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.     

Electrolytic MgO/ZrO2 duplex-layer coating on AZ91D magnesium alloy for corrosion resistance

By a two-step fabrication process of electrolytic deposition and annealing treatment, an MgO/ZrO₂ duplex-layer coating has been prepared on AZ91D magnesium alloy as a protective film against corrosion. Owing to the chemical bonding formed after the condensation of precursory hydroxides, the adhesion strength, thickness and compactness of MgO coating on the substrate are significantly enhanced by the intermediate ZrO₂ layer which prevents the formation of corrosion product Mg₂(OH)₃Cl·4H₂O. As a result, the MgO/ZrO₂ duplex-layer coated specimen reveals relatively high corrosion resistance and superior stability in 3.5 wt% NaCl solution with respect to the MgO single-layer coated specimen.     

Thermal stability behaviors of Cr(N,O)/CrN double-layered coatings by TGA/DTA analysis

In this study, Cr(N,O)/CrN double-layered coatings were synthesized using the cathodic arc deposition (CAD) process. CrN film was first deposited onto a substrate as an interlayer to ensure better adhesion, and Cr(N,O) film was subsequently deposited on top of the CrN layer as the surface layer. Variation in the Cr(N,O) coating composition was achieved through changing the O₂/N₂ flow ratio during the last stage of processing. Phase structure, chemical composition, and morphology of the resulting coatings were analyzed and observed using the X-ray diffractometer, Auger electron spectrometer and SEM. In addition, oxidation behavior of the coatings was investigated using TGA/DTA methods. The tests were carried out by increasing temperature up to 1000 °C in ambient air. With the introduction of oxygen gas during the CAD process, a superficial layer was produced in the Cr(N,O) constituent containing CrN and Cr₂O₃ phases. The formation of the oxide phase attributed to the reaction of chromium and oxygen was more favorable than that of chromium and nitrogen. The results also showed that Cr(N,O)/CrN double-layered coatings exhibited superior oxidation resistance at elevated temperature than that of CrN single-layer coated specimen (870 °C vs. 750 °C).     

Enhanced sulphidation/oxidation resistance of Ti–45Al–8Nb alloy by multilayered coatings at 850°C for up to 675 h

The high temperature sulphidation/oxidation behaviour of three multilayered coatings CrAlYN/CrN etched by Y⁺, CrAlYN/CrN etched by Cr⁺ and CrAlYN/CrN etched CrAl⁺ and the uncoated γ-TiAl (Ti–45Al–8Nb (at-%) used as reference sample was studied at 850°C for 675 h. Sulphidation/oxidation test was performed in the environment of H₂/H₂S/H₂O, yielding pS₂?=?10^?1 Pa and pO₂?=?10^?18 Pa. Kinetic data obtained by discontinuous gravimetric method showed that the multilayered coatings effectively enhanced the sulphidation/oxidation resistance of γ-TiAl alloy. The corrosion resistance decreasing in order: CrAlYN/CrN etched by Y⁺>CrAlYN/CrN etched by CrAl⁺>CrAlYN/CrN etched by Cr⁺>γ-TiAl. Scale development studies using SEM, EDX and X-ray diffraction confirmed two regions of the coated materials: ‘affected,’ where coating cracked and developed non-protective TiO₂ scale, and ‘unaffected,’ where protective (Al,Cr)₂O₃ scale formed. The uncoated γ-TiAl material, after exposure, showed a typical multilayered structure consisting of layers of TiO₂ and Al₂O₃.     

Corrosion protection of AZ31 magnesium alloy by a TiO2 coating prepared by LPD method

TiO₂ layer was prepared as a protective coating for AZ31 magnesium alloy by the liquid phase deposition (LPD) method followed by an annealing treatment. The structural evolution and crystallization of coating brought by annealing were investigated by field emission scanning electron microscopy (FE-SEM) and X-ray diffraction (XRD), respectively. The corrosion protection performance was evaluated in a three-electrode electrochemical examination system. The anatase TiO₂ layer shows evident corrosion resistance. With the increase of the annealing temperature and prolongation of annealing time, the anticorrosion property was improved. The improvements of the anticorrosion properties were related with the structural evolution of the coating brought by the annealing treatment.     

