Hemocompatibility investigation of the NiTi alloy implanted with tantalum

A composite TiO₂/Ta₂O₅ nano-film has been formed on the NiTi shape memory alloy by Ta implantation. The wettability, protein adsorption, platelets adhesion and hemolysis tests are conducted to evaluate the hemocompatibility. The contact angle measurements showed that the surface of the NiTi alloy kept hydrophilic before and after Ta implantation, although the water contact angle increased with the increasing of implantation current. Both of the surface energy and the interfacial tension decreased after Ta implantation. The protein adsorption behavior was investigated by ¹²⁵I isotope labeling. The fibrinogen adsorption was enhanced by a high surface roughness or a large interfacial tension, while the albumin adsorption was insensitive to the surface modification. Platelet adhesion and activation were weakened and the hemolysis rate was reduced at least 46% after Ta implantation due to the decreased surface energy and improved corrosion resistance ability, respectively.     

Formation of a nano-pattering NiTi surface with Ni-depleted superficial layer to promote corrosion resistance and endothelial cell-material interaction

Zirconium ion implantation was performed on NiTi alloy to suppress Ni ion release as well as to improve corrosion resistance and cell-material interaction. A thicker Ni-depleted nano-scale composite layer formed after Zr implantation and the corrosion resistance was evidently increased in aspects of increased E _br ? E _corr (difference between corrosion potential and breakdown potential) and decreased corrosion current density. 2.5/2 NiTi sample possessed the highest E _br ? E _corr, more than 500 mV higher than that of untreated NiTi, suggesting a significant improvement on pitting corrosion resistance. Ni ion release rate of Zr–NiTi was decreased due to the depletion of Ni in the superficial surface layer and the diffusion resistance effect of the ZrO₂/TiO₂ nano-film. Increased surface wettability induced by increased surface roughness was obtained after Zr implantation. Zr–NiTi samples were found to be favorable to endothelial cells (ECs) proliferation, especially after 5 and 7 days culture.     

Characterization of TiO2/Ta2O5 Films Synthesized by Ion Beam on NiTi Alloy for Biomedical Applications

The biocompatibility of implants is determined by their corrosion resistance and surface characteristics. In this study, the surface composition, morphology and microstructure of TiO2/Ta2O5 films synthesized by ion beam enhanced deposition on NiTi alloy were studied. The scratch test results indicate that the interface adhesive strength of TiO2/Ta2O5 film increases with the increasing Ta content. The electrochemical corrosion measurement shows that the TiO2-36%Ta2O5 film is optimal for improving corrosion resistance of NiTi alloy.     

Formation and electrochemical behavior of Al and O plasma-implanted biodegradable Mg-Y-RE alloy

Mg-Y-RE alloy is potentially useful in biodegradable implants but the fast degradation rate in the physiological environment restrains actual applications. In order to enhance the corrosion resistance, aluminum and oxygen ion implantation is employed to modify the surface of the Mg-Y-RE alloy. X-ray photoelectron spectroscopy (XPS) is conducted to obtain elemental depth profiles and determine chemical state changes. Electrochemical impedance spectroscopy and potentiodynamic polarization are employed to investigate the electrochemical behavior in simulated body fluids (SBF). After polarization, the corroded surface is further studied by scanning electron microscopy (SEM). The results indicate Al and O ion implantation produces an Al₂O₃-containing protection layer which improves the corrosion resistance of Mg-Y-RE alloy. After the surface treatment, localized corrosion becomes the dominant corrosion mechanism instead of general corrosion.     

Ti6Al4V钛合金表面Ta2O5/Ta2O5-Ti/Ti多涂层的制备与性能研究

采用磁控溅射技术在Ti6Al4V钛合金表面制备了Ta_2O_5/Ta_2O_5-Ti/Ti多层涂层;利用扫描电子显微镜(SEM)、X射线衍射仪(XRD)和X射线光电子能谱仪 (XPS),分析了涂层的微观结构、物性组成和化学价态;通过划痕仪、纳米压痕仪、摩擦磨损试验机和电化学工作站,检测了涂层的结合强度、力学性能、摩擦系数和耐腐蚀性。研究结果表明,Ta_2O_5/Ta_2O_5-Ti/Ti多层涂层表面由峰型颗粒组成,粒径大小均匀,涂层结构致密。与Ti6Al4V相比,Ta_2O_5/Ta_2O_5-Ti/Ti多层涂层试样具有较小的摩擦系数,较高的腐蚀电位和较小的腐蚀电流密度,表现出良好的耐磨和耐腐蚀性能,能对Ti6Al4V合金植入材料起到较好的保护作用。     

