Effect of calcium-ion implantation on the corrosion resistance and bioactivity of the Ti6Al4V alloy

The corrosion resistance and bioactivity of Ti6Al4V alloy after calcium-ion implantation were examined. Polished samples were implanted with a dose of 10¹⁷ Na⁺/cm² at a beam energy of 25 keV. The chemical composition of the surface layer formed during the implantation was determined by XPS and SIMS. The bioactivity of the samples was evaluated by soaking them in a simulated body fluid (SBF) at 37 °C for 168 and 720 h. The corrosion resistance in SBF at 37 °C was determined by electrochemical methods after exposure in SBF for various times. The surfaces of the samples before and after examinations were observed by optical microscopy, SEM-EDS and AFM.The results of the corrosion examinations indicated that under stationary conditions and after short-term exposures, the calcium-ion implanted titanium alloy had an increased corrosion resistance, but during the anodic polarization, calcium-implanted samples underwent pitting corrosion. The microscopic observations show that the precipitations of calcium phosphates are present on the surface, but they do not form a continuous layer.     

Surface analysis of argon-implanted zircalloy-2 and influence of bubble formation on the corrosion behavior

In order to simulate the irradiation damage, argon ions were implanted into zircalloy-2 alloy with a fluence ranging from 1×10¹⁶ to 1×10¹⁷ ions/cm², using an implanter at an extraction voltage of 190 kV, at liquid nitrogen temperature. Then the effect of argon ion implantation on the aqueous corrosion behavior of zircalloy-2 alloy was studied. The valence states of elements in the surface layer of the samples were analyzed by X-ray photoelectron spectroscopy (XPS). Transmission electron microscopy (TEM) was used to examine the microstructure of the argon-implanted samples. Glancing angle X-ray diffraction (GAXRD) was employed to examine the phase transformation due to the argon ion implantation. The potentiodynamic polarization technique was employed to evaluate the aqueous corrosion resistance of implanted zircalloy-2 alloy in a 1 M H₂SO₄ solution. It was found that the bubbles were formed on the surface of implanted samples; the bubbles grew larger with increasing argon fluence. The microstructure of argon-implanted samples changed from amorphous to partial amorphous, then to polycrystalline and finally to amorphous. The bubble forming and changing and microstructure changes affected the corrosion properties of implanted samples. Finally, the mechanism of the corrosion behavior of argon-implanted zircalloy-2 alloy is discussed.     

Implantation of silicon ions into a surface layer of the Ti6A14V titanium alloy and its effect upon the corrosion resistance and structure of this layer

The effect of silicon ion implantation upon the corrosion resistance and structure of the surface layers formed during the implantation in the Ti6A14V titanium alloy was examined. The silicon doses were 0.5, 1.5, 3.0 and 4.5 × 10¹⁷Si⁺/cm², and the ion beam energy was 100 keV. The corrosion resistance of the samples exposed to a 0.9% NaCl solution at a temperature of 37 °C was measured using electrochemical methods. The structure of the surface layers formed during the implantation was examined by a transmission electron microscope (TEM). The results of the corrosion resistance examinations have shown that the unimplanted and 0.5 × 10¹⁷Si⁺/cm² implanted samples undergo uniform corrosion. At higher silicon doses, the samples show pitting corrosion. The highest corrosion resistance was shown by the alloy implanted with 0.5 × 10¹⁷Si⁺/cm². It has been found that, after a long-term (1200 h) exposure to a 0.9% NaCl solution, the corrosion resistance of the samples is greater than that observed after a short-term exposure. TEM examinations have shown that, beginning from a dose of 1.5 × 10¹⁷Si⁺/cm², the surface of the Ti6A14V alloy samples becomes amorphous. Heating of the 1.5 × 10¹⁷Si⁺/cm² implanted samples at 200 and 500 °C does not change their structure, whereas after heating at 650 °C, the amorphous phase vanishes.     

