S. Results show that the presence of La induces an effective delay of early corrosion of metallic substrates demonstrated by accelerated corrosion tests in acid and basic media. Tsavalas. J. J.A. S. 448 (1998) 163. Carmona. 5 we deduce that changes in the structure due to variations in the densification temperature are much larger than those due to different precursors. Villegas. Acknowledgements The authors acknowledge the Spanish Ministry of Economy and Competitiveness and Consejo Superior de Investigaciones Científicas for the financial support and for provision of synchrotron radiation facilities and we would like to thank the BM25-Spline staff for the technical support. R. [12] S. Navrotsky. Esp. This result points out that both La isopropoxide and La acetate hydrate can be used to prepare anticorrosive coatings. F.J. J. 4. [4] G. Bol. J.V. for pre-doctoral fellowships. from Fig. CRG Handbook of chemistry and physics.42 (±0. García. Resistance to Attack by a Boiling Aqueous Solution of Mixed Alkali. W. Simoni. C. Method of Test and Classification. / Thin Solid Films 520 (2012) 5267–5271 5271 with La–O bond distances of 2. Vidrio 39 (5) (2000) 641. project NANOBIOMAGNET (S2009/MAT-1726). Nevertheless. Fernández Navarro. Sibu. T. Lytle. Kumar. This work has been supported by the Spanish Ministry of Economy and Competitiveness through the projects FIS-2008- . M.K. E. Larson. Augustiniak. Mukerjee. 1975. 14 (2002) 2876.G. Chen. Ellison. P. [15] C. H.). Skorb. Taylor & Francis Group. A. Lide. M. 13 (2001) 3422.A. Interfaces 11 (2009) 2618. J. Ramón y Cajal program ref. Chem. Conclusions References To summarize. Glass. [8] ISO 1776. Soc. J. [11] Q. Auwer.R. G. Greegor. Villegas. Solids 353 (2007) 344. M. Ceram. Mater.M. J. Mu. Chen. Anticorrosive test above described shown good results for both precursors. Shen. Warrier. Lin. C. XAS studies confirmed the incorporation of La ions into silica sites to be crucial for the anticorrosive properties of the material. J.R. Thin Solid Films 515 (2006) 1320. [1] E. 06249 and Comunidad de Madrid. Fernández Navarro.B.V.M. Llopis. These properties are scarcely dependent on the La precursor used which can be then selected considering economical reasons. we have prepared sol–gel silica thin films doped with 1 mol% of lanthanum oxide starting from La (III) acetate hydrate and La (III) isopropoxide. A. [14] P. Delaye. [3] N. Chem. Skirtach. Glass.M. J. Jollivet. Chem. 1985.M.M. Electroanal.C.A. Resistance to Attack by Hydrolytic Acid at 100 Degrees C. . [6] G. McBreen. Solids 130 (1991) 260. Thin Solid Films 458 (2004) 121. New York. . Thin Solid Films 489 (2005) 130. Shchukin. Wang. Schottner. NonCryst. Flame Emission of Flame Atomic Absorption. Non Cryst.G.03 Å) and a coordination number lower than 7 for the La (III) ions. Y. Nanotechnology 20 (2009) 345602 (7 pp. [5] N.X. Möhwlad. A. Ming. Mukundan. [13] D. Mater. Paje. Y. Sviridov. D. 89th Ed.