X-ray photoelectron spectroscopy study of the corrosion behaviour of galvanised steel implanted with rare earths

The present paper studies the effect of ion implantation of 2 × 10¹⁶ ions/cm² of Ce⁺ and 2 × 10¹⁶ ions/cm² of La⁺ at 150 keV on the corrosion behaviour of hot-dip galvanised steel. After implantation, galvanised steel was characterised by means of XPS previous to and following immersion in the medium. The results revealed incorporation of cerium and lanthanum on the surface as Ce₂O₃ and La₂O₃, respectively. Electrochemical impedance spectroscopy was carried out in order to evaluate its corrosion behaviour in 0.6 M NaCl during 1 month of immersion. The corrosion resistance was improved by an increase in the charge transfer resistance of the implanted specimens in the medium. This effect could be associated with changes in the morphology/microstructure of the corrosion products layer rather than in its composition variations.     

Corrosion behaviour of nitrogen ion implanted AISI type 304L stainless steel in nitric acid medium

The effects of nitrogen ion implantation on corrosion behaviour of 304L stainless steel in 1 N HNO₃ medium were investigated using surface analytical and electrochemical techniques. Nitrogen ion was implanted at 70 keV in the dose range of 1 × 10¹⁵, 1 × 10¹⁶, 1 × 10¹⁷ and 2.5 × 10¹⁷ N⁺/cm², respectively. Grazing incidence X-ray diffraction results for unimplanted and up to dose of 1 × 10¹⁶ N⁺/cm² showed co-existence of γ-Fe and α′-Fe and, at higher doses (1 × 10¹⁷ and 2.5 × 10¹⁷) preferential formation of chromium nitride was observed. X-ray photoelectron spectroscopy investigation confirmed the formation of chromium nitride at higher doses. Electrochemical corrosion investigation revealed nobler open circuit potential, decrease in corrosion current densities, passive current densities and increase in polarization resistance with increase in dose rate. Surface morphology analysis after polarization study using atomic force microscope showed grain boundary dissolution for unimplanted specimens and resistance to surface dissolution with increase in dose rate for implanted specimens.     

Corrosion resistance of Al ion implanted AZ31 magnesium alloy at elevated temperature

The Al ion implantation into AZ31 magnesium alloy was carried out in a MEVVA 80-10 ion implantation system at an ion energy of 40-50 keV with an ion implantation dose ranging from 2 × 10¹⁶ to 1 × 10¹⁷ ions/cm² at an elevated temperature of 300 °C induced by an ion current density of 26 μA/cm². The concentration-depth profile of implanted Al in AZ31 alloy measured by Rutherford backscattering spectrometry (RBS) is a Gaussian-type-like distribution in a depth up to about 1200 nm with the maximum Al concentration of about 8 at.%. The X-ray diffraction (XRD) analysis revealed the formation of α-Mg(Al) phase, intermetallic β-Mg₁₇Al₁₂, and MgO phase on the Al ion implanted samples. The potentiodynamic anodic polarization curves of the Al ion implanted samples in the 0.01 mol/l NaCl solution with a pH value of 12 showed increases of the corrosion potential and the pitting breakdown potential, and a decrease of the passive current density, respectively. The Al ion implanted samples with 6 × 10¹⁶ ions/cm² achieved the high pitting breakdown potential to about − 480 mV (SCE). In the 0.08 mol/l NaCl solution with pH = 12, the Al ion implanted samples with 1 × 10¹⁷ ions/cm² showed an increased pitting breakdown potential to about − 1290 mV (SCE), from around − 1540 mV (SCE) of unimplanted samples. It is indicated that different corrosion mechanisms are responsible for improvement in corrosion resistance of the AZ31 magnesium alloy in the NaCl solutions with the varied concentrations.     

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.     