Phase formation and modification of corrosion property of nitrogen implanted Ti-Al-V alloy

In the present investigation, polished samples were implanted with nitrogen ion at an energy of 60 keV and implantation doses were 1×10¹⁶, 5×10¹⁶, 1×10¹⁷ and 6×10¹⁷ ions/cm². Glancing incidence X-ray diffraction was employed on the implanted specimens to understand the phases formed with increasing dose. The valence states of nitrogen, titanium and carbon on the sample surfaces were analyzed by X-ray photoemission spectroscopy. The corrosion resistance was examined by the electrochemical methods in a solution with pH=10 at room temperature in order to determine the optimum dose that can give good corrosion resistance in a simulated nuclear reactor condition. Scanning electron microscopy was used to observe the topographies of nitrogen-implanted Ti-Al-Zr after potentiodynamic measurement. It was found that implanted nitrogen dissolved in titanium matrix with increasing dose and the resultant nitrides such as TiN and Ti₂N precipitated. Implantation of nitrogen ions into the surface of Ti-Al-V alloy improves its corrosion resistance, and the increase of the corrosion resistance depends on the nitrogen dose employed; the maximum improvement of the corrosion resistance was observed at a dose of 1×10¹⁷ N⁺/cm².     

Microstructure and electrochemical properties of Zircaloy-4 under Fe ion irradiation

To investigate the microstructure and electrochemical properties of Zircaloy-4 induced by Fe ion irradiation with the energy of 150 keV at liquid nitrogen temperature, transmission electron microscope analysis (TEM) was employed to analyze the surface layer of the samples irradiated at a dose ranging from 1×10¹³ to 1×10¹⁶ ions/cm², and potentiodynamic polarization measurements were used to evaluate the corrosion resistance of Zircaloy-4 in a 1 N H₂SO₄ solution at room temperature. TEM analyses show that Fe ion irradiation lead to a structural change and amorphous phase formation on the surface of the samples. Moreover, it is indicated from the corrosion tests that with an increase of the irradiation dose, the passive current density increases at first and then decreases rapidly, while the natural corrosion potential goes down at first and then up rapidly. The critical point, where the corrosion properties are transformed from a damaging stage to protecting stage, is at the damage level of 3.19 dpa. Finally, the mechanism for the change of corrosion resistance of the Zircaloy-4 samples is discussed.     

Role of aluminum ion implantation on microstructure, microhardness and corrosion properties of titanium alloy

Ti-Al-Zr alloy was implanted with Al at cumulative doses between 1 × 10¹⁷ and 1 × 10¹⁸ ions/cm². The results indicate that the Al-implanted layers are ∼0.1 μm thick and are composed almost entirely of an amorphous layer. Implanted layer hardness is dose dependent and is increased by more than a factor of 4 for the high-dose implanted specimen when compared with that of the substrate material. The corrosion resistance of the sample was markedly improved after aluminum implantation.     

Comparison of corrosion behavior of zirconium bombarded with self-ion and molybdenum ion

In order to study the effects of zirconium and molybdenum ion bombardment on the aqueous corrosion behavior of zirconium, one group of specimens was implanted with zirconium ions with ions surface densities ranging from 1 × 10¹⁵ to 2 × 10¹⁷ ions/cm² at about 170 °C, using a metal vapor vacuum arc (MEVVA) source operated at an extraction voltage of 50 kV. The other group of specimens was bombarded with molybdenum ion with ions surface densities ranging from 1 × 10¹⁶ to 5 × 10¹⁷ ions/cm² at about 160 °C, using a MEVVA source operated at an extraction voltage of 40 kV. The valence states and depth distribution of elements in the surface of the samples were analyzed by X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES), respectively. Polarization curves measurement was employed to evaluate the aqueous corrosion resistance of the zirconium samples in a 1N H₂SO₄ solution. It was found that the aqueous corrosion resistance of zirconium implanted with 5 × 10¹⁶ Zr ions/cm² is the best in first group samples. For molybdenum ion implantation, the aqueous corrosion resistance of samples declined with raising ions surface densities. The natural corrosion potentials of zirconium samples bombarded with self-ions are more negative than that of the as-received zirconium. While, as for molybdenum ion implantation, the results are opposite. Finally, the mechanisms of the corrosion behavior of the zirconium samples implanted with zirconium and molybdenum ions are discussed.     

The effect of sodium-ion implantation on the properties of titanium

This paper deals with the surface modification of titanium by sodium-ion implantation and with the effect of this modification on structure, corrosion resistance, bioactivity and cytocompatibility. The Na ions were implanted with doses of 1 x 10(17) and 4 x 10(17) ions/cm(2) at an energy of 25 keV. The chemical composition of the surface layers formed during the implantation was examined by secondary-ion mass spectrometry (SIMS) and X-ray photoelectron spectroscopy (XPS), and their microstructure--by transmission electron microscopy (TEM). The corrosion resistance was determined by electrochemical methods in a simulated body fluid (SBF) at a temperature of 37 degrees C, after exposure in SBF for various times. The surfaces of the samples were examined by optical microscopy, by scanning electron microscopy (SEM-EDS), and by atomic force microscopy (AFM). Biocompatibility of the modified surface was evaluated in vitro in a culture of the MG-63 cell line and human osteoblast cells. The TEM results indicate that the surface layers formed during the implantation of Na-ions are amorphous. The results of the electrochemical examinations obtained for the Na-implanted titanium samples indicate that the implantation increases corrosion resistance. Sodium-ion implantation improves bioactivity and does not reduce biocompatibility.     

Fabrication of hydrophobic/super-hydrophobic nanofilms on magnesium alloys by polymer plating

Hydrophobic/super-hydrophobic nanofilms with improved corrosion resistance were fabricated on the surfaces of Mg-Mn-Ce magnesium alloy by a surface modification technique, named as polymer plating, which has been developed to modify superficial characteristics of magnesium alloys with polymeric nanofilms through synthesized organic compounds of triazine dithiol containing functional groups. The nanofilms were prepared by the electrochemical and polymerization reactions during polymer plating analyzed from characteristics of Fourier transform infrared spectrophotometer, X-ray photoelectron spectroscopy and scanning electron microscopy. The fabricated nanofilms changed the surface wettability of blank magnesium alloy from hydrophilic to hydrophobic with contact angle 119.0° of distilled water with lower surface free energy of 20.59 mJ/m² and even super-hydrophobic with contact angle 158.3° with lowest surface free energy of 4.68 mJ/m² by different functional nanofilms on their surfaces. Alteration of wettability from hydrophilic to hydrophobic and super-hydrophobic resulted from their low surface free energy and surface morphology with micro- and nano-rough structures. The corrosion behaviors from potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) show that the super-hydrophobic nanofilm has higher corrosion resistance and stability in 0.1 mol/L NaCl solution and lower corrosion current density (I_corr) with R_ct increasing two orders of magnitude of 16,500 Ω·cm² compared to that obtained for blank of 485 Ω·cm².     

Surface modification of magnesium alloy AZ31 by hydrofluoric acid treatment and its effect on the corrosion behaviour

In the present study, the effect of hydrofluoric acid (HF) treatment on the surface composition and corrosion behaviour of the magnesium alloy AZ 31 was investigated. The HF treatment of the samples was performed with various concentrations and at different treatment times. The samples surfaces were analysed by Fourier transform infrared spectroscopy, optical emission spectroscopy, X-ray photoelectron spectroscopy and scanning electron microscopy. The results showed the formation of hydroxides, oxides and compounds of the general formula Mg(OH)_xF_2 − x on the samples surfaces, as well as variations on impurities concentrations. The process led to distinct surfaces, each having its specific corrosion resistance, which was evaluated by electrochemical impedance spectroscopy and potentio-dynamic polarization. The most improved corrosion protection was achieved using the concentrations of 14 and 20 mol L^− 1 and 24 h of treatment time, resulting in corrosion rates 20 times lower than those of untreated samples. These two solutions also resulted in an improved corrosion protection for further polymeric coatings, showing that this treatment is an excellent pre-treatment for corrosion protective layers on magnesium alloys.     

The effect of extrusion speed on the structure and corrosion properties of aged and non-aged 6063 aluminum alloy

Extrusion is used in processing of Al alloy for consolidation, redistribution of reinforcements, and shape forming. The important parameter that controls the extrusion process is extrusion rate, which is a function of extrusion equipment and parameters. Homogenized AA6063 alloy billets were extruded at different ram speeds related to extrusion speed (3, 6, 10 mm s⁻¹) and then aged at 185 °C for 6 h. The extruded samples were studied for their corrosion, microstructure, and mechanical properties. The effects of extrusion speed and aging on the corrosion behavior of AA6063 were investigated using dynamic polarization and impedance techniques in 0.5 M NaCl aqueous solution. The surface structures were then characterized by means of surface profilometer. The electrochemical measurements showed that the decreasing ram speed for the aged sample improved the corrosion resistance. In addition, the aging improved the corrosion resistance of aluminum in 0.5 NaCl environments.     

Studies on the corrosion behavior of cerium-implanted zircaloy-4 with GAXRD

In order to study the influence of cerium ion implantation on the aqueous corrosion behavior of zircaloy-4, specimens were implanted by cerium ions with a fluence range from 1×10¹⁶ to 1×10¹⁷ ions/cm² at maximum 150°C, using MEVVA source at an extracted voltage of 40 kV. The valence and elements penetration distribution of the surface layer were analyzed by X-ray photoelectron spectroscopy (XPS) and auger electron spectroscopy (AES) respectively. Glancing angle X-ray diffraction (GAXRD) was employed to examine the phase transformation due to the cerium ion implantation in the oxide films. Three-sweep potentiodynamic polarization measurement was employed to value the aqueous corrosion resistance of zircaloy-4 in a 1 N H₂SO₄ solution. It was found that a significant improvement in the aqueous corrosion behavior of zircaloy-4 implanted with cerium ions compared with that of the as-received zircaloy-4. The improvement effect will declined with raising the implantation fluence. The bigger is the fluence, the less is the improvement. Finally, the mechanism of the corrosion behavior of the cerium-implanted zircaloy-4 is discussed.     

Corrosion and impedance studies on magnesium alloy in oxalate solution

Corrosion behavior of AZ91E alloy was investigated in oxalate solution using potentiodynamic polarization and electrochemical impedance measurements (EIS). The effect of oxalate concentration was studied, where the corrosion rate increases with increasing oxalate concentration. The effect of added ions (Br⁻, Cl⁻ or SiO₃²⁻) on the electrochemical behavior of magnesium alloy in 0.1 M Na₂C₂O₄ solution at 298 K, was investigated. It was found that the corrosion rate of 0.1 M oxalate solution containing silicate ion is lower than the blank (0.1 M Na₂C₂O₄). This was confirmed by scanning electron microscope (SEM) observations. However, for the other added ions Br⁻ or Cl⁻, the corrosion rate is higher than the blank.     

The estimation of corrosion behaviour of ZrTi binary alloys for dental applications using electrochemical techniques

Titanium and zirconium are in the same group in the periodic table of elements and are known to have similar physical and chemical properties. Both Ti and Zr usually have their surfaces covered by a thin oxide film spontaneously formed in air. However, the cytotoxicity of ZrO₂ is lower than that of TiO₂ rutile. Treatments with fluoride are known as the main methods to prevent plaque formation and dental caries. The corrosion behaviour of ZrTi alloys with Ti contents of 5, 25 and 45 wt.% and cp-Ti was investigated for dental applications. All samples were tested by linear potentiodynamic polarisation and electrochemical impedance spectroscopy (EIS) performed in artificial saliva with different pH levels (5.6 and 3.4) and different fluoride (1000 ppm F⁻) and albumin protein (0.6%) contents. In addition, scanning electron microscopy (SEM) was employed to observe the surface morphology of the test materials after linear potentiodynamic polarisation. The corrosion current densities for the ZrTi alloys increased with the titanium content. The Zr5Ti and Zr25Ti alloys were susceptible to localised corrosion. The role that Ti plays as an alloying element is that of increasing the resistance of ZrTi alloy to localised corrosion. The presence of 0.6% albumin protein in fluoridated acidified artificial saliva with 1000 ppm F⁻ could protect the cp-Ti and ZrTi alloys from attack by fluoride ions.     

Electrochemical corrosion behavior of carbon-based thin films in chloride ions containing electrolytes

Commercially available carbon-based thin films consisting of single layers of amorphous diamond-like carbon or multilayers of crystalline TiAlN or CrN with diamond-like carbon top coatings were evaluated in relation to their electrochemical corrosion behavior in chloride ions containing electrolytes. The hardened working steel (an alloy of 0.9% C, 4.1% Cr, 4.9% Mo, 1.8% V, 6.4% W) was used as a substrate material.The potentiodynamic corrosion behavior of coated samples was tested in 3.5 wt.% NaCl solution and Hank's balanced body solution, HBBS (0.89 wt.% NaCl, further chlorides, sulfates, carbonates and phosphates). The multi-layers TiAlN + a-C:H:W and CrN + a-C:H:W exhibited only a minor improvement in corrosion resistance. Single layers of amorphous diamond-like carbon coating without hydrogen (a-C) spall off during the corrosion tests in chloride containing media. A minor improvement of the corrosion resistance is possible. The a-C:H and the a-C:H:Si, which contain hydrogen, showed the best corrosion resistance with a 100 times lower corrosion current density.     

