The effect of dye molecules in titania-silica hybrid coatings for corrosion protection

Tapan Kumar Rout

Research, Development and Technology, Tata Steel Ltd (Europe), Ijmuiden, The Netherlands
Abstract Purpose The purpose of this paper is to develop a corrosion resistant zinc-free coating for interstitial free steel. Design/methodology/approach The objective was achieved by developing a titania-silica hybrid coating through a sol-gel process by incorporating a dye molecule. The role of dye molecules was particularly important for enhancing the anti-corrosion properties of the coating. The approach of current research was to develop a low-temperature coating process that can bring similar performance to that obtained in case of zinc coating. Titania and silica precursors were mixed by stirring under a nitrogen atmosphere at 808C to formulate a low-temperature coating. The dye molecules were added before addition of water for subsequent hydrolysis. This complete formulation was applied over steel sheets using a roll coater as the application method. Findings The ranking order of improved corrosion resistance was found to be PATMS . EETMS . GPTMS and the addition of trace amount of tartrazine dye (60-65 mg/l of liquid) in PATMS increased the corrosion service life in saline environments from 168 to 216 h, thus showing a promising improvement. Scanning Kelvin Probe results indicated that the corrosion reaction is controlled cathodically in presence of dye and, electrochemical impedance spectroscopy results exhibited a charge transfer resistance (Ct) of coating with dye of 419V cm2, which was higher than that of a similar coating without dye (360V cm2), indicating increased corrosion protection. Research limitations/implications This coating had improved barrier protection but lacked cut edge protection. Future work will focus on adding sacricial protection by introducing compatible corrosion inhibitors, especially dye molecules, which are photosensitive. Practical implications This coating has huge potential for use in the automotive sector, especially for certain automotive parts (i.e. helm anges), which suffer from poor durability in salty and high-humidity atmospheres. Social implications Since this coating formulation utilises a partially aqueous base, some environmental impact cannot be avoided, but it will have less impact than a complete solvent base formulation. Originality/value The novelty of the work was the introduction of dye molecules as the corrosion inhibitor and their compatibility in the hybrid coating system. Keywords Inhibitors, Steels, Coatings technology, Dyes, Corrosion protection Paper type Research paper

Introduction
There are many composite coatings, which have been studied for the corrosion protection of carbon steel, as discussed by Carbajal et al. (2002). The unique properties of the composite coatings are that they exploit synergetic effects that can lead to innovative multifunctional materials. Rare earth sesquioxide (RE2O3) nanomaterials, such as europium sesquioxide (Eu2O3) and gadolinium sesquioxide (Gd2O3), HfO2 and ZrO2 are explored by many researchers for their potential use in such composite coatings. The thermal and chemical resistance of viable materials such as alumina, titania, cerium oxide, zinc oxide, copper oxide, antimony, tin oxide, chromate, montmorillonites and silicates most commonly are used for multifunctional building coatings via sol-gel, electrodeposition and dispersion techniques, etc. as discussed by Ye and Xie (2006), and Ono et al. (2004). In the progressing scientic world, from the Stone Age to the steel age (industrial revolution), to silicon age (telecom revolution), and now to now the polymer age, the challenge has been to nd engineered
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polymers and their composite coatings for anti-corrosion applications with similar performance to conventional metallic coatings. The introduction of organic components via direct blending or the chemically modied backbone of polymers for those inorganic components that are commonly known as hybrid coatings/composite coatings, has been explained by Kumar et al. (2008) and Zhou et al. (2009). Cutting-edge research is going on at many universities throughout the world. The application of these coatings over bare carbon steel substrates with properties that are similar to conventional metallic coatings (e.g. galvanizing) is a topic of much interest to the scientic community. The effectiveness of the composite coatings, in terms of their corrosion resistance, is largely due to the integrity and adhesion of the lm and to its neutrality towards corrosive solutions. Other important contributions to lm integrity are the degree of concentration of residual stresses at the substrate/lm interface and the morphology of the lm itself. These affect the structural resistance of the layer and the tendency for the lm to crack and allow localized corrosion. The roles of precursors in the hybrid sol-gel formulations, with respect to molecular conrmation, functionality, compatibility, crystallographic structure and layer-to-layer spacing, etc. are important criteria for homogeneous stable sol-gel coating. Some in situ sol-gel formulations utilizing catalytic polymerization have been attractive to the coating industries
The authors would like to thank Nitu Rani for corrosion tests and SEM/ EDX for Vikram, Tata Steel Ltd, India.