Surface characterization of passive film formed on nitrogen ion implanted Ti-6Al-4V and Ti-6Al-7Nb alloys using SIMS

The aim of this paper is to study the effect of N⁺ ion implantation on corrosion and phase formation on the implanted surfaces of Ti-6Al-4V and Ti-6Al-7Nb alloys. Nitrogen ion was implanted on Ti-6Al-4V and Ti-6Al-7Nb alloys at an energy of 70 and 100 keV, respectively using a 150 keV accelerator at different doses ranging from 5 × 10¹⁵ to 2.5 × 10¹⁷ ions/cm². Electrochemical studies have been carried out in Ringer’s solution in order to determine the optimum dose that can give good corrosion resistance in a simulated body fluid condition. The implanted surfaces of such modified doses were electrochemically passivated at 1.0 V for an hour. Secondary ion mass spectroscopy was used to study and characterize titanium oxide and titanium nitride layers produced on implanted surface and to correlate them with the corrosion resistance. The nature of the passive film of the implanted-passivated specimen was compared with the unimplanted-passivated as well as as-implanted specimens.     

Surface characteristics and corrosion behavior of Ti-Al-Zr alloy implanted with Al and Nb

Ti-Al-Zr alloys were implanted with Al and Nb to doses ranging from 1 × 10¹⁷ to 1 × 10¹⁸ ions cm⁻². The valence states of element on the sample surfaces were analyzed by X-ray photoelectron spectroscopy (XPS). Glancing angle X-ray diffraction (GAXRD) was employed on the as-implanted specimens to understand phase formation. X-ray diffraction (XRD) measurement revealed α-Ti on Al-implanted samples and (α + β)-Ti on Nb-implanted samples. The tendency was observed in increasing corrosion resistance from α- toward (α + β)-phase. In deaerated 5 M HCl, the ion-implanted Ti-Al-Zr surface containing Nb-stabilized β-phase was spontaneously passive, while Al-implanted surface displaying an active/passive behavior. In the aerated solution with pH = 10, all the implanted surfaces are passive. Enhanced reoxidation was confirmed on implanted surfaces by Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS) analysis. The corrosion in the solution with pH = 10 was governed by a predominantly TiO₂ surface film. The cathodic kinetics was seen to affect the corrosion behavior in 5 M HCl.     

Composition and structure of Al ions implanted Fe at elevated temperatures

Al ions with ion energy of 120 keV are implanted into Fe under ion current density of 3.18 μA/cm² to implantation doses of 5 × 10¹⁶ and 1 × 10¹⁷ ions/cm² at room temperature and elevated temperatures of 250 and 500 °C, respectively. At 250 °C, the distribution depth of implanted Al reaches 160 nm with a peak concentration of 6 at.% at the dose of 5 × 10¹⁶ ions/cm², and 180 nm with 10 at.% at 1 × 10¹⁷ ions/cm², analyzed by Rutherford backscattering spectroscopy, respectively. At 500 °C, the implantation depth is 200 nm and the maximum concentration of Al is 10 at.% at the dose of 1 × 10¹⁷ ions/cm². With 5 × 10¹⁶ ions/cm², the intermetallics Al₁₃Fe₄ is formed in the Fe samples at 500 °C, revealed by X-ray diffraction. With 1 × 10¹⁷ ions/cm², the phase is also detected at 250 °C. The concentration-depth profiles of implanted Al in Fe samples at the room temperature, 250 °C and 500 °C are calculated by a mass transfer model that is built based on the transport of ions in matter and the irradiation enhanced diffusion. The calculated concentration-depth profiles are in reasonable agreement with those obtained from the experiments.     

The beneficial role of Y-implantation on the aqueous corrosion of stainless steel

The corrosion behaviour of Y-implanted austenitic stainless steel AISI 321 samples was investigated in 0.5 M H₂SO₄ at ambient temperature using potentiodynamic polarization and cyclic voltammetry. The implantation of 1 × 10¹⁶ Y-ions/cm² of 40 keV energy did not lead to an improvement of the corrosion resistance of the material because of sputtering effects. On the other hand, a significant improvement of the corrosion resistance was observed by increasing of the dose (2 × 10¹⁷ Y-ions/cm² implanted in the presence of oxygen) and the implantation energy (55 and 80 keV). The elemental composition of the near-surface layers of the implanted steel samples prior and after the corrosion attack was determined by Rutherford backscattering spectrometry (RBS) and Nuclear Reaction Analysis (NRA) using alpha particles, protons and deuterons as projectiles. The surface morphology and microstructure of the non-corroded and corroded samples were examined by Scanning Electron Microscopy (SEM). The corrosion resistance of the implanted materials was found to be related with the thickness and the composition of the implanted layer.     

Corrosion behavior and surface characterization of tantalum implanted TiNi alloy

TiNi shape memory alloy has been modified by Ta plasma immersion ion implantation technology to improve corrosion resistance. The results of the polarization tests show that the corrosion resistance of TiNi alloy in Ringer's solution at 310 K has been improved by the Ta ion implantation and the Ta/TiNi sample with a moderate incident dose of 1.5 × 10¹⁷ ions/cm² exhibits the best corrosion resistance ability. The surface characterization and chemical composition of the Ta/TiNi samples were determined by Auger electron spectroscopy (AES), Atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS) methods. AFM images reveal that compact aggregates of nano-grains uniformly disperse on the surface of the Ta/TiNi samples. AES and XPS analyses on the Ta/TiNi sample show that the component of the surface layer is mainly composed of TiO₂ and Ta₂O₅, which is benefit to the corrosion resistance ability and biocompatibility.     

Surface characterization of ultra high molecular weight polyethylene modified by swift heavy ion beam bombardment

The damage processes induced by swift heavy ions (SHI), can be very different to those induced by classical low ionising particles. This is due to the high electronic stopping power of SHI. Ultra high molecular weight polyethylene (UHMWPE) was irradiated with 6.77 MeV helium and 12.5 MeV carbon beams and fluences ranging from 10¹¹ to 10¹³ cm^− 2 and 2 × 10¹⁰ to 5 × 10¹³ cm^− 2, respectively. Structural changes at the polymer near surface region were studied by means of infrared spectroscopy measurements and wear resistance tests. With FTIR spectroscopy we studied the changes in crystallinity, double bond CC, trans-vynilene and graphite formation and the evolution of methylene group as a function of fluence. The experiments have determined that exists an optimum ion fluence value, that depends on the ion mass and energy, at which the wear resistance increases of about 85% respect to the unirradiated polymer. For helium this value is 2 × 10¹² cm^− 2 and for carbon 4 × 10¹¹ cm^− 2. At these fluence values no sign of graphite was found by FTIR studies. Using a Monte Carlo simulation program we determined that the surface area affected by the track core of the incoming ions was less than 19 and 35% for helium and carbon respectively.     

Corrosion behavior of electroless Ni-P alloy coatings containing tungsten or nano-scattered alumina composite in 3.5% NaCl solution

The corrosion protection performance of electroless deposited nickel-phosphorus (Ni-P) alloy coatings containing tungsten (Ni-P-W) or nano-scattered alumina (Ni-P-Al₂O₃) composite coatings on low carbon steel was studied. The effect of heat treatment on the coating performance was also studied. The optimum conditions under which such coatings can provide good corrosion protection to the substrate were determined after two weeks of immersion in 3.5% NaCl solution. Electrochemical impedance spectroscopy (EIS) and polarization measurements have been used to evaluate the coating performance before and after heat treatment. The Ni-P-W coatings showed the highest surface resistance compared with Ni-P-Al₂O₃ and Ni-P. The surface resistance of Ni-P-W coatings was 12.0 × 10⁴ Ω cm² which is about the double of the resistance showed by Ni-P-Al₂O₃ (7.00 × 10⁴ Ω cm²) and twenty times greater than the surface resistance of Ni-P (0.78 × 10⁴ Ω cm²). XRD analysis of non-heat-treated samples revealed formation of a protective tungsten phosphide phase. Heat treatment has an adverse effect on the corrosion protection performance of tungsten and alumina composite coatings. The surface resistance decreased sharply after heat treatment.     

Improving wear resistance and corrosion resistance of AZ31 magnesium alloy by DLC/AlN/Al coating

A novel protective coating, consisting of three layers (top: diamond-like carbon, middle: aluminum nitride, bottom: aluminum), was deposited on the surface of AZ31 magnesium alloy layer by layer. Nano-indenter, electrochemical system and tribological tester were performed to investigate the hardness, wear resistance and corrosion resistance of the coated AZ31 magnesium alloy, respectively. The DLC/AlN/Al coating improved the magnesium alloy's surface hardness and reduced its friction coefficient, which consequently induced a great improvement of the magnesium alloy's wear resistance. Furthermore, the corrosion resistance of the AZ31 magnesium alloy with the DLC/AlN/Al coating was also enhanced with the corrosion current density decreasing from 2.25 × 10⁻⁵ A/cm² to 1.28 × 10⁻⁶ A/cm² in a 3.5 wt.% NaCl solution.     

Electrochemical behaviour of Cu-40Zn in 3% NaCl solution polluted by sulphides: Effect of aminotriazole

The electrochemical behaviour of Cu-40Zn alloy, in 3% NaCl medium pure and polluted by 2 ppm of S²⁻ ions, has been studied in the absence and presence of the 3-amino-1,2,4 triazole (ATA) as corrosion inhibitor. Electrochemical measurements (polarisation curves and electrochemical impedance spectroscopy) showed that sulphides accelerate the alloy corrosion. The studies revealed that ATA inhibits both cathodic and anodic reactions, indicating a mixed type of inhibition. The inhibiting effect was higher in presence of S²⁻ ions than in its absence. Scanning electron microscopy analysis showed that the inhibitor acts by preventing the adsorption of S²⁻ ions, and formation of Cu₂S at the alloy surface. The inhibition efficiency reaches 98% at a concentration of 5 × 10⁻³ M.     

Nitrogen ion implantation and in vitro corrosion behavior of as-cast Ti-6Al-7Nb alloy

In the present investigation, surface modification of Ti-6Al-7Nb alloy with nitrogen ions is considered as a method to improve its performance with respect to corrosion. Nitrogen ion was implanted on Ti-6Al-7Nb alloy at an energy of 70 and 100 keV using a 150 keV accelerator at different doses between 1×10¹⁶ and 3×10¹⁷ ions/cm². Gracing incidence X-ray diffraction was employed on the implanted specimens to understand the phases formed with increasing doses. The implanted samples were subjected to electrochemical study in Ringer's solution in order to determine the optimum dose that can give good corrosion resistance in a simulated body fluid condition. The OCP of the implanted specimens were found to shift in the noble direction in comparison with unimplanted specimen. The passive current density and area of the repassivation loop were found to decrease as the dose values increased. The electrochemical impedance spectroscopic results indicate that the polarization resistance was higher for the dose of 2.5×10¹⁷ ions/cm² implanted at both energy of 70 and 100 keV. Nitrogen ion implantation enhanced the passivability and reduces the corrosion kinetics of the alloy surface with increasing tendency for repassivation. Nature of the surface and reason for the variation and improvement in corrosion resistance are discussed in detail.     

Corrosion protection of magnesium alloy AZ31 sheets by spin coating process with poly(ether imide) [PEI]

In the present study, the potential of poly(ether imide) as corrosion protective coating for magnesium alloys was evaluated using the spin coating technique. The influence of different parameters on the coating properties was evaluated and the corrosion behaviour of the coatings was investigated using electrochemical impedance spectroscopy. The best corrosion protection was obtained preparing the coatings under N₂ atmosphere, using 15 wt.% solution in N′N′-dimethylacetamide (DMAc) which resulted in a coating of approximately 2 μm thickness, with an initial impedance of 10⁹ Ω cm² and of 10⁵ Ω cm² after 240 h of exposure to a 3.5% NaCl solution.     

Modification of the electrical properties of polyimide by irradiation with 80 keV Xe ions

We modify the electrical properties of polyimide (PI) films by irradiation with 80 keV Xe ions. The surface resistivity of irradiated PI film at room temperature decreases remarkably from 1.2 × 10¹⁴ Ω/□ for virgin PI film to 3.15 × 10⁶ Ω/□ for PI film irradiated by 5.0 × 10¹⁶ ions/cm², and the temperature dependence of the resistivity of the treated films is well-fit using Mott's Equation. The irradiated PI film structure is studied using Raman spectroscopy, X-ray diffraction, and Rutherford Backscattering Spectrometry. The concentration of O in the irradiated layer decreases with increasing fluence, while the variation of N concentration is negligible. Graphite-like carbon-rich phases are created in the irradiated layers, leading to the modification of the electrical properties.     

Effect of plasma electrolytic oxidation coating on the stress corrosion cracking behaviour of wrought AZ61 magnesium alloy

An attempt was made to understand the effect of silicate based plasma electrolytic oxidation (PEO) coating on the stress corrosion cracking (SCC) behaviour of an AZ61 wrought magnesium alloy. The SCC behaviour of untreated and PEO coated specimens was assessed using slow strain rate tensile tests at two different nominal strain rates, viz. 1 × 10⁻⁶ s⁻¹ and 1 × 10⁻⁷ s⁻¹, in ASTM D1384 test solution at ambient conditions. The PEO coating was found to improve the general corrosion resistance to a significant extent; however, the improvement in the resistance to stress corrosion cracking was only marginal.     