Experimental investigation on corrosion and hardness of ion implanted AISI 316L stainless steel

The AISI 316L stainless steel has been widely used both in artificial knee and hip joints in bio-medical applications. In the present study AISI 316L SS was implanted with two different ions: nitrogen and helium at 100 keV with a dose of 1 × 10¹⁷ ions/cm² at room temperature. The crystallographic orientation and surface morphology were studied using X-ray diffraction (XRD) and scanning electron microscope (SEM). The effects of ion implantation on the corrosion performance of AISI 316L stainless steel was evaluated in 0.9% NaCl solution using electro chemical test both on the virgin and implanted samples. The subsequent Tafel analysis shows that the ion implanted specimens were more corrosion resistant when compared to the bare specimens. Microhardness was also measured by Vickers method by varying the loads. The results of the studies indicated that there was a significant improvement in both corrosion resistance and hardness of implanted samples.     

Application of plasma polymerized siloxane films for the corrosion protection of titanium alloy

Organosilicon film and SiO_x-like film are deposited on titanium alloy (Ti6Al4V) surfaces by atmospheric pressure (~ 10⁵ Pa) dielectric barrier discharge to improve its corrosion resistance in Hanks solution. Hexamethyldisiloxane (HMDSO) is used to be the chemical precursor. The organosilicon film deposited in Ar/HMDSO system has high growth rate (75 nm/min) and low surface roughness (3 nm), while the SiO_x-like film deposited in Ar/O₂/HMDSO system has lower growth rate (35 nm/min) and slightly higher surface roughness (9 nm). The potentiodynamic polarization tests show that both the two siloxane films coated Ti6Al4V samples have more positive corrosion potential and one order of magnitude lower corrosion current density than the substrate, indicating the corrosion resistance of Ti6Al4V can be improved by depositing siloxane film on its surface. In particular, as the surface is more compact and cross-linked, the SiO_x-like film has better corrosion resistance than the organosilicon film.     

Influence of surface roughness on the corrosion behaviour of magnesium alloy

In this study, the influence of surface roughness on the passivation and pitting corrosion behaviour of AZ91 magnesium alloy in chloride-containing environment was examined using electrochemical techniques. Potentiodynamic polarisation and electrochemical impedance spectroscopy tests suggested that the passivation behaviour of the alloy was affected by increasing the surface roughness. Consequently, the corrosion current and the pitting tendency of the alloy also increased with increase in the surface roughness. Scanning electron micrographs of 24 h immersion test samples clearly revealed pitting corrosion in the highest surface roughness (Sa 430) alloy, whereas in the lowest surface roughness (Sa 80) alloy no evidence of pitting corrosion was observed. Interestingly, when the passivity of the alloy was disturbed by galvanostatically holding the sample at anodic current for 1 h, the alloy underwent high pitting corrosion irrespective of their surface roughness. Thus the study suggests that the surface roughness plays a critical role in the passivation behaviour of the alloy and hence the pitting tendency.     

Microstructure modifications and corrosion behaviors of Cr4Mo4V steel treated by high current pulsed electron beam

In this work, Cr4Mo4V steel was irradiated by high energy current pulsed electron beam (HCPEB) with energy density of 6 J/cm². Morphology and phase composition of the surface layer were analyzed using scanning electron microscopy (SEM) and glancing angle X-ray diffraction (GXRD). The crater-like morphology was observed on surface after HCPEB treatment, and the thickness of melted layer was ∼7 μm. Results from GXRD revealed that HCPEB treatment could suppress martensite transition and the content of retained austenite in the melted layer increased with irradiation number. The corrosion resistance was evaluated by electrochemical polarization tests in neutral 3.5% NaCl solution. Compared with the untreated Cr4Mo4V steel, corrosion potential of the samples treated by HCPEB improved and the corrosion current density decreased. The improved corrosion resistance is attributed to the absence of the carbide, formation of retained austenite and dissolution of alloy elements, particularly of Cr and Mo, into the matrix.     

Nitrogen ion implantation for improvement of the mechanical surface properties of aluminum

The results of the surface treatment of commercial aluminum by nitrogen ion implantation at 120 keV and implanted fluences ranging from 3×l0¹⁷ to 1.1×10¹⁸ ions/cm² are reported. The treatment was found to lead to the formation of the hexagonal phase AIN, a decrease in strain and an increase of crystallite sizes. The modification of the surface layer so produced was thought to be a cause of a measured increase in surface microhardness and corresponding decrease in friction coefficient and wear measured in pure methanol. Oxygen found in the surface layers was also thought to play a significant role in determining tribological performance.