Electrochemical and XPS studies of corrosion behavior of Ti–23Nb–0.7Ta–2Zr–O alloy in Ringer's solution

Corrosion behavior of a newly developed multifunctional β-type Ti–23Nb–0.7Ta–2Zr–O (mol%, TNTZO) alloy in Ringer's physiological solution was evaluated by open circuit potential, potentiodynamic polarization and X-ray photoelectron spectroscopy (XPS) techniques. Corrosion property of Ti–6Al–4V was also measured for comparison. The results showed that the TNTZO alloy possesses much better corrosion property than the Ti–6Al–4V alloy, corroborated by a high corrosion potential and broad passive region, which is attributed to the stable and inert passive TiO₂ film modified by the oxides of Nb, Ta and Zr on the surface of the TNTZO alloy.     

Effect of ceramic conversion treatments on the surface damage and nickel ion release of NiTi alloys under fretting corrosion conditions

Recent researches have demonstrated that surface modification can improve the fretting wear resistance of NiTi alloys in air or enhance their aqueous corrosion resistance without fretting. However, little is known about the behaviour of surface engineered NiTi under fretting corrosion conditions. This is important for such body implants as orthodontic arch wires and orthopedic bone fixation devices because they need to withstand the combined attack of corrosion from body fluid and mechanical fretting. In this study, a NiTi alloy was ceramic conversion (CC) treated at 400 and 650 °C. The effect of the surface treatment on the fretting corrosion behaviour of NiTi alloy was investigated using fretting corrosion tests in the Ringer’s solution. The experimental results have shown that the CC treatment can convert the surface of NiTi into a TiO₂ layer, which can effectively improve the fretting corrosion resistance of NiTi alloy and significantly reduce Ni ion release into the Ringer’s solution. Detailed SEM observations revealed that the untreated samples were severely damaged by adhesion and delamination; the high temperature (HT) (650 °C/1 h) treated samples were damaged mainly by spallation and adhesion; and the low temperature (LT) (400 °C/50 h) treated samples were characterised by mild abrasion. Mild oxidation and corrosion were also observed for all three types of samples tested under fretting corrosion conditions.     

Improving the corrosion resistance of Mg–4.0Zn–0.2Ca alloy by micro-arc oxidation

In this paper, corrosion resistance of the Mg–4.0Zn–0.2Ca alloy was modified by micro-arc oxidation (MAO) process. The microstructure and phase constituents of MAO layer were characterized by SEM, XRD and X-ray photoelectron spectroscopy (XPS). The corrosion resistance of MAO treated Mg–4.0Zn–0.2Ca alloy in the simulated body fluid were characterized by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) techniques. The microstructure results indicated that a kind of ceramic film was composed by MgO and MgF₂ was formed on the surface of Mg–4.0Zn–0.2Ca alloy after MAO treatment. The electrochemical test reveals that the corrosion resistance of MAO treated samples increase 1 order of magnitude. The mechanical intensity test showed that the MAO treated samples has suitable mechanical properties.     

Structure and properties of TiC/Ti coatings fabricated on NiTi by plasma immersion ion implantation and deposition

A titanium carbide (TiC) nanostructured coating and Ti intermediate layer are fabricated on NiTi by plasma immersion ion implantation and deposition (PIII&D) to improve the surface properties. The chemical composition and structure are determined by X-ray diffraction, Auger electron spectroscopy, scanning electron microscopy, and atomic force microscopy. Nano-indentation is used to evaluate the mechanical properties of the thin film and the biological characteristics are assessed by electrochemical measurement and soaking tests in simulated body fluids. Based on the potentiodynamic polarization and Ni release data after the polarization test, the Ti/TiC nanostructure coating has better corrosion resistance compared to the NiTi substrate and there is significantly less Ni ion release from the NiTi substrate into the simulated body fluids than the uncoated NiTi alloy.     