Anti-Corrosion Methods and Materials 57/6 (2010) 267 274 q Emerald Group Publishing Limited [ISSN 0003-5599] [DOI 10.1108/00035591011087118]

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Dye molecules in titania-silica hybrid coatings Tapan Kumar Rout

Anti-Corrosion Methods and Materials Volume 57 Number 6 2010 267 274

for obtaining desired functionality. Thin lm coatings of pure (TiO2) less than 100 nm in thickness are virtually transparent and form a TiZOZSi bridge with a glassy surface, which has already taken a position in the market, having added advantages such as reduced fragility and low solar heating through window glass, as discussed by Huang et al. (1998). According to Huang et al. carbon steel can be protected by titania coatings from atmospheric corrosion, as discussed also by Bu et al. (2005) and ORegan and Gratzel (1991). It was shown that under solar light the titania coating acts as a nonsacricial anode and provides cathodic protection to metals. The amorphous layer of titania helps in maintaining the photopotential by inhibiting oxygen reduction. Therefore, the titania coating (anatase) increases corrosion protection during both day and night periods. The stability as well as the adhesion of coatings onto metal substrates can be improved by chelating agents and adhesion promoters such as acetyl acetone, 1,2propanediol, ethylene glycol, ethanolamine, diethanolamine, triethanolamine, acetic acid, citrate acid, ethanol, n-butanol, and many silicone additives (Rout, 2007; Khramov et al., 2003; Abdel-Mohdy et al., 1998; Hirashima et al., 2003; Chou et al., 2003). The incorporation of dye molecules into the hybrid gel is interesting because of their physical, chemical and potential properties, as reported by Hirashima et al. (2003). This paper reports the preparation and characterization of composite titania-silica coatings on pre-phosphated interstitial free (IF) steel surfaces using a stable sol-gel and discusses the effect of dye molecules on corrosion behavior and probable corrosion prevention mechanisms.

Experimental
The sol-gel process A sol was prepared by mixing Ti-precursor with a compatible solvent in a glove box under nitrogen atmosphere. Hydrolysis and condensation reactions were controlled by the addition of water and a complexing agent, i.e. acetyl acetone/acetic acid. 3-Glycidoxy propyl trimethoxy silane (GPTMS) and other silane-coupling agents are added, and the sol temperature was set at 608C. The detailed analysis of the sol was explained elsewhere, as discussed by Rout et al. (2008). IF steel sheet was used for the present investigation. The composition of the IF steel was C: 0.0035 percent, Mn: 0.15 percent, Si: 0.015 percent, S: 0.02 percent, P: 0.018 percent, Al: 0.02 percent, and included N: 40 ppm, and microalloying elements: 0.15 percent. The steel had mechanical properties of yild strength: 160 MPa, ultimate tensile strength: 320 (max) MPa and r-bar: 1.8. The sample sheets were cleaned and dipped into the tri-cationic phosphating solution to obtain a thin phosphate coating of 2-3 g/m2 as discussed by Mukherjee (1980) prior to application of the nano-composite titania coating. Application of the sol on the steel substrate The sol was applied on the treated (phosphated) mild steel surface by dipping in a bath of sol for 1 min at room temperature. The dip-coated samples were heated to 1008C at a rate of 58C/min then held at that temperature for 30 min.

understand the inuence of coating elements, including light elements, and their inuence on substrate-coating interfacial adhesion. Scanning electron microscopy (SEM)/energy dispersive X-ray spectroscopy (EDX) was used to study microstructure and elemental composition in the coating cross-section. X-ray photoelectron spectroscopy (XPS) was used to determine the presence of light and heavy elements at the locus of failure on the substrate side. The sample number four was chosen for this investigation because it provides good corrosion resistance compared to others. A thin layer of gold was deposited on the coating to suppress charging effects during characterization. The basic coating contained C, O, Si and Ti. Although the EDX spectra do not supply information about the chemical state of these elements it can be expected that Si and Ti are present as oxides and the C is from the organic system. Oxygen usually is present in organic polymers as hydroxyl (ZOH) or ester groups. Fourier transform infrared spectroscopy (FT-IR) supplies more detailed information about the chemical groups in the organic coating. Crosssections were prepared and analyzed with LIM and SEM/EDX. The results are shown in Figure 1. This shows that the thickness of the hybrid organic coating was 8.8 ^ 0.5 mm. The thickness of the phosphate coating was 0.73 ^ 0.25 mm. EDX-spectra of the coating showed the presence of C, O, Si and Ti and minor amounts of Fe. The phosphate layer contained P, O, Zn and Mn. The microstructure of the substrate could be visualised only after acid etching treatment, as seen in Figure 1(b). The average grain size of the steel grains was approximately 10 mm. The result of the etching was to reveal the prominent phosphate layer. The phosphate layer could not be measured but its position still could be recognised by the shape of the holes that were left behind after etching. The phosphate crystals were much smaller than the grain size of the steel. There was no clear relationship between grain orientation and the phosphate crystals. It was observed also that the hybrid coating was a continuous matrix and had a uniform morphology throughout the thickness cross-section and it was attached strongly to the phosphate layer. The coating and phosphate interface was analysed using SEM and EDX after removal of the coating to conrm the bond strength and the delamination properties, and the ndings are shown in Figure 2.

Determination of locus of failure with XPS and SEM/EDX

The delamination of the coating was achieved using a Betamate 1496 resin. This resin was applied to the coating and was cured at 1808C for 30 min. When the resin is cooled in liquid nitrogen, it shrinks heavily and this applies the necessary peeling force. The SEM image shows that approximately 85 percent of the steel substrate is still covered by the phosphate layer and approximately 8 percent of the coating was detected on the phosphate layer. These ndings conrm that hybrid coating had experienced adhesive failure. The chemical composition of the residual (bright location) material on the substrate surface was analysed and is shown in Figure 2. Figure 2(a) and (b) shows surface microstructures obtained from backscattered (quadrant back scattering detector (QBSD)) and secondary electrode (SE) modes, respectively. The phosphate layer was observed mostly on the surface as dark areas with small crystal phosphate needles, indicating the locus of failure was between the phosphate layer and the coating. The atomic concentration of nitrogen, carbon, titanium and silicon were high at bright locations on the 268

Results
Characterization of coatings and their adhesion The hybrid coatings were investigated to identify the composition of the coating near to the substrate, in order to

Dye molecules in titania-silica hybrid coatings Tapan Kumar Rout

Anti-Corrosion Methods and Materials Volume 57 Number 6 2010 267 274

Figure 1 (a) SEM (SE-image) shows cross-sectional analysis of coatings and (b) SEM (SE-image) shows the microstructure of the steel substrate
Phosphate coating removed by acid etching

Reflective Au-layer

Ti-hybrid coating

Phosphate coating Steel substrate

(a)

(b)

Note: The phosphate layer is dissolved but the shape of the holes still marks the position of the crystals

Figure 2 SEM pictures and EDX spectra

Counts 0 Counts Fe 576 512 427 448 Fe 366 384 305 320 244 256 192 0 128 Na c 64 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 KeV P Fe 61 Au Ti Ti 5.00 Mn 6.00 Fe 7.00 8.00 Au Au 9.00 KeV 183 C 122 Si Au Au Fe Mn P Fe 488 549

