Corrosion resistance and photocatalytic activity evaluation of electrophoretically deposited TiO2-rGO nanocomposite on 316L stainless steel substrate

TiO₂-rGO nanocomposite coatings were obtained by electrophoretic deposition (EPD) technique of TiO₂ nanoparticles and graphene oxide (GO) on stainless steel substrate. First, GO particles were synthesized using a modified Hummers' method. GO was reduced electrochemically to form a coating in the presence of nano-sized TiO₂ particles. The influences of different parameters such as GO concentration, coupling co-electro-deposition parameters (electrophoretic duration and voltage) on thickness, surface morphology and, corrosion behavior of the as-synthesized TiO₂-rGO nanocomposite coatings were systematically surveyed. The morphology and microstructure were investigated by field emission scanning electron microscopy (FE-SEM), Raman spectra and X-ray diffraction (XRD) techniques. Atomic force microscopy (AFM) was harnessed to evaluate the topography of the as-prepared GO powder. The bonding characteristics of as-synthesized and as-reduced GO were examined after deposition, by Energy Dispersive Analysis of X-Ray (EDX) and Fourier-transform infrared spectroscopy (FT-IR). Corrosion behavior of coatings and that of the pure TiO₂ layer were evaluated by electrochemical impedance spectroscopy (EIS) and polarization techniques (by applying potentiodynamic polarization spectroscopy (PDS)). Detailed SEM studies showed that increasing EPD voltage brings about a coating with increased porosity and microcracks with higher thickness. In addition to that, the presence of rGO reduced corrosion current density (i_corr) and shifted corrosion potential (E_corr) toward more noble values in 3.5% NaCl at room temperature. Also, Analyses revealed that the optimum electrophoretically synthesized coating was obtained at GO concentration of 1 g/L, 30 V and 30 min at room temperature. The corrosion current density of the corresponding coating was remediated up to 0.2 μA cm⁻², which means an anti-corrosion ability of about 30 times compared to TiO₂-coated and bare 316L stainless steel. The results of impedance spectroscopic studies demonstrated that this coating renders as a barrier layer and resistance increased from 2.95 KΩ cm² for TiO₂-coated layer to 10.49 KΩ cm² for the optimized layer.     

Corrosion behavior of titania films coated by liquid‐phase deposition on AISI304 stainless steel substrates

Fouling deposition and localized corrosion on the heat‐transfer surfaces of the stainless steel equipments often simultaneously exist, which can introduce additional thermal resistance to heat‐transfer and damage heat‐transfer surfaces. It is a good anticorrosion way to coat a barrier layer of certain materials on the metal surface. In this article, the TiO₂ coatings with nanoscale thicknesses were obtained by liquid‐phase deposition method on the substrates of AISI304 stainless steel (ASS). The coating thickness, surface roughness, surface morphology, crystal phase, and chemical element were characterized with the film thickness measuring instrument, roughmeter, atomic force microscopy, field emission scanning electron microscopy, X‐ray diffraction, and energy‐dispersive X‐ray spectroscopy analyzer, respectively. Corrosion behavior of the TiO₂ coatings was evaluated by potentiodynamic polarization, cyclic voltammograms scanning, and electrochemical impedance spectroscopy tests with the mixed corrosion solution composed of 3.5 wt. % NaCl and 0.05 M NaOH. It is shown that the TiO₂ coating is composed of the nanoparticles with smooth, crack‐free, dense, and uniform surface topography; the roughness of coating surface increases slightly compared with that of the polished ASS substrate. The anatase‐phase TiO₂ coatings are obtained when sintering temperature being varied from 573.15 to 923.15 K and exhibit better anticorrosion behavior compared with ASS surfaces. The corrosion current density decreases and the polarization resistance increases with the increase of the coating thickness. The corrosion resistance of the TiO₂ coatings deteriorates with the increase of the corrosion time. The capacitance and the resistance of the corrosion product layer between the interface of the ASS substrate and the TiO₂ coating are found after the corrosion time of 240 h. A corrosion model was introduced, and a possible new explanation on the anticorrosion mechanisms of the TiO₂ coating was also analyzed. The corrosion mechanism of the TiO₂ coating might comply with the multistage corrosion process. © 2011 American Institute of Chemical Engineers AIChE J, 58: 1907–1920, 2012     

Corrosion Protection of Stainless Steel by Poly(Carbazole-co-pyrrole) Films Deposited on TiO2 Sol–Gel Film