Alumina coating formed on medical NiTi alloy by micro-arc oxidation

Al₂O₃ coatings were prepared on NiTi alloy by micro-arc oxidation in an aluminate solution. Thin-film X-ray diffraction (TF-XRD) indicated that the coating consisted of only Al₂O₃ crystal phase. Energy dispersive X-ray spectrometer (EDS) showed that there was about 2.53 at.% Ni in the surface layer, which was greatly lower than that of NiTi substrate. Scanning electron microscopy (SEM) showed that the coating exhibited a typical porous surface and excellent adhesive interface between the coating and the substrate. Direct pull-off test showed that the coating had a mean coating-substrate bonding strength of 28 ± 2 MPa. The results of electrochemical impedance spectroscopy (EIS) study and potentiodynamic polarization test indicated that the corrosion resistance of the coated sample was increased by two orders of magnitude compared with uncoated sample.     

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.     

Electropolishing of NiTi for Improving Biocompatibility

A modified electrolyte （CH3COOH-HClO4-A-B） for electropolishing （EP） of NiTi was presented for improving the corrosion resistance and biocompatibility of the alloy. Using the proposed parameters, a homogeneous and uniform surface was obtained. Atomic force microscopy （AFM） revealed that the surface roughness （Ra） for EP sample （23.21 nm） was close to mechanical polishing （MP） sample （19.36 nm）. Analysis by X-ray photoelectron spectroscopy （XPS） showed that Ti/Ni ratio increased from 3.1 for MP sample to 27.6 for EP sample. Measurements using potentiodynamic polarization in Hanks＇ solution showed that no pitting occurred for EP sample even though the applied potential increased up to 1500 mV （vs SCE）, while the MP sample was broken down at 650 mV. The present study indicates that electropolishing NiTi with this modified electrolyte contributes to the improved biocompatibility of NiTi.     

Characterization and corrosion behavior of NiTi-Ti2Ni-Ni3Ti multiphase intermetallics produced by vacuum sintering

An in-situ synthesis method was employed to produce NiTi-Ti₂Ni-Ni₃Ti multiphase intermetallics. In this regard, the amorphous/nanocrystalline Ni-Ti powders were sintered at 1300 °C for 2 hrs to obtain Ni-Ti alloys with dense structure. Tafel polarization tests were employed to study corrosion behavior of multiphase materials in 3.5% NaCl and 0.1 M H₂SO₄ corrosive media. The results indicated that the microstructure of sintered samples consists of NiTi(Fe) and Ti₂Ni/Ti₄Ni₂O_x phases embedded in a Ni₃Ti matrix. The synthesized multiphase materials had microhardness up to 873 HV1 kg.Further investigations showed the corrosion performance of multiphase samples in 3.5% NaCl solution was inferior to that of wrought NiTi alloy. In contrast, the corrosion resistance of multiphase samples in 0.1 M H₂SO₄ solution was comparable to that of wrought NiTi alloy.     

Corrosion properties and corrosion evolution of as-cast AZ91 alloy with rare earth yttrium

The corrosion resistance property and the corrosion evolution of as-cast AZ91 alloy with rare earth Y addition are investigated by using immersion tests, electrochemical impedance spectroscopy (EIS), and X-ray photoelectron spectroscopy (XPS). The results show that the proper amount of Y in the alloys can improve the corrosion resistance of AZ91 alloys effectively. With the increment of Y, the corrosion rate of the modified AZ91 alloys by Y addition was markedly less than that of AZ91 alloy. The corrosion rate of AZ91 alloy with 0.3 wt.% Y was the slightest, but further addition of Y content over 0.3 wt.% make the corrosion heavier. The XPS analysis suggests that the compound film of AZ91 alloy with 0.3 wt.% Y is mainly composed of Mg(OH)₂ and MgCO₃ without any Al(OH)₃ and Al₂O₃, in addition, Y₂O₃ phase is found in the compound film of AZ91 alloy with 0.3 wt.% Y, which benefits to stabilize the surface film.     