1.00

2.00

3.00

4.00

(a) Notes: (a) QBSD mode; (b) SE mode on the delaminated surface

(b)

phosphate layer, as compared to other elements in the dark areas, which indicated that these elements potentially were participating in bonding with substrate. In the main, titanium and silicone were present as their respective oxide states, as 269

conrmed through XPS using a Kratos XSAM-800 spectrometer. Figure 3(b) shows that the spectrum of Ti 2p in TiO2 could be tted to the peaks at 460 and 466 eV, which was larger than was the standard value (459 ^ 1 eV). This means that

Dye molecules in titania-silica hybrid coatings Tapan Kumar Rout

Anti-Corrosion Methods and Materials Volume 57 Number 6 2010 267 274

Figure 3 XPS surface prole analysis to observe atomic state of elements on the left over coating after delamination
Si 2p Ti 2p

110

105

100

95

90

470

460

450

440

Binding energy/eV

Binding energy/eV

absorption bands of the OZH stretching (3,700-3,200 cm2 1), CO stretching (1,647 cm2 1) and NH in stretching vibration mode at 2,920 cm2 1. The bands corresponding to TiZOZTi vibrations were observed at 550-900 cm2 1 and SiZOZSi vibrations were at 1,000-1,200 cm2 1 (Rout et al., 2008). A heat-up prole was recorded in the FT-IR spectrometer to investigate the thermo stability of the coating. The prole presented in Figure 4 shows that between 100 and 2008C, the hydroxyl group (3,447 cm2 1) was being removed from the coating, as shown by the right curve (abs vs temp), additional heating indicating removal of the water molecules, and above 4008C the organic material was removed, as evidenced by changing of amine functionality (2,920 cm2 1). It was observed that there was a nominal change in the carbonyl group (1,647 cm2 1) in the temperature range 200-4008C. Simulated saline atmosphere (ASTM B117) This test was to access indirectly the wet-adhesion behavior of the hybrid coating on substrates in salt environments by observing coating delamination after certain intervals of hours. The test results of four different coatings are presented in Table I and the photographs of exposed surfaces are shown in Figure 5.

the surface acidity of TiO2 was enhanced and thus it was easy for the dye molecules to interact with and be adsorbed on the surface (Lu et al., 2000; Baek et al., 1995). The binding energy of 103.5 eV for the Si2 (SiZO) 2p peak implied that Si was present in the completely oxidised state, as shown in Figure 3(a). FIIR spectroscopy was used to describe further the network structure (TiZOZSi) and the role of dye molecules in the hybrid coating. Properties of the coating using FT-IR FT-IR was performed on a Perkin Elmer i2000-series with an IR-microscope with a m-attenuated total reectance crystal. The heat-up experiments were performed in a diffuse reectance infrared fourier transform spectroscopy cell that could be heated up to 4758C while recording FT-IR spectra. The experiments were performed in air. The FT-IR spectrum in Figure 4 show the Figure 4 FT-IR heat-up prole
Abs

Impedance analysis
Electrochemical impedance spectroscopy (EIS) analysis was carried out after 168 h of exposure in 3.5 percent NaCl solution to understand corrosion behavior of the coatings from an electrochemical standpoint. An equivalent circuit model was developed, which represents the substrate-coating-solution

Temp (C)

1.5 1.2 1.0

1.4150

1.2883

Abs
1.1616 1.0349 0.9082

0.8 0.6

475

410

0.4 0.1 4,000 0.86 0.79 0.70 0.60

0.5281

345
0.7815

3,000

2,000 1,500 Wavenumber

1,000

500

285
0.6548

2,920 cm1 (NH)

220 Abs

0.50 155
0.4014

3,447 cm1( OH)

0.40 0.30

0.2747

90
0.1480

0.20 0.10 1,647cm1(CO)

25 4,000

3,500

3,000

2,500

2,000

1,500

1,000

500

0.03 25 90 155 220 285 345 410 475 Temo PCI

Wavenumber

Notes: The coloured area on the left is a continuous presentation of all the FT-IR spectra; FT-IR spectra of three horizontal lines at three different temperatures are presented separately at right-hand side above, while three vertical line profiles correspond to three functional groups changing with temperature at right-hand side bottom

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Table I Intensity of corrosion product over time on exposed panels to SST

Sample no. Solution used for coating 24 h 72 h 1 2 3 4 Ti Ti Ti Ti Sol GPTMS Sol EETMS Sol PATMS Sol PATMS TZ OK OK OK OK 10 percent BR (failed) OK OK OK 96 h 168 h 196 h 216 h 10 percent BR (failed)

10 percent BR (failed) 2 percent BR 10 percent BR (faild) OK OK 2 percent BR

Figure 5 SST (3.5 percent NaCl solution) results on titania composite coating on steel

Figure 7 Nyquist plot to evaluate circuit elements

80 70 60 Z imaginary 50 40 30 20 10 0 0 10 R 20 30 40 50 60 70 Z Real 80 90 100 110 120 R + Rp max max Z = 1/CRp, = 2fmax Decreasing frequency max Z''

Mag: 2.5x 72 hrs

Mag: 2.5 96 hrs

Mag: 2.5x 168 hrs

Mag: 2.5 216 hrs

for different circuit elements (Figure 6). Different electrical circuit elements were evaluated by using the Nyquist plot, which presents data in the real vs imaginary axis (Figure 7), which describe an approximate semicircle. The parameter, (RV < Rct), gives an indication of the electrochemical corrosion processes occurring at the steel surface. This parameter can be used to study the effectiveness of some coatings and their protection of metals. The diameter of the semicircle was quite large, indicating the protective behavior of coating (Cc 1/2PCt fmax), though the coating capacitance (Cc) was very low.

Rp = 2/Z/tan

Discussion
The use of the dye molecule (tartrazine (TZ)) in the hybrid coating formulation has given a new dimension not only to obtaining colour appearance but also for its action as a corrosion inhibitor. The coating delamination in the salt spray test indicated that the dye contributed signicantly in delaying corrosion. From FT-IR analysis, it was observed that the stability of the coating between 200 and 4008C may be due to presence of dye (TZ), which acts to extend secondary bonding interaction through H-bonding, therefore making the coating Figure 6 Electrical circuit network model for coated steel substrate

Ccc Rs Z

Rct

Steel Coating Notes: R Rs, solution resistance; Rp Ct, coating charge transfer resistance; Cc, coating capacitance; Zw, Warburg impedance

network stronger. A schematic picture is presented in Figure 8, showing the H-bonding between dye molecules and the functional group of titania and silica precursors, and the TiZOZSi network structure in the coating matrix. As was observed from the salt spray results, Ti-sol with GPTMS gave 72 h of coating life whereas the coating with EETMS and PATMS showed an enhanced service life of 98, and 144 h, respectively. The TZ dye molecule in the PATMS formulation showed a signicant improvement in salt spray coating life (216 h). The GPTMS-based formulation had corroded partly after 72 h of exposure in salt spray chamber. This may be due to ne cracks that developed in the coating during sintering, as discussed by Rout (2007). This observation may be extended to EETMS and PATMS formulations, whereas formulations that included dye molecules enhanced the SST time. Here, the role of the dye was pronounced, in terms of corrosion protection, and this was evaluated further using EIS. Figure 9 shows the decrease in the value of Rct for the GPTMS-based coating, with respect to other coatings, indicating that the coating failed after a short time of immersion (72 h). Salt spray test results conrmed this nding (Figure 5) which showed obvious coating degradation and the formation of red rust. The effect of coating chemistry on the performance of the hybrid coating was evident, and it can be seen from the values of Rct, that the charge transfer resistance value (Ct) was quite high (419V cm2) in the case of the PATMS coating incorporating the dye (TZ), as compared to coatings without dye (360V cm2). Coatings based on two other silane coupling agents, EETMS and GPTMS, showed lower charge transfer resistance and the Nyquist plot was dominated by mass transfer behavior, 271

