Corrosion resistance of TiO2 films grown on stainless steel by atomic layer deposition

Titanium dioxide (TiO₂) films have been deposited onto stainless steel substrates using atomic layer deposition (ALD) technique. Composition analysis shows that the films shield the substrates entirely. The TiO₂ films are amorphous in structure as characterized by X-ray diffraction. The electrochemical measurements show that the equilibrium corrosion potential positively shifts from − 0.96 eV for bare stainless steel to − 0.63 eV for TiO₂ coated stainless steel, and the corrosion current density decreases from 7.0 × 10^− 7 A/cm² to 6.3 × 10^− 8 A/cm². The corrosion resistance obtained by fitting the impedance spectra also reveals that the TiO₂ films provide good protection for stainless steel against corrosion in sodium chloride solution. The above results indicate that TiO₂ films deposited by ALD are effective in protecting stainless steel from corrosion.     

Corrosion studies of stainless steel protected by a TiO2 thin film deposited on a sulfonate-functionalized self-assembled monolayer

Thioacetate hexadecyltrimethoxysilane was deposited on SiO₂-coated stainless steel to form a thioacetate-functionalized monolayer. In situ oxidation of the thioacetate yielded a sulfonate-functionalized monolayer. Solution deposition of TiO₂ on this monolayer covered the stainless steel with a thin layer of the metal oxide (5-10 nm). Cyclic voltammetry (CV) and potentiostatic current transient demonstrated the efficiency of the corrosion protection in sodium chloride media, including protection against pitting corrosion.     

Photogenerated cathodic protection of flower-like, nanostructured, N-doped TiO2 film on stainless steel

Flower-like, nanostructured, N-doped TiO₂ (N-TiO₂) films were fabricated using a low-temperature hydrothermal method. The morphology, crystalline phase, and composition of these flower-like nanostructured films were characterized systematically by scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and UV-vis spectroscopy. The photoelectrochemical properties of N-TiO₂ films in 0.5 M NaCl solution were evaluated under illumination and in the dark through electrochemical measurements. Flower-like nanostructured TiO₂ films exhibited a drastically enhanced photocurrent in the UV light region and a notable absorption in the visible light region (600-700 nm). The negative shifts of the electrode potentials of 316L stainless steel coupled with N-doped TiO₂ photoanodes are 470 and 180 mV under UV and visible light irradiation, respectively. The flower-like, nanostructured, N-doped TiO₂ films were able to function effectively as photogenerated cathodic protection for metals under UV and visible light illumination. Such photogenerated cathodic protection could last a period of 5.5 h even in darkness.     

Photocathodic protection properties of TiO2–V2O5 composite coatings

TiO₂/vanadium pentoxide (V₂O₅) and TiO₂–V₂O₅ coatings were prepared on type 304 stainless steel substrates via a sol–gel method, respectively. The TiO₂/V₂O₅ coating is compared with the TiO₂–V₂O₅ coating in terms of the photo‐electrochemical performance. The two coatings can be stored with photogenerated electrons under UV irradiation in 3 wt% aqueous NaCl. The self‐discharging time of the TiO₂/V₂O₅ coating is slower than that of the TiO₂–V₂O₅ coating. The slow discharging may be suitable for an anti‐corrosion application for stainless steel. In the case while the two coatings are electrochemically charged under UV irradiation for 1 h, the TiO₂/V₂O₅ coating can maintain a good cathodic protection for type 304 stainless steel for 6 h in the dark, while the TiO₂–V₂O₅ coating can only maintain a good cathode protection for 0.5 h in the dark.     

Energy storage ability and anti‐corrosion protection properties of TiO2–SnO2 system

TiO₂/SnO₂ and TiO₂–SnO₂ coatings were prepared on type 304 stainless steel by sol–gel method, respectively. TiO₂/SnO₂ coating is compared with TiO₂–SnO₂ coating in terms of energy storage ability and anti‐corrosion property. The two coatings can be charged with reductive energy under UV irradiation in 3 wt% aqueous NaCl. The self‐discharging time of the TiO₂/SnO₂ coating is slower than that of the TiO₂–SnO₂ coating. The slow discharging may be suitable for an anti‐corrosion application for metal. In the case where TiO₂/SnO₂ coating electrode is electrochemically charged at ?0.38 V (vs. SCE) for 1 h, it can maintain a good cathodic protection for type 304 stainless steel for 7 h in the dark, while the TiO₂–SnO₂ coating electrode can only maintain a good cathode protection for 0.5 h in the dark.     