医用多孔NiTi合金表面微弧氧化改性研究

为解决多孔Ni Ti合金耐蚀性降低和Ni离子释放量增大而引起的使用安全性问题.本文采用微弧氧化技术对医用多孔Ni Ti合金进行表面改性处理,研究结果表明,微弧氧化处理并未改变多孔Ni Ti合金原有的孔隙结构和孔隙率,只在其外表面和孔隙内表面均形成了典型的微弧氧化多孔涂层.该涂层主要由氧化铝相组成,并含有少量的Ti和Ni元素,且外表面涂层的Ti和Ni含量要略低于孔隙内表面涂层.微弧氧化涂层提高了多孔Ni Ti合金的表面接触角,将原有的亲水表面转变成了疏水表面.经微弧处理后,多孔Ni Ti合金的耐蚀性较基体提高了1个数量级以上,Ni离子释放量也较基体降低了1个数量级以上.     

Effect of sodium-ion implantation on the properties of the surface layers formed on CoCrMo alloy (Endocast SL)

This paper is concerned with the surface modification of a cobalt alloy (Endocast) by sodium-ion implantation and with the effect of this modification on its corrosion resistance. The Na ions were implanted at doses of 1×10¹⁷ and 2×10¹⁷ ions/cm² at 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 °C. Prior to the measurements, the samples were exposed to the test conditions for 13 h to allow the corrosion potential E_corr to stabilize, and for 181, 733 and 2200 h to investigate how the long-time exposures affect the corrosion resistance. The surfaces of the samples were examined by optical microscopy and by SEM-EDS. The TEM results indicate that the surface layers formed during the Na-implantation are amorphous. The results of the electrochemical examinations obtained for the Na-implanted Endocast samples indicate that the corrosion resistance of the alloy is reduced.     

Characterization of Sol-gel-derived TiO2 and TiO2-SiO2 Films for Biomedical Applications

In order to improve the corrosion resistance and biocompatibility of NiTi surgical alloy, TiO2 and TiO2-SiO2 thin films were prepared by sol-gel method. The surface characteristics of the film, which include surface composition, microstructure and surface morphology, were studied by X-ray diffraction (XRD), atomic force microscopy (AFM) and X-ray photoelectron spectra (XPS), respectively. A scratching test was used to assess the interface adhesive strength between the film and substrate. The corrosion resistance of NiTi alloy coated with oxide films were studied by anodic polarization curves measurement in biological solution. Additionally, a preliminary study of the in vitro bioactivity of the films was conducted. The results indicated that TiO2 and TiO2-SiO2 (Ti/Si=4:1) films have higher electrochemical corrosion resistance and can be used as protective layers on NiTi alloy. In addition, TiO2-SiO2 composite films have better bioactivity than TiO2 film.     

Surface characteristics and electrochemical corrosion behavior of NiTi alloy coated with IrO2

The aim of this work is to investigate the surface characteristics and corrosion behavior of NiTi (50.6 at.% Ni) shape memory alloy coated by a ceramic-like and highly biocompatible material, iridium oxide (IrO₂). IrO₂ coatings were prepared by thermal decomposition of H₂IrCl₆ · 6H₂O precursor solution at the temperature of 300 °C, 400 °C and 500 °C, respectively. The surface morphology and microstructure of the coatings were investigated by scanning electron microscope (SEM) and glancing angle X-ray diffraction (GAXRD). X-ray photoelectron spectroscopy (XPS) was employed to determine the surface elemental composition. Corrosion resistance property of the coated samples was studied in a simulated body fluid at 37 ± 1 °C by electrochemical method. It was found that the morphology and microstructure of the coatings were closely related to the oxidizing temperatures. A relatively smooth, intact and amorphous coating was obtained when the H₂IrCl₆·6H₂O precursor solution (0.03 mol/L) was thermally decomposed at 300 °C for 0.5 h. Compared with the bare NiTi alloy, IrO₂ coated samples exhibited better corrosion resistance behavior to some extent.     

Characterization and corrosion behavior of NiTi–Ti2Ni–Ni3Ti multiphase intermetallics produced by vacuum sintering

An in-situ synthesis method was employed to produce NiTi–Ti₂Ni–Ni₃Ti multiphase intermetallics. In this regard, the amorphous/nanocrystalline Ni–Ti powders were sintered at 1300 °C for 2 hrs to obtain Ni–Ti alloys with dense structure. Tafel polarization tests were employed to study corrosion behavior of multiphase materials in 3.5% NaCl and 0.1 M H₂SO₄ corrosive media. The results indicated that the microstructure of sintered samples consists of NiTi(Fe) and Ti₂Ni/Ti₄Ni₂O_x phases embedded in a Ni₃Ti matrix. The synthesized multiphase materials had microhardