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.     

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 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.     

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.     

Nano-wear, nano-hardness and corrosion-resistance of electroplated nickel surfaces after co-implantation of Cr and N2 ions

In this work, a successful sequential co-implantation treatment of Cr⁺ and N₂⁺ ions into electrodeposited nickel plates is presented. The goal of this treatment is the simultaneous enhancement of the wear resistance, mechanical stability and corrosion-protection properties of the Ni surfaces. The ion-implanted surfaces have been characterized by glow-discharge optical-emission spectroscopy, X-ray diffraction, nano-hardness, roughness, nano-wear and potentio-dynamic corrosion tests. It has been observed that the implantation of Cr⁺ or N₂⁺ alone is not sufficient to achieve simultaneously the enhancement of both the wear-resistance and the corrosion-protection properties. Conversely, the sequential implantation of Cr⁺ and N₂⁺ at 140 keV and fluencies of 3 × 10¹⁷ and 1.5 × 10¹⁷ ions/cm² respectively, permits the formation of a functional surface capable of reducing both the corrosion rate and the wear rates, with respect to those exhibited by the un-implanted Ni surfaces.This treatment can be used to protect the surfaces of micro-embossing/stamping dies based on electroformed Nickel, as an alternative to other coating strategies. Furthermore, the ion implantation assures the non-modification of the net-shape and surface finish of these types of dies, which is of crucial importance when they are used for high-precision micro-texturing/imprinting applications.     

Surface characteristics, nano-indentation and corrosion behavior of Nb implanted NiTi alloy

NiTi shape memory alloy has been modified by Nb implantation with different implantation parameters including incident dose and current. The surface morphology and chemical components are determined by atomic force microscopy (AFM), Auger Electron Spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS). The results show that Nb implantation leads to the formation of compact Nb₂O₅/TiO₂ thin film about 30 nm in thickness on the surface of the NiTi alloy and decreases the surface concentration of Ni. A larger incident dose or incident current causes a higher surface roughness and a higher Nb content in the implantation layer of NiTi alloy. The nano-indentation measurements indicate the obvious reduction of both nano-hardness and Young's modulus of the Nb implanted NiTi alloy in the implantation layer and even in deeper NiTi matrix. The results of potentiodynamic polarization test show that the corrosion resistance of NiTi alloy in Hanks's solution has been evidently improved by Nb implantation. The NiTi alloy with a moderate implantation parameter of 1.5 × 10¹⁷ ions/cm² and 2 mA exhibits the best corrosion resistance ability.     

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.     

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.     

Dielectric function and the crystal structure of MeV ion implanted LiNbO3

The behavior of the dielectric functions of MeV ion-implanted LiNbO₃ was studied using THz spectroscopy. Single crystal LiNbO₃ specimens were implanted with 3 MeV Au ions at four different levels of ion fluence (1 × 10¹², 1 × 10¹³, 1 × 10¹⁴ and 1 × 10¹⁵ cm^− 2). The optical spectra of the specimens were then measured in two ranged values: (1) reflectance THz range spectra from 40 to 700 cm^− 1 and (2) reflectance ultraviolet, visible, and near-infrared spectra from 250 to 2000 nm. The THz spectra were analyzed by fitting with the dielectric function model proposed by Brendel. The dielectric function model explained well the experimental spectra of the ion-implanted LiNbO₃. The dielectric function shows that the ion-implanted layers were amorphous phase at the fluence of 1 × 10¹⁴ and 1 × 10¹⁵ cm^− 2, whereas the layers at 1 × 10¹² and 1 × 10¹³ cm^− 2 maintained the crystal phase but significantly suppressed the phonon resonances. The volume of ion-implanted layers expanded about 8% with the fluence of 1 × 10¹⁴ and 1 × 10¹⁵ cm^− 2, i.e. after amorphization, These results show that the ion implantation significantly affected the lattice vibration mode and the structure even at very low ion fluence.     

Prevention of passive film breakdown and corrosion of iron in 0.1 M KClO4 with and without Cl by covering with an ultrathin two-dimensional polymer coating and healing treatment in 0.1 M NaNO3

A two-dimensional polymer coating, the self-assembled monolayer of 16-hydroxy hexadecanoate ion HO(CH₂)₁₅ modified with 1,2-bis(triethoxysilyl)ethane (C₂H₅O)₃Si(CH₂)₂Si(OC₂H₅)₃ and octadecyltriethoxysilane C₁₈H₃₇Si(OC₂H₅)₃ was prepared on the passivated iron electrode and further, the passive film was healed by additional treatment in 0.1 M NaNO₃. This electrode was immersed in oxygenated 0.1 M KClO₄ solutions with and without 1 × 10⁻⁴ to 1 × 10⁻² M of Cl⁻. Protection of passive film against breakdown by covering the electrode with the polymer coating was examined by monitoring the open-circuit potential during immersion in the solutions for many hours to determine the time for passive film breakdown, t_bd. Repeated polarization measurements were carried out during immersion in these solutions for obtaining the protective efficiency, P. The t_bd value of the passivated, polymer-coated and healed electrode in 0.1 M KClO₄ solutions with and without Cl⁻ increased with a decrease in the concentration of Cl⁻. No breakdown occurred on the electrode during immersion in 0.1 M KClO₄ solutions with and without 1 × 10⁻⁴ of Cl⁻ for 360 h. The P values were extremely high, more than 99.9% before t_bd, indicating complete protection of iron from corrosion. The effect of healing treatment in 0.1 M NaNO₃ on passive film breakdown was investigated by electron-probe microanalysis.     

Influence of N ion implantation on the corrosion and nano-structure of Ti samples

Nitrogen ions of 30 keV with different fluxes ranging from 5 × 10¹⁶ to 8 × 10¹⁷ ions/cm² were implanted in Ti foil of 1.8 mm thickness. X-ray diffraction (XRD) was used to obtain the structural characteristics, while atomic force microscope (AFM) was employed to obtain the surface morphology of the samples. The potentiodynamic method was employed to obtain corrosion resistance of the samples in NaCl (3.5%) solution. Titanium nitride formation was enhanced with increasing the nitrogen ion flux, while grain size and surface roughness of the samples were also increased. Optimum corrosion resistance was obtained for 5 × 10¹⁶ (N⁺ ions/cm²).     

Inhibiting effects of butyl triphenyl phosphonium bromide on corrosion of mild steel in 0.5 M sulphuric acid solution and its adsorption characteristics

Butyl triphenyl phosphonium bromide (BuTPPB) has been evaluated as a corrosion inhibitor for mild steel in 0.5 M H₂SO₄ solutions using galvanostatic polarisation and potentiostatic polarisation measurements. The study was also complemented by infra red (IR) spectroscopy, scanning electron microscopy (SEM) and quantum chemical calculations. Galvanostatic polarisation measurements showed that the presence of BuTPPB in aerated 0.5 M H₂SO₄ solutions decreases corrosion currents to a great extent and the corrosion rate decreases with increasing inhibitor concentration at a constant temperature. At 298K, inhibition efficiency was found to be 94.5% for 10⁻⁷ M BuTPPB which increased to about 99% for the BuTPPB concentration of 10⁻² M. The effect of temperature on the corrosion behaviour of mild steel was studied at five different temperatures ranging from 298 to 338K. The polarisation curves clearly indicate that BuTPPB acts as a mixed type inhibitor. Adsorption of BuTPPB on the mild steel surface follows the Langmuir isotherm.Potentiostatic polarisation measurements showed that passivation was observed only for lower BuTPPB concentrations (10⁻⁵ and 10⁻⁷ mol l⁻¹) for the mild steel in 0.5 M H₂SO₄. IR and SEM investigations also confirmed the adsorption of BuTPPB on the mild steel surface in 0.5 M H₂SO₄ solutions. The molecular parameters obtained using PM3 semi-empirical method, were correlated with the experimentally measured inhibitor efficiencies.     

H2S and O2 influence on the corrosion of carbon steel immersed in a solution containing 3 M diethanolamine

Aqueous solutions with 3 mol L⁻¹ (M) diethanolamine (DEA) concentration are extensively used in the gas processing industry to remove acid gases. However, the degradation of the DEA and the formation of heat-stable salts (HSS) lead to severe corrosion problems. Even worse, equipment corrosion can be magnified by the unavoidable presence of sulphide acid and dissolved oxygen as a result of hydrocarbon (natural gases and crude oil) processing. The aim of this work is to study the combined corrosion effects of DEA, sulphide acid and oxygen on carbon steel. Electrochemical methods revealed that in the 3 M DEA medium without oxygen, corrosion processes are modulated by adsorbed DEA film formation. Furthermore, it was shown that the addition of oxygen and 15 × 10⁻³ mol L⁻¹ (15 mM) H₂S produced the formation of an adherent film on the carbon steel surface. Chemical analyses by EDAX revealed a homogeneous film of corrosion products composed of iron oxide and sulphide formed in DEA solution containing O₂ and H₂S, respectively. Equivalent circuits were used to estimate the parameters associated with ion diffusion through the formed corrosion films. The results showed that the presence of H₂S induced the formation of thin iron sulphide films that provide protective properties to the metal. It is concluded that the presence of oxygen in a sweetening plant should be avoided as DEA degradation can be produced with the subsequent decrease in chelating process efficiency and the increase in corrosion problems.     

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.     

The aqueous corrosion behaviour of an ion implanted 12% chromium steel

Ion implantation has shown beneficial effects in the field of wear and oxidation. This paper is a study of the influence of ion implantation on the corrosion performance of a 12% chromium ferritic steel, 3CR12. 80 keV ions were implanted at concentrations of 5 × 10¹² to 1 × 10¹⁷ ions cm^?2. The effect of implantation of 4 ion types (Mo, V, Ph, N) each at 4 dosages was studied potentiostatically in 1 N H₂SO₄ and 0.1 N NaCl solutions. Uniform corrosion loss calculations would imply that the effect of implantation is not long lasting in 1 N H₂SO₄. This could imply that changes in the potentiostatic curves are brought about by ions in solution. Pb-Implanted 3CR12 showed increased pitting resistance with increasing dosage, whereas Pb-implanted 3CR12 showed poorer pitting resistance. Mo and V implantation showed similar behaviour for the lower doses in that both species enhanced pitting resistance but the results showed poorer pitting resistance for the higher doses. The most important limitation of ion implantation is the shallow depth of penetration and whether or not implantation effects last over sufficent periods of time for practical application is still in question.     

Relation between corrosion behavior and microstructure of Mg-Zn-Y alloys prepared by rapid solidification at various cooling rates

The relation between corrosion resistance and microstructure of Mg-Zn-Y alloys with a long period stacking ordered (LPSO) phase has been investigated. In order to clarify the influence of microstructure evolution by rapid solidification on the occurrence of localized corrosion such as filiform corrosion, several Mg_97.25Zn_0.75Y₂ (at. %) alloys with different cooling rates were fabricated by the gravity casting, copper mould injection casting and melt-spinning techniques and their corrosion behavior and microstructures were examined by the salt immersion tests, electrochemical measurements, XRD and TEM. When the cooling rate was less than 3 × 10⁴ K s⁻¹, filiform corrosion propagated in the early stage of salt immersion test, due to formation of a massive block-shaped LPSO phase during casting. On the other hand, when the cooling rate was increased up to 3 × 10⁴ K s⁻¹, rapidly solidified (RS) alloys exhibited excellent corrosion resistance because of grain refinement and formation of a supersaturated single-phase solid solution. Large-sized Mg_97.25Zn_0.75Y₂ alloys fabricated by consolidation of the RS ribbons also exhibited excellent corrosion resistance with passivity. Enhancement of microstructural and electrochemical homogeneities in the Mg-Zn-Y alloys by rapid solidification techniques results in the passivity of substrate materials.     

Corrosion behaviour of aluminium in copper containing environment

Corrosion behaviour of pure aluminium galvanically connected to metallic copper or in the presence of Cu²⁺ ions was investigated by electrochemical measurements in Na₂SO₄ and Na₂SO₄ + NaCl test solutions. It has been found that in aerated Cl⁻ ion containing solutions pitting corrosion of aluminium emerged immediately, while in the absence of oxygen this process was less violent. Effect of passivating pre-treatment of aluminium surface on corrosion behaviour Cu-Al bimetallic system is also demonstrated.     

The corrosion of Fe3Al alloy in liquid zinc

A systematic study of the isothermal corrosion testing and microscopic examination of Fe₃Al alloy in liquid zinc containing small amounts of aluminum (less than 0.2 wt.%) at 450 °C was carried out in this work. The results showed the corrosion of Fe₃Al alloy in molten zinc was controlled by the dissolution mechanism. The alloy exhibited a regular corrosion layer, constituted of small metallic particles (diameter: 2-5 μm) separated by channels filled with liquid zinc, which represented a porosity of about 29%. The XRD result of the corrosion layer formed at the interface confirmed the presence of Zn and FeZn_6.67. The corrosion rate of Fe₃Al alloy in molten zinc was calculated to be approximately 1.5 × 10⁻⁷ g cm⁻² s⁻¹. Three steps could occur in the whole process: the superficial dissolution of metallic Cr in the corrosion layer, the new phase formation of FeZn_6.67 and the diffusion of the dissolved species in the channels of the corrosion layer.