Dye molecules in titania-silica hybrid coatings Tapan Kumar Rout

Anti-Corrosion Methods and Materials Volume 57 Number 6 2010 267 274

Figure 8 A hypothetical mechanism to explain role of dye in the coating

O O S O
Na +

OH N N O C O Na+ N N

O S O
Na

OCH3 O
+

H N

H3CO

Si OCH3

Tartrazine (TZ)

3-(Phenylamino) propyl trimethoxy silane

O NH Si

O O

H N

O Ti O S i

O Hydrogen bonding OH N N O C O Na+ Hydrogen bonding NH Si O O Si O NH N N O O S O O S O

Na +

Hydrogen bonding OH N N O C O O
+ Na

O S O
Na

N N

O O S O Na+

O
+

O Na+

Hydrogen bonding

O Si O

Ti O Si Network structure

O Si O

O O

O S i O Ti O O

as conrmed by the appearance of the tail (Warburg resistance) at the low-frequency portion of the plot (Figure 9) (Mansfeld et al., 1982; Rout et al., 2006). This indicated that the coating was vulnerable to the diffusion of ions and water, which accelerate the mass-transfer reaction. The charge transfer resistance is inversely proportional to the corrosion rate (Ct a 1=icorr ), and therefore it could be concluded that the coating with the dye molecules offered better protective coatings than those without. The contact potential (CP)/work function of the coating is determined by using the Scanning Kelvin Probe (SKP) technique and is related to the corrosion potential (Doherty 272

and Sykes, 2004; McMurray and Williams, 2004). Larger coating surfaces were scanned (4 4 mm) using a SKP in order to evaluate macro variations in surface potential before and after exposure. It can be observed from Figure 10 that the coating surface potential shifted uniformly towards more negative potential values after exposure to the saline environment. This implies that the corrosion reaction is cathodically controlled. The effect could be due to the electrocatalytic inuence of the inhibitor (dye), which changes the activation energy barriers of the cathodic reactions of the corrosion process (Abd El-Maksoud, 2008).

Dye molecules in titania-silica hybrid coatings Tapan Kumar Rout

Anti-Corrosion Methods and Materials Volume 57 Number 6 2010 267 274

Figure 9 Nyquist plot in 3.5 percent NaCl solution

10,00,000 9,00,000 8,00,000 Ct = 119 7,00,000 6,00,000 Zimg 5,00,000 4,00,000 3,000,00 2,00,000 1,00,000 0 0 Note: After 168 h 1E+08 2E+08 3E+08 4E+08 Zrel 5E+08 6E+08 7E+08 8E+08 Ti sol-EETMS Ti sol-GPTMS Ti sol-PATMS Ti sol-PATMS+TZ Ct = 98 fmax

Ct = 360

Ct = 419

Figure 10 SKP surface CP

0 50 100 150 WF WF 4 3 1 0 1 2 Y 3 mm (a) Notes: (a) Before exposure; (b) after exposure (168 h) 40 2 X 200 250 300 350 400

0 100 200 300 400 3 500 600 0 1 2 Y 3 mm (b) 40 1 2 X 4

Conclusions
Titania hybrid coatings, consisting of three different adhesion prompters, were applied on an IF steel substrate. PATMS was found to improve coating life signicantly in the presence of dye (TZ), compared to coating that was formulated without the dye. A hypothetical mechanism was proposed to explain the mechanism of corrosion protection by coatings containing dye. It was observed from salt spray results that the dye could improve coating life from 168 to 216 h and this was conrmed by the increase in charge transfer resistance from 360 to 419V cm2. The corrosion protection mechanism of dye in coating could be explained using SKP data, and the observed 273

corrosion potential shift towards more negative indicated that steel corrosion was controlled cathodically.

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Further reading
Subasri, R. and Shinohara, T. (2003), Investigations on SnO2ZTiO2 composite photoelectrodes for corrosion protection, Electrochemistry Communications, Vol. 5 No. 10, pp. 897-902.

Corresponding author
Tapan Kumar Rout can be contacted at: tkrout5@yahoo.com

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