Characterization of electronic properties of TiO2 nanotube films

By anodization of titanium, TiO₂ nanotube layers were grown that consist of arrays of individual tubes with a length of ≈2.5 μm, a diameter of ≈100 nm and a wall thickness of ≈15 nm. The electronic properties of TiO₂ nanotube layers were characterized using photoelectrochemical and impedance measurements. Photocurrents for as-anodized tubes are dominated by their amorphous state and a high number of defects. Conversion to anatase by annealing decreases the defect density drastically which results in an enhanced photocurrent.     

Application of polyaniline to galvanic anodic protection on stainless steel in H2SO4 solutions

A stand-alone polyaniline (PANI) film electrode was made and then applied to protect 1Cr13 stainless steel (a type of stainless steel typically used in China, 0–15% C, 13% Cr) from corrosion in highly acidic solution, up to 5 M H₂SO₄. The stand-alone PANI electrode and 1Cr13 were coupled to study their galvanic interactions. PANI is a cathode while 1Cr13 is an anodic. The results indicate that PANI with a certain area can quickly passivate the stainless steel and effectively maintain the steady passive state for a long period of time. This specific method of PANI preventing 1Cr13 from corrosion is called galvanic anodic protection (GAP). Moreover, the efficiency, mechanism, and security of GAP were discussed. The results demonstrate that the stand-alone PANI electrode may have a potential application to galvanic anodic protection on stainless steel in highly corrosive H₂SO₄ solutions.     

Photogenerated cathodic protection of stainless steel by liquid-phase-deposited sodium polyacrylate/TiO2 hybrid films

Sodium polyacrylate/TiO₂ hybrid films that served as photoanodes for cathodic protection application were prepared by liquid phase deposition. Under white-light illumination, the open-circuit potential of the hybrid films coupled with SUS304 stainless steel could shift to a more negative value and offer an effective photogenerated cathodic protection for stainless steel. Moreover, the hybrid films also exhibited stronger photocurrents in both the ultraviolet-light and visible-light regions compared to that of control TiO₂ films. In summary, the addition of sodium polyacrylate could greatly improve the photogenerated cathodic protection properties of the liquid-phase-deposited TiO₂ films.     

Notched tensile tests of cold-rolled 304L stainless steel in 40 wt.% 80 °C MgCl2 solution

The effects of cold-rolling (20% thickness reduction) and sensitization treatment (600 °C/10 h) on the microstructure, tensile properties and susceptibility to stress corrosion cracking of 304 stainless steel in 80 °C MgCl₂ (40 wt.%) solution were investigated. The increase in hydrogen traps, which retarded hydrogen diffusion to the strained region, accounted for the low loss in notched tensile strength (NTS) of such a cold-rolled specimen, as compared to the solution-treated specimen in the corrosive environment. By contrast, the high NTS loss of sensitized specimens in MgCl₂ solution was attributed mainly to the formation of stress-induced martensite near grain boundary regions.     

A study on mechanism of corrosion protection of polyaniline coating and its failure

Polyaniline (PANI) coatings were electrochemically deposited on substrates of stainless steel and platinum in solutions of 0.2 M H₂SO₄ and 0.1 M aniline by cyclic voltammetry. The corrosion protection of the PANI coatings and their failure were investigated in 0.2 M H₂SO₄ solution. It was observed that the corrosion protection ability of the coating to steel substrate was increased with the increase of the coating thickness. The corrosion protection ability was mainly attributed to the passivating effect of PANI due to its oxidizing ability in its emeraldine state. During its operation, the PANI coating in emeraldine state tended to gradually lose its corrosion protection ability. This gradual failure of the PANI coating, but faster than expected, was confirmed to be related to a gradual reduction of the emeraldine PANI and a gradually increased resistance between the PANI coating and the stainless steel substrate. These findings lead to a new mechanism for the corrosion protection of PANI coating and its failure.     

Poly(N-methylaniline) coatings on stainless steel by electropolymerization

Poly(N-methylaniline) (PNMA) coatings have been electropolymerized on 304 stainless steel alloy by potentiodynamic, galvanostatic and potentiostatic synthesis techniques from aqueous solutions of 0.1 M N-methylaniline (NMA) and 0.3 M oxalic acid. Characterization of PNMA coatings was carried out by cyclic voltammetry, UV-Vis and FTIR spectroscopy techniques. Corrosion behavior of PNMA coated stainless steel electrodes was investigated using linear anodic potentiodynamic polarization, Tafel test, chronoamperometry and electrochemical impedance spectroscopy (EIS) techniques in 0.5 M aqueous HCl solutions. Corrosion test results showed that PNMA coatings possessed protection to uncoated stainless steel against corrosion.     

Discontinuous oxidation and erosion-oxidation of a CeO2-dispersion-strengthened chromium coating

A CeO₂-dispersion-strengthened chromium coating was developed on a carbon steel using a two-step process: prior electrodeposition of a Ni-CeO₂ nanocomposite film and subsequent chromization using a conventional pack cementation method. Compared to the CeO₂-free coatings prepared on the carbon steel without and with pre-electrodeposition of a pure Ni film, the CeO₂ dispersed chromium coating offered profoundly improved discontinuous oxidation resistance at 900 °C in 5% O₂ + N₂ and in 5% O₂ + 1000 ppm SO₂ + N₂, and erosion-oxidation resistance in a laboratory-scale fluidized-bed combustor (FBC), mainly because of the development of a denser, less wrinkled and more adherent chromia scale.     

Effect of Mo and Mn additions on the corrosion behaviour of AISI 304 and 316 stainless steels in H2SO4

The work addresses the influence of Mn and Mo additions on corrosion resistance of AISI 304 and 316 stainless steels in 30 wt.% H₂SO₄ at 25 and 50 °C. Corrosion mechanism was determined by gravimetric tests, DC polarization measurements and electrochemical impedance spectroscopy (EIS). The morphology and nature of the reaction products formed on the material surface were analysed by scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDX) and X-ray photoelectron spectroscopy (XPS). Reduction of temperature from 50 to 25 °C drastically decreased the corrosion rate of AISI 304 and 316 stainless steels in sulphuric acid solution. Mn additions did not affect significantly the general corrosion resistance due to its low ability to form insoluble compounds in acid medium. Meanwhile, the formation of molybdenum insoluble oxides enhanced the corrosion performance.     

Effect of thermal annealing on the corrosion protection of stainless steel by poly(3-octyl thiophene)

Poly(3-octyl thiophene) (P3OT) coatings have been chemically deposited by drop casting onto 304-type stainless steel. P3OT films were thermally annealed at 55, 80 and 100 °C in air during 30 h and their corrosion resistance was estimated by using polarization curves, linear polarization resistance (LPR), and electrochemical impedance spectroscopy measurements, EIS. P3OT films decreased the corrosion rate of the substrate by at least one order of magnitude, although the best corrosion protection was given by annealing it at 100 °C whereas the worst corrosion protection was given by annealing the coating at 80 °C.     

Determination of the sensitized zone extension in welded AISI 304 stainless steel using non-destructive electrochemical techniques

Extension of sensitized zone (SZ) in welded AISI 304 stainless steel was determined by two non-destructive electrochemical tests: double loop electrochemical potentiokinetic reactivation technique (DLEPR) and local electrochemical impedance spectroscopy (LEIS). Welding was carried out using the shielded metal arc with two selected welding energies: the first one (0.7 kJ mm⁻¹) does not promote the sensitization of the 304 steel and it constitutes the reference sample and the second one (2.2 kJ mm⁻¹) which leads to the precipitation of chromium carbides in the grain boundaries after the welding process. The non-destructive DLEPR and LEIS tests allowed the length of the SZ to be determined and a good agreement between the two techniques and the microstructure of the two welded samples was shown. The presence of an inductive loop on the local impedance diagrams seems to reflect a galvanic coupling between the weld string (anode) and the welded stainless steel plates (cathode) which will be very prejudicial to a good corrosion resistance of the welded system. The results showed that the two electrochemical tests could be applied in practical cases in industrial field.     

Development and oxidation resistance of air plasma sprayed Mo-Si-Al coating on an Nbss/Nb5Si3 in situ composite

A Mo-Si-Al coating, which is mainly composed of Mo(Si,Al)₂ and Mo₅(Si,Al)₃, was developed to protect a Nb_ss/Nb₅Si₃ in situ composite by air plasma spraying. After oxidation at 1250 °C, the oxidation curve followed parabolic law and even after oxidation for 100 h, the weight gain of Mo-Si-Al coating was 8.24 mg/cm². The surface of the oxidized samples became flatter and smoother as time increased due to the formation of SiO₂ glass. Moreover, the microstructure of Mo-Si-Al coating changed and a layer structured interdiffusion zone was formed at the substrate-coating interface after oxidation.     