Surface modification of NiTi/PZT heterostructure thin films using various protective layers for potential MEMS applications

The present study explored the in-situ deposition of hard and adherent nanocrystalline protective coatings on NiTi/PZT/TiO_x thin film heterostructure prepared by dc/rf magnetron sputtering. Protective layers (AlN, CrN and TiCrN) of approximate thickness (~ 200 nm) were used to improve the surface, mechanical and corrosion properties of NiTi/PZT/TiO_x heterostructure without sacrificing the shape memory effect and ferroelectricity of the NiTi and PZT layers, respectively. The influence of the protective layer on structural, electrical and mechanical properties of NiTi/PZT/TiO_x heterostructure was systematically investigated and the results were compared. Nanoindentation studies were performed at room temperature to determine the hardness and reduced modulus. The surface modified NiTi/PZT/TiO_x heterostructures were found to exhibit high hardness, high elastic modulus and thereby better wear resistance as compared to pure NiTi/PZT/TiO_x films. From the results of potentiodynamic polarization test conducted in 1 M NaCl solution, the CrTiN coated NiTi/PZT/TiO_x heterostructure showed the best corrosion resistance with the lowest corrosion current density (1.52 × 10^? 8 A cm^? 2) and the highest protective efficiency (96.8%). The results presented here prove the potential of a surface modified NiTi/PZT/TiO_x heterostructure to be used in various microelectromechanical (MEMS) applications.     

Short‐term oxidation and hot corrosion resistance of a gradient CrN/Cr1−xAlxN coating

A CrN/Cr_1?xAl_xN coating comprised of an inner layer of CrN and an outer layer of Cr_1?xAl_xN with a gradient distribution of Al was deposited on two different alloys by a reactive sputtering method. Oxidation and hot‐corrosion tests of the gradient CrN/Cr_1?xAl_xN coating were performed at different temperatures. The phase compositions and morphologies of the as‐deposited coating and the corrosion products were investigated by using XRD and SEM/EDS. The results showed that the gradient CrN/Cr_1?xAl_xN coating exhibited good oxidation resistance at temperatures above 1000 °C owing to the formation of an α‐Al₂O₃‐rich oxide scale. The coating possessed good hot‐corrosion resistance in molten sulfate because the inner CrN layer could supply enough Cr to form a relatively protective Cr₂O₃ after the Al₂O₃‐enriched scale failed due to its dissolution in the molten sulfate.     

Influence of oxygen ion irradiation on the corrosion aspects of Ti-5%Ta-2%Nb alloy and oxide coated titanium

The corrosion resistance of Ti-5%Ta-2%Nb alloy and DOCTOR (double oxide coating on titanium for reconditioning) coated titanium by O⁵⁺ ion irradiation were compared and investigated for their corrosion behaviour. O⁵⁺ ion irradiations were carried out at a dose rate of 1 × 10¹⁷, 1 × 10¹⁸ and 1 × 10¹⁹ ions/m² at 116 MeV. The surface properties and corrosion resistance were evaluated by using scanning electron microscopy (SEM), atomic force microscopy (AFM), energy dispersive X-ray (EDX), glancing-angle X-ray diffraction (GXRD) and electrochemical testing methods. The results of electrochemical investigations in 11.5 N HNO₃ indicated that the open circuit potential (OCP) of DOCTOR coated titanium is nobler than Ti-5%Ta-2%Nb alloy. The potentiodynamic polarization study of Ti-5%Ta-2%Nb alloy and DOCTOR coated specimen indicated decrease in passive current density with increase in ion doses (1 × 10¹⁷ to 1 × 10¹⁹ ions/m²) indicating decrease in anodic dissolution. Nyquist arc behaviour in the electrochemical impedance study substantiated the enhancement in oxide layer stability by O⁵⁺ ion irradiation. AFM results revealed that the DOCTOR coated Ti surface was dense without gross voids, and the surface roughness decreased by O⁵⁺ ion irradiation, but increased after corrosion test. EDX and GXRD patterns of DOCTOR coated Ti sample indicated that the coating was mainly composed of rutile TiO₂. Based on the above results, the O⁵⁺ ion irradiation effect on corrosion behavior of Ti-5%Ta-2%Nb alloy and DOCTOR coated titanium are discussed in this paper.     