The poly(carbazole-co-pyrrole) copolymer was synthesized on TiO₂ sol–gel precoated 304 stainless steel (TiO₂) by cyclic voltammetry in tetrabutylammonium perchlorate containing acetonitrile solution. The synthesized coating was characterized by attenuated total reflectance–Fourier transform infrared spectroscopy, scanning electron microscopy, and solid-state conductivity measurements. Corrosion protection behavior of the TiO₂/poly(carbazole-co-pyrrole)-coated steel was evaluated by open circuit potential–time curves, potentiodynamic polarization, and electrochemical impedance spectroscopy methods. Corrosion test results showed that TiO₂/poly(carbazole-co-pyrrole) composite film enhanced corrosion resistance of stainless steel up to 50 days of immersion in 0.1M HCl corrosive medium.     

Sol-gel TiO2-SiO2 films as protective coatings against corrosion of 316L stainless steel in H2SO4 solutions

Sol-gel TiO₂-SiO₂ films were deposited on 316L stainless steel by dip coating process from a sono-catalysed sol of composition 30TiO₂-70SiO₂ prepared from a mixture of Ti(OC₂H₅)₄ and Si(OC₂H₅)₄, absolute ethanol C₂H₅OH and glacial acetic acid CH₃COOH as precursors and solvents. The films, densified at 800° C in air for 2 h, are composed of small orthorhombic titania (anatase) crystallites embedded in a SiO₂ amorphous matrix as identified by X-ray diffraction. The temperature dependence of the film morphology was observed using scanning electron microscopy (SEM) and the content was determined by FTIR reflection spectroscopy. The corrosion behaviour of 316L stainless steel samples coated with densified 30TiO₂-70SiO₂ films was studied in 15% H₂SO₄ by potentiodynamic polarization curves at 25, 40 and 50°C. The measured corrosion rates show a considerable decrease for the protected steel samples in comparison to the bare substrate. The effect of time of heat treatment of the films on the corrosion parameters is also reported.     

Fouling Resistance on Chemically Etched Hydrophobic Surfaces in Nucleate Pool Boiling

Chemical etching, liquid phase deposition, and dipping techniques were utilized to fabricate highly hydrophobic micro‐ and nanoscale coating surfaces on stainless‐steel substrates. Heat transfer and fouling characteristics on these surfaces in pool boiling of deionized water and CaSO₄ solution were studied. High roughness and hydrophobicity of coated surfaces were obtained on chemically etched substrates. Compared to the polished stainless‐steel surface, the chemically etched coating surface provided a three times enhanced nucleate boiling coefficient at high heat flux. Obvious decrease of CaSO₄ fouling resistance was obtained on chemically etched surfaces due to the higher roughness and hydrophobicity before the fouling resistance reaches the asymptotic value. Slightly high asymptotic fouling resistance was observed compared with coating surfaces without chemical etching of substrates.     

The effect of concentration and source of calcium ions on anticorrosion properties of Ca-doped TiO2 bioactive sol-gel coatings

Titanium dioxide (TiO₂) coating with an enhanced anticorrosion properties and bioactivity was developed by doping it with calcium ions through a sol–gel method. The effect of annealing temperature, anions, as well as calcium ions concentration on microstructural and anticorrosion properties of Ca-doped TiO₂ coatings have been investigated. The phase composition and morphology of the coatings were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and atomic force microscopy (AFM). The corrosion resistance of M30NW biomedical alloy coated with Ca-doped TiO₂ coatings was evaluated using electrochemical methods in conditions similar to the normal physiological environments (PBS solution, pH 7.4, temperature of 37 °C). The obtained results show that the annealing temperature and the source of calcium ions influence the anticorrosion properties of Ca-doped TiO₂ coatings. The best anticorrosion properties were registered for coatings with the highest concentration of Ca ions. At the same time all the examined coatings presented good bioactivity in SBF solution test.     