Corrosion behavior of iron-based alloys in the LiBr + ethylene glycol + H2O mixture

The corrosion resistance of 1018 carbon steel, 304 and 316 type stainless steels in the LiBr (55 wt.%) + ethylene glycol + H₂O mixture at 25, 50 and 80 °C has been studied using electrochemical techniques which included potentiodynamic polarization curves, electrochemical noise and electrochemical impedance spectroscopy techniques. Results showed that, at all tested temperature, the three steels exhibited an active-passive behavior. Carbon steel showed the highest corrosion rate, since both the passive and corrosion current density values were between two and four orders of magnitude higher than those found for both stainless steels. Similarly, the most active pitting potential values was for 1018 carbon steel. For 1018 carbon steel, the corrosion process was under a mixed diffusion and charge transfer at 25 °C, whereas at 50 and 80 °C a pure diffusion controlled process could be observed. For 316 type stainless steel, at 25 and 50 °C a species adsorption controlled process was observed, whereas at 80 °C a diffusion controlled mechanism was present. Additionally, at 25 °C, the three steels were more susceptible to uniform type of corrosion, whereas at 50 and 80 °C they were very susceptible to localized type of corrosion.     

Oxidation, carburisation and metal dusting of 304 stainless steel in CO/CO2 and CO/H2/H2O gas mixtures

The oxidation and carburisation behaviour of 304 stainless steel was studied during thermal cycling in CO/CO₂ at 700 °C, and also in CO/H₂/H₂O at 680 °C. Thermal cycling caused repeated scale separation which accelerated chromium depletion from the alloy subsurface regions. The CO/CO₂ gas, with a_C=7 and , caused internal precipitation of oxides and carbides, some surface damage, but no dusting. In contrast, the CO/H₂/H₂O gas, with a_C = 19 and caused rapid graphite deposition and metal dusting. This was accompanied by internal oxidation and carburisation. The internal oxide was identified as spinel, which forms in the short term, but not at long reaction time. Its formation produced a significant volume expansion, which disrupted the material and resulted in surface damage in both gas atmospheres. In CO/H₂/H₂O, however, direct graphite deposition and metal disintegration into dust was the main reaction. The very different reaction morphologies produced by the two gas mixtures are discussed in terms of competing gas-alloy reaction steps.     

Photosensitive nanostructured TiO2 grown at room temperature by novel “bottom-up” approached CBD method

The current paper incorporates with a “bottom-up” approached chemical bath deposition method to grow titanium dioxide (TiO₂) nanostructure at room temperature on glass and stainless steel substrates. The room temperature deposited TiO₂ films are heat treated at 673 K for 1 h in air and the corresponding change in structural, morphological and optical properties are studied by means of X-ray diffraction (XRD), Fourier transform infrared (FTIR), scanning electron microscopy (SEM), and UV-VIS-NIR spectrophotometer. The heat-treated films are utilized as a photocathode in photoelectrochemical (PEC) cell in 1 M NaOH electrolyte. The experimental results show that, the CBD method allows formation of photosensitive, anatase TiO₂ thin film, which can be potentially tuned in many functional applications with feasibility.     

Laser-induced enhancement of the surface hardness of nanoparticulate TiO2 self-cleaning layer

We here report that the abrasion resistance of nanoparticulate TiO₂ self-cleaning layers can be highly enhanced without a considerable loss of photocatalytic capability. TiO₂ coating layers solution-deposited onto the glass substrate were irradiated by a pulsed ultraviolet (UV) laser at 355 nm, which modified the surface morphologies via laser-induced local melting of TiO₂ nanoparticles. The surface hardness, measured by pencil scratch test, improved with increasing laser power (P). While an unmodified TiO₂ layer revealed a hardness of 6B, it increased to 2H after the surface was irradiated at P = 0.3 W. Almost all of the stearic acid deposited on an unmodified sample disappeared after UV exposure for 12 h. The photocatalytic decomposition was slowed down on laser-irradiated TiO₂ surfaces and this is attributed to the reduction of specific surface areas as a result of the morphological modifications. However, a TiO₂ layer hardened to 2H still exhibited fairly good photocatalytic activity, decomposing more than 75% of the stearic acid after exposure for the same duration.