Enhancing Biocompatibility and Corrosion Resistance of Ti-6Al-4V Alloy by Surface Modification Route

Titanium (Ti) and its alloys are widely used as candidate materials for biomedical implants. Despite their good biocompatibility and corrosion resistance, these materials suffer from corrosion after implantation in biological environments. The aim of this research work is to study the effect of two coatings on biocompatibility and corrosion behavior of Ti-6Al-4V biomedical implant material. Hydroxyapatite (HA) and hydroxyapatite/titanium dioxide (HA/TiO₂) coatings were thermal-sprayed on Ti-6Al-4V substrates. In the latter case, TiO₂ was used as a bond coat between the substrate and HA top coat. The corrosion behavior of coated and un-coated samples in Ringer’s solution was studied by potentiodynamic and linear polarization techniques. Before and after corrosion testing, XRD and SEM/EDS techniques were used for the analysis of phases formed and to investigate microstructure/compositional changes in the coated specimens. The cellular response was analyzed by the MTT (microculture tetrazolium) assay. The results showed that both the HA, as well as, the HA/TiO₂ coatings significantly increased the corrosion resistance of the substrate material. The HA coating was found to be more biocompatible as compared to the un-coated and HA/TiO₂-coated Ti-6Al-4V alloy.     

阳极氧化法制备TiO2膜在模拟深海热液区的耐腐蚀性能

以恒压阳极氧化方法在钛基体上制备TiO₂氧化膜,使用水热釜模拟深海热液区的条件研究其耐腐蚀性能。采用XRD、SEM、接触角测定仪对氧化膜以及腐蚀试样产物进行晶型、表面结构、化学成分和亲疏水性能测定,使用动电位扫描方法对其进行极化曲线测试。结果表明,钛试样和阳极氧化钛试样在模拟深海环境条件下,经过腐蚀反应在表面都生成了一层非致密的TiO₂ 膜,对基体并不能起到保护作用,而阳极氧化生成的致密TiO₂ 膜对基体能够起到很好的保护作用。经腐蚀后钛试样表面有TiH₂相的形成,腐蚀电位负移0.45 V。而阳极氧化钛试样表面没有TiH₂相的形成,且腐蚀电位负移较小,表现出良好的耐腐蚀性能。     

Corrosion behavior and resistance of hot-dip Al−Cr coated steel sheet under a salt corrosive environment

The corrosion behavior and resistance of hot-dip Al and Al−Cr coated steel sheets (SS) were investigated via scanning electron microscopy (SEM), energy dispersive X-ray spectrometry (EDX), electron probe micro analysis (EPMA), glow discharge light spectroscopy (GDLS), and X-ray diffraction patterns (XRD). The Al−Cr coated layer was composed of the following three phases. Al phase comprised the surface layer, Al₁₃Cr₂ the middle layer, and Al₁₃Fe₄ and Al₅Fe₂ phases the interfacial layer between the Fe substrate and the coated layer. The corrosion behavior of the Al−Cr coated layer showed different aspects compared with the Al coated layer. In the Al−Cr coated layer, Cr was observed at an intermediate layer having a band shape. From the analysis of the polarization curve, the initial corrosion current of the Al−Cr coated SS was 10 times lower than that of Al in the early stage, and the corrosion resistance was superior to that of Al. The Al coated SS formed an Al−Fe−Si IMC layer, and the coated layer was almost destroyed. Many cracks were produced, and the corroded parts were enlarged from the cracks. The upper part of the Al−Cr coated SS, an Al−Si coated layer, was corroded. In contrast, the Cr-rich intermediate layer was not destroyed. Consequently, the high corrosion resistance was attributed to the densely covered Al(OH)₃ and the intermetallic compound layer of Al₁₃Cr₂. These results significantly contribute toward attaining a detailed understanding of the corrosion behavior and resistance Al−Cr coated steel sheets.     

Corrosion behaviour of single and double layer hydroxyapatite coatings on 316L stainless steel by plasma spray

AISI316L stainless steel is extensively used in orthopedic and dental applications. However, this alloy exhibits low integration behaviour when it comes in contact with surrounding bone tissue and implant healing duration can be as much as few months. The aim of this study is the fabrication of biocompatible hydroxyapatite (HA) coatings on stainless steel substrate in order to accelerate the process of osseointegration of implants. The biocompatible single layer of Titania (TiO₂), Hydroxyapatite and bi-layer TiO₂/HA coatings were deposited by atmospheric plasma spray on 316L stainless steel. Coated and uncoated stainless steel specimens were incubated in simulated body fluids and 0.9% NaCl solutions for 1h and 7 days. In vitro electrochemical-corrosion evaluation of coated and uncoated stainless steel specimens have been investigated by Tafel extrapolation and linear polarization methods. Results indicates that corrosion resistance of single layer HA coated stainless steel specimens are superior to single layer TiO₂ and bi-layer HA/TiO₂ coated stainless steel specimens.     

Oxidation and Sulfidation Behavior of AlTiN-Coated Ti–46.7Al–1.9W–0.5Si Intermetallic with CrN and NbN Diffusion Barriers at 850°C

Attempts have been made to improve the high-temperature corrosion behavior of an intermetallic alloy, Ti–46.7Al–1.9W–0.5Si, in an H₂/H₂S/H₂O atmosphere at 850°C using AlTiN coating with and without CrN and NbN diffusion barriers. The oxidation and sulfidation behavior of the uncoated Ti–46.7Al–1.9W–0.5Si alloy followed protective kinetics with a parabolic rate constant of 6×10^–11 g²/cm⁴/s. A multi-layered scale developed: an outer rutile (TiO₂) layer, a continuous layer of -Al₂O₃ beneath the rutile layer, and an inner TiS layer, in which pure W was scattered. Fast outward diffusion of Ti within the substrate resulted in the formation of a zone of high concentration of aluminum (TiAl₃ and TiAl₂) between the scale and substrate.The use of an AlTiN coating greatly increased the oxidation and sulfidation resistance of Ti–46.7Al–1.9W–0.5Si. The use of NbN and CrN diffusion barriers further enhanced its corrosion resistance. The protection of the double-layer coatings persisted even after 240 hr exposure. However the mismatch of thermal expansion coefficients between the coating and substrate led to the development of cracks in some locations within the coatings. A 2.5 m thick AlTiN coating on the Ti–46.7Al–1.9W–0.5Si substrate with an embedded defect was modeled using the general finite element (FE) program ABAQUS. The modeling results showed rapid mode I failure of the coating at a temperature of 774°C. The through-fracture of the nitride film caused the nitride coating to shrink back leading to delamination around the crack in the nitride coating. The cracks formed acted as diffusion paths, for the ingress of oxygen and sulfur species and the outward diffusion of substrate elements, which resulted in the formation of nodular corrosion products with similar morphologies and microstructures to the uncoated alloy in those locations where cracks developed.     

Role of chlorine in the oxidation resistance of Ti-45at.% Al-1.6at.%Mn intermetallic compound

In order to investigate the role of chlorine in the oxidation resistance of Ti-45at.%Al-1.6at.%Mn intermetallic compounds, specimens with and without chlorine were prepared by a reactive sintering and a remelting process, respectively, and then isothermally oxidized at temperatures of 800 to 1000°C. The oxidation resistance of reactive-sintered Ti-45at.%Al-1.6at.%Mn containing 0.02 wt.%Cl was superior to that of remelted specimens due to the formation of a protective Al₂O₃, layer. From the results of an EPMA line scan of a cross-section of the oxide layer, carbon and chlorine peaks were detected on the TiO₂ layer of the reactive-sintered specimens suggesting that TiO₂ can decompose to TiCl₄ through the reaction with Cl₂ and C (or CO). As a result of the chlorination of TiO₂, the growth of TiO₂ could be constrained and a protective A1₂O₃ scale was easily formed on the reactive-sintered alloy.     

Effect of Na2SO4 and Water Vapor on the Corrosion of Ti3SiC2

The corrosion behavior of polycrystalline Ti₃SiC₂ was studied in the presence of Na₂SO₄ deposit and water vapor at 900°C and 1000°C. The mass gain per unit area of the samples superficially coated with Na₂SO₄ exposed to water vapor was slightly lower than that of the samples corroded without water vapor. The microstructure and composition of the scales were investigated by SEM/EDS and XRD. Pores were observed in the corroded sample surfaces. The main corrosion phases on the sample surface were identified by XRD as TiO₂, Na₂Si₂O₅ and Na₂TiO₃. After Ti₃SiC₂ corroded in the presence of the Na₂SO₄ deposit and water vapor, the scale had a three-layer microstructure, which was different from the duplex corrosion scale formed on Ti₃SiC₂ beneath the Na₂SO₄ film without water vapor. Because water vapor penetrated the corrosion layer and then reacted with SiO₂ to form volatile Si(OH)₄, an intermediate porous and TiO₂-enriched layer formed in the corrosion layer.     

Influence of potassium pyrophosphate in electrolyte on coated layer of AZ91 Mg alloy formed by plasma electrolytic oxidation

The effect of potassium pyrophosphate in the electrolyte on plasma electrolytic oxidation (PEO) process for AZ91 Mg alloy was investigated. The morphologies and chemical compositions of the coating layer on the AZ91 Mg alloy were evaluated and corrosion resistance was also estimated by potentiodynamic polarization analysis. The coating layer on AZ91 Mg alloy coated from the Bath 2 containing 0.03 mol/L of potassium pyrophosphate for 360 s exhibited considerably dense structure and contained 11%–18% (mass fraction) of phosphorous. The higher content of phosphorous of coating layer coated from Bath 2 could be detected at the bottom of oxide layer, which strongly implied that the phosphorous ion might be concentrated at the barrier layer. Corrosion potential of coating layer of AZ91 Mg alloy increased and corrosion current density decreased with increasing the concentration of potassium pyrophosphate. The polarization resistance (R_p) of coating layer of AZ91 Mg alloy coated from Bath 2 was 4.65×10⁷ Ω/cm², which was higher than that (R_p=3.56×10⁴ Ω/cm²) of the sample coated from electrolyte without potassium pyrophosphate. The coating layer coated from Bath 2 containing 0.03 mol/L potassium pyrophosphate exhibited the best corrosion resistance.     

Characterization of Thermal-Sprayed HAP and HAP/TiO<Subscript>2</Subscript> Coatings for Biomedical Applications

In the present study, hydroxyapatite (HAP) coating along with HAP/TiO₂ coating has been deposited by high-velocity flame spray (HVFS) technique onto 316LSS. Titania was used as a bond coat and HAP as top coat in HAP/TiO₂ coating. The main aim of the study is to investigate the corrosion behavior of thermal spray coating of HAP and HAP/TiO₂ on steel. Electrochemical corrosion testing was carried out using potentiodynamic polarization test. The corrosion behavior of bare and as-sprayed specimens was analyzed in simulated body fluid known as Hank’s solution. As-sprayed specimens along with corroded specimens were further characterized by XRD, SEM/EDS, and x-ray mapping analysis. It was observed that the HAP/TiO₂ coating possessed higher microhardness (280 Hv) as compared to HAP coating (254 Hv). Surface roughness also got enhanced in case of HAP/TiO₂ coating (9.35 μm) as compared to pure HAP coating (7.37 μm). The porosity of the HAP coating was found to be higher than the bond coating. It was observed that the Ca/P ratio almost resembled that of the natural bone composition. The corrosion resistance of steel increased after the deposition of HAP and HAP/TiO₂ coatings. The maximum corrosion resistance was exhibited by HAP/TiO₂ coating.     

Microstructure and corrosion behaviour of Al2O3–13 wt-% TiO2 laser alloyed magnesium alloys

Nanostructured Al₂O₃–13?wt-% TiO₂ was prepared on AZ91D magnesium alloy surface by laser surface alloying to improve its corrosion resistance. The microstructure of the laser surface alloyed specimens before and after corrosion tests was characterised by scanning electron microscope and optical microscope (OM). The phase and element composition were investigated by X-ray diffractometer and energy-dispersive spectrometry. An electrochemical workstation was used to evaluate the corrosion behaviour of the specimens. Results showed that the laser surface alloyed layer was primarily composed of Mg and Mg₁₇Al₁₂. Al₂O₃ and TiO₂ existed in the form of agglomerated particles. The corrosion resistance was improved after laser surface alloying.     

Composite cerium oxide/titanium oxide thin films for corrosion protection of AZ91D magnesium alloy via sol–gel process

Anti‐corrosive composite cerium oxide/titanium oxide (CeO₂/TiO₂) thin films were successfully prepared on an AZ91D magnesium alloy substrate by applying cerium oxide (CeO₂) thin films as the inner layer with a sol–gel process. Composition and surface morphology of the thin films were analyzed using X‐ray diffraction (XRD) and scanning electron microscope (SEM). XRD showed that the composite films consisted of cerianite and anatase phases. The wettability of the thin films was evaluated by water contact angles measurements. Potentiodynamic polarization curves and electrochemical impedance spectroscopy (EIS) tests were used to evaluate the corrosion behavior of the bare substrate and coated samples in 3.5 wt% sodium chloride solution (3.5 wt% NaCl). The results demonstrated that titanium oxide (TiO₂) thin film mainly dominated the corrosion resistance of samples and the composite films with excellent hydrophilicity could significantly improve the corrosion resistance of AZ91D magnesium alloy.     

Advance Complex Liquid Nitriding of Stainless Steel AISI 321 Surface at 430 °C

Liquid nitriding of type 321 austenite stainless steel was conducted at low temperature at 430 °C, using a type of a complex chemical heat-treatment; and the properties of the nitrided surface were evaluated. Experimental results revealed that a modified layer was formed on the surface with the thickness ranging from 2 to 30 μm varying with changing treatment time. When the stainless steel subjected to the advanced liquid nitriding less than 8 h at 430 °C, the main phase of the nitrided coating layer was the S phase generally. When the treatment time prolonged up to 16 h, S phase formed and partially transformed to CrN subsequently; and then the fine secondary CrN phase precipitated. All treatments performed in the current study can effectively improve the surface hardness. The nitrided layer thickness changed intensively with the increasing nitrided time. The growth of the nitride layer took place mainly by nitrogen diffusion according to the expected parabolic rate law. The highest hardness value obtained in this experiment was about 1400 Hv_0.25. Low-temperature nitriding can improve the corrosion resistance of the 321 stainless steel against diluted vitriolic acid. The immerse test results revealed that the sample nitrided for 16 h had the best corrosion resistance than the others. SEM examinations indicated that after nitriding, the corrosion mechanisms of the steel had changed from serious general corrosion of untreated sample to selectivity corrosion of nitrided samples in the diluted vitriolic acid.