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.     

Characterization and corrosion studies of fluoride conversion coating on degradable Mg implants

Fluoride conversion coating was synthesized on magnesium (Mg) by immersion treatment in hydrofluoric acid (HF) at room temperature, with the aim of improving the corrosion resistance of Mg in applications as degradable implant material. After an immersion period of 24 h in 48% HF, the samples carried a bronze color, and the conversion coating was dense and free of cracks. Field-emission scanning-electron microscopy (FE-SEM) of the cross-section revealed a coating thickness of about 1.5 μm. Atomic-force microscopy (AFM) recorded an average surface roughness of ∼ 21 nm for the coated sample, similar to that of the untreated one (∼ 17 nm). The coating was mainly composed of magnesium fluoride (MgF₂) as identified by thin-film X-ray diffractometry (TF-XRD), consistent with compositional analysis using X-ray photoelectron spectroscopy (XPS). The MgF₂ was in the form of crystallites of a few nm. A small amount of oxygen was present inside the coating, suggesting that some F⁻ ions are replaced by hydroxyl (OH⁻) ions in the MgF₂ structure, or that a small amount of Mg(OH)₂ was present. The corrosion resistance of untreated and conversion coated Mg in Hanks' solution was studied using electrochemical impedance spectroscopy (EIS), potentiodynamic polarization tests, and immersion tests. EIS results showed a polarization resistance of 0.18 kΩ cm² for the untreated Mg and 5.2 kΩ cm² for the coated sample, giving an improvement of about 30 times. Polarization tests also recorded a reduction in corrosion current density from 400 μA/cm² to 10 μA/cm², showing an improvement of about 40 times. The galvanic effect between untreated and fluoride-coated Mg samples was small. Immersion tests in Hanks' solution also resulted in a much milder and more uniform corrosion damage on the fluoride-coated samples. The results of the present study showed that fluoride coating by conversion treatment is a simple and promising way of enhancing the corrosion resistance of Mg in Hanks' solution, or that it may be employed as a pretreatment step for subsequent coating.     

Ion beam modification of ePTFE for improving the blood compatibility

Expanded polytetrafluoroethylene (ePTFE), which is a durable biomaterial because of its excellent biological inertness, is now widely used for prostheses in clinical medicine. However, conversely, the inert nature of ePTFE results in poor adaptability to the surrounding tissue due to lack of a cell-adhesive property. In this study, the surface of ePTFE was modified with ion beam irradiation to improve the blood compatibility. The surface modification of ePTFE sheets by He⁺, Ne⁺, Ar⁺ and Kr⁺ ion beams was performed at an energy of 150 keV with fluences of 1 × 10¹⁴, 5 × 10¹⁴ and 1 × 10¹⁵ ions/cm². To investigate anti-thrombogenicity, Ca²⁺-replenished platelet-rich plasma (PRP) was placed in contact with the surfaces for 10 min. Compared to the non-modified ePTFE surface, platelet response was inhibited on the surfaces modified with He⁺, Ne⁺ and Ar⁺: 5 × 10¹⁴ and 1 × 10¹⁵ ions/cm², and Kr⁺: 5 × 10¹⁴ ions/cm²; however, platelet response was promoted on the surfaces modified with He⁺, Ne⁺ and Ar⁺: 1 × 10¹⁴ ions/cm², and Kr⁺: 1 × 10¹⁴ and 1 × 10¹⁵ ions/cm². The significant morphological changes in ePTFE surface associated with ion beam modification are thought to be one of the reasons for the inhibition of platelet response. Endothelial cells were cultured on the surfaces for 3 days to evaluate the cellular response. Endothelial cell growth was significantly promoted on all of the surfaces of ion beam-modified ePTFE, although the non-modified ePTFE surface dramatically inhibited this growth. It is concluded that ion beam modification of ePTFE surface can improve the blood compatibility through not only the promotion of endothelial cell growth but also the inhibition of platelet response.