Evaluation of the corrosion resistance of Ni-Co-B coatings in simulated PEMFC environment

The corrosion resistance behavior of Ni-Co-B coated carbon steel, Al 6061 alloy and 304 stainless steel was evaluated in simulated proton exchange membrane fuel cell (PEMFC) environment. The phase structure of the NiCoB based alloy was determined by Rietveld analysis. The PEMFC environment was constituted of 0.5 M H₂SO₄ at 60 °C and the evaluation techniques employed included potentiodynamic polarization, linear polarization resistance, open circuit potential measurements and electrochemical impedance spectroscopy. The results showed that in all cases the corrosion resistance of the Ni-Co-B coating was higher than that of the uncoated alloys; about two orders of magnitude with respect to carbon steel and an order of magnitude compared to 304 stainless steel. Except for the uncoated 304 type stainless steel, the polarization curves for the coated specimens did not exhibit a passive region but only anodic dissolution. The corrosion potential value, E_corr, was always nobler for the coated samples than for the uncoated specimens. This was true for the stainless steel in the passive region, but in the active state for the carbon steel and Al 6061 alloy. The corrosion of the underlying alloy occurred due to filtering of the solution through coating defects like microcracks, pinholes, etc. During the filtering process the E_corr value of the coating decreased slowly until it reached a steady state value, close to the E_corr value of the underlying alloy.     

Preparation and photoelectrochemical characterisation of electrosynthesised titanium dioxide deposits on stainless steel substrates

TiO₂ films on stainless steel 304 substrates have been prepared from acidic aqueous solutions of TiOSO₄ and H₂O₂ by room temperature potentiostatic cathodic electrosynthesis. Coatings of varied thickness were produced by repeating the deposition step two or three times accompanied by drying steps in between. The resulting gel films were annealed at 400 °C to obtain crystalline TiO₂ (anatase) films with loadings in the 0.1-1 mg cm⁻² range. The deposits had a macro-particulate structure and adhered well on stainless steel 304. The electroactive surface area of the composite electrodes was estimated by cyclic voltammetry in the dark, while their photoelectrochemical behaviour was investigated by photo-voltammetry under UV illumination, both in the presence and absence of oxidizable organics. The effect of deposit thickness on photocurrent and an indicative comparison of electrosynthesised TiO₂/stainless steel 304 photoelectrodes with thermal and particulate TiO₂/Ti electrodes are also presented.     

The effect of incorporating carbon nanotubes in titania films used for the photocathode protection of 304 stainless steel

Composite films of TiO₂ and multiwall carbon nanotubes (MWCNTs) were prepared on 304 stainless steel (304 SS) by the sol–gel method and heat treatment. Their crystal phase and surface structure were characterized by X-ray diffraction and electron microscopy. The photoelectrochemical performance of the composite films in 3.0% NaCl solution was evaluated by electrochemical measurements under UV irradiation and dark conditions. Since highly conductive MWCNTs in the TiO₂ films can transport the photo-generated electrons easily and quickly to the metal substrate, the MWCNT/TiO₂ composite films exhibited three times the photocurrent and the half the charge transfer resistance of pure TiO₂ films, and provide a much better photocathode protection for 304 SS.     

Protection of stainless steel by polyaniline films against corrosion in aqueous environments

Polyaniline (PANI) thin films were electrochemically deposited by cyclic voltammetry on stainless steel electrode previously covered by a thin film of polyvinyl acetate (PVAc). The corrosion resistance of PANI covered stainless steel substrates was estimated by using potentiodynamic polarization curves and its linear polarization resistance (LPR) was measured in 0.5 M H₂SO₄, 0.5 M NaCl and 0.5 M NaOH aqueous solutions at room temperature. The results indicate that the PANI-PVAc films did improve the corrosion resistance of the stainless steel in NaOH, behaving even worst, in the case of PANI film, than the uncoated substrate. In H₂SO₄ both PANI and PANI-PVAc coatings gave good protection for the stainless steel electrode, with a slightly better performance of PANI-PVAc than PANI. In NaCl solution both PANI and PANI-PVAc films provided a good protection against corrosion. The better performance of PANI-PVAc coatings for corrosion protection in basic media may be due to its major chemical stability compared to simple PANI films, which lose their conductivity in high pH solutions. The E _corr (free corrosion potential) value of the coated substrate was in the passive region of the uncoated substrate in acidic environment but in the active region in neutral or basic environment.     

Siloxane-based thin films for corrosion protection of stainless steel in chloride media

The corrosion protection of stainless steel (SS 316L) provided by layers of SiO₂ and by siloxane-anchored self-assembled monolayer (SAMs) was assessed by cyclic voltammetry (CV) and by potentiostatic current transient in sodium chloride media. The SAMs were composed of octadecyltrimethoxysilane anchored onto a thin (1–2 nm) layer of SiO₂. The initial SiO₂ layer was obtained by treatment with tetraethoxyorthosilicate. Successive layers were added by applying the alkylsiloxane and then oxidatively removed by treatment using a UV-ozone cleaner. Though SAMs have been used as corrosion barriers in other contexts, it is shown that successive cycles of SAM deposition and ablation provide an extended SiO₂ thin-covering layer that protects stainless steel against pitting and general corrosion.     

12‐crown‐4–ether and tri(ethylene glycol) dimethyl–ether plasma‐coated stainless steel surfaces and their ability to reduce bacterial biofilm deposition

It has been demonstrated that surfaces coated with poly(ethylene glycol) (PEG) are capable of reducing protein adsorption, bacterial attachment, and biofilm formation. In this communication cold‐plasma–enhanced processes were employed for the deposition of PEG‐like structures onto stainless steel surfaces. Stainless steel samples were coated under 1,4,7,10‐tetraoxacyclododecane (12‐crown‐4)–ether and tri(ethylene glycol) dimethyl ether (triglyme)–radio frequency (RF)–plasma conditions. The chemistry and characteristics of plasma‐coated samples and biofilms were investigated using electron spectroscopy for chemical analysis (ESCA), atomic force microscopy (AFM), and water contact angle analysis. ESCA analysis indicated that the plasma modification resulted in the deposition of PEG‐like structures, built up mainly of –CH₂? CH₂? O– linkages. Plasma‐coated stainless steel surfaces were more hydrophilic and had lower surface roughness values compared to those of unmodified substrates. Compared to the unmodified surfaces, they not only significantly reduced bacterial attachment and biofilm formation in the presence of a mixed culture of Salmonella typhimurium, Staphylococcus epidermidis, and Pseudomonas fluorescens but also influenced the chemical characteristics of the biofilm. Thus, plasma deposition of PEG‐like structures will be of use to the food‐processing and medical industries searching for new technologies to reduce bacterial contamination. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3425–3438, 2001     

Balance of mechanical and electrical performance in polyimide/nano titanium dioxide prepared by an in‐sol method

Hybrid polyimide (PI)/titanium dioxide (TiO₂) films were prepared by in situ polymerization and sol–gel and in‐sol methods (where in‐sol method indicates that in situ polymerization and the sol–gel method were used in the same samples). The mechanical and electrical properties were found to be sensitive to the processing methods and the dispersion of nano titanium dioxide (nano‐TiO₂) in the PI matrix. For the PI/TiO₂ films prepared by the in situ polymerization method, their tensile strength increased with increasing TiO_{2‐in situ} (“TiO_{2‐in situ}” is “the TiO₂ nano‐particles prepared by in situ polymerization method”) concentration. However, the optimal corona lifetime of the PI/TiO₂ films was 15 min at 20 kHz and 2 kV because of poor dispersion. For the PI/TiO₂ films prepared by the sol–gel method, the corona lifetime reached 113 min because of superior dispersion and a tensile strength of about 19.63 MPa. A balance of mechanical and electrical performances was achieved with the in‐sol method. The corona‐resistant life of the PI/TiO₂ films was 43 min, which was about six times longer than that of the neat PI. Their tensile strength was 83.5 MPa; these films showed no decrease in this value compared with the pure PI films. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44666.     

Physical properties and photocatalytic performance of TiO2 coated stainless steel plate

This research was conducted for the development of TiO₂ thin film coated stainless steel useful in environmental and sanitary fields such as removal of indoor air pollutants and prevention of harmful microorganisms in the kitchen and bathroom. For this purpose, the research was focused on the examination of physical properties of coated surfaces as well as the photocatalytic performance of the steel plates. The coated steel’s cohesiveness and anti-corrosion effect were good enough to be used even in the hard environments. To test the photocatalytic performance of the TiO₂ thin film coated stainless steel plate, photodegradations ofm-xylene, a typical air pollutant produced by automobiles, andE. coli, under 365 nm UV irradiation, were conducted. The TiO₂ coated stainless steel plate considerably enhanced the degradation efficiencies ofm-xylene andE. coli.     

A highly efficient ZnS/CdS@TiO2 photoelectrode for photogenerated cathodic protection of metals

Shell-core nanostructured ZnS/CdS quantum dots (QDs) were assembled uniformly on the surface of TiO₂ nanotube arrays by sequence chemical bath deposition (CBD) of CdS and ZnS in alcohol solution system. The morphology and chemical composition of the obtained composite thin films were characterized by scanning electron microscopy, transmission electron microscopy and energy dispersive X-ray spectroscopy. The effect of solvent and immersion cycles for the photoanode preparation on the photoelectrochemical activity and photogenerated cathodic protection property was investigated. It is found that the nanostructured CdS QDs (20 cycles) coated on TiO₂ nanotube arrays show a remarkably enhanced photoelectrochemical activity. The coating of ZnS QD shells (5 cycles) is able to improve the stability of the CdS@TiO₂ photoanode under white-light irradiation. After the irradiation light is turned off, the photogenerated cathodic protection of 403 stainless steel (403SS) can be remained for several hours.     

Electrochemical investigations of pitting corrosion behaviour of type UNS S31603 stainless steel in thiosulfate-chloride environment

The pitting corrosion behaviour of type UNS S31603 stainless steel (316L SS) in 0.01, 0.05 and 0.1 M thiosulfate ion (S₂O₃ ^2–) in the absence and presence of various concentrations of chloride ion (Cl^–) was studied using the cyclic potentiodynamic polarization method. The influence of major factors which affect pitting corrosion such as pH and temperature, were also investigated. It was found that both the pitting potential (E _pit) and the repassivation potential (E _rp) decreased with increase in Cl^– concentration and solution temperature and a more pronounced difference in E _pit values for various concentrations of S₂O₃ ^2– in 1.0 M Cl^– was obtained at lower temperatures. The effect of pH on E _pit, E _corr and E _rp values for different concentrations of S₂O₃ ^2– in the presence of 1.0 M Cl^– was also determined.     

Morphological characteristics of copper deposition on stainless steel cathodes

The results of a metallographic study of cathodic copper deposition on 316 stainless steel are presented. In magnetically assisted d.c. electrolysis, characteristic screen-type deposition patterns are observed. Simultaneous hydrogen evolution causes tunnel-type deposits at 30–45° to the horizontal.Nomenclature B _z magnetic flux density, vertical field lines pointing downwards - C electrolyte concentration - CVD cell voltage drop - i _c cathode current density - s cathode-anode separation distance - T temperature - t _e length of electrolysis time     

Corrosion behaviour and biocompatibility of nanoporous niobium incorporated titanium oxide coating for orthopaedic applications

This study investigates the surface characteristics, in vitro biocompatibility and electrochemical behaviour of nanoporous niobium incorporated titanium dioxide (Nb-incorporated TiO₂) coated 316L stainless steel (SS) for orthopaedic applications. The coating material was synthesized by sol-gel methodology and was deposited on 316L SS by using spin coating technique and heat treatment. The experimental conditions were optimized to obtain a coating with nanoporous morphology. The coating was characterized using attenuated total reflectance-Infrared spectroscopy (ATR-IR), X-ray diffraction analysis (XRD), scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDX), atomic force microscopy (AFM) and transmission electron microscopy (TEM). The analysis confirmed the formation of a crystalline nanoporous Nb-incorporated TiO₂ coating with hydrophilic nature. Mechanical studies validated that the coating has excellent adhesion to the specimen and appreciable hardness value. In vitro bioactivity test confirmed that the nanoporous morphology of the coating facilitated enhanced hydroxyapatite (HAp) growth. Electrochemical studies established that the insulative nature of the coating provides excellent corrosion resistance to 316L SS.     

Crystallisation kinetics of hydroxyapatite thin films prepared by sol-gel process

Abstract

Abstract

In this study, the crystallisation of nano hydroxyapatite (HA) films on stainless steel 316L was studied. The film was prepared by sol-gel technique. The process was started with preparation of an HA sol. After aging of the sol at room temperature, a stainless steel 316L substrate was dip coated and then was heat treated from 350 to 450°C at different periods of time in air. The crystallisation behaviour and the transformation-temperature-time diagram of HA films were achieved and analysed using the avrami equation. The results showed that the crystallisation of HA began at 250°C and was increased up to 450°C. The obtained HA film showed a nanostructure character with a suitable crystalinity after heat treatment.     

AUGMENTATION OF PHOTOCATALYTIC ACTIVITY OF TiO2 THIN FILMS PREPARED BY A SOL-GEL TECHNIQUE

In order to increase the photocatalytic activity on TiO₂ thin film per its external surface area, the structure of flat thin film was modified by adding a small amount of polyethylene glycol (PEG) to TiO₂ sol solution. By firing PEG contained in a TiO₂ gel film, a porous structure was developed. The photocatalytic activities of the thin films prepared thus were evaluated by the degradation of 2-propanol in the aqueous solutions under black light illumination. The photocatalytic activity of TiO₂ thin film prepared with added PEG 400 by 2.6 wt% or PEG 2000 by 9.5 wt% was increased by about 30% as compared to that prepared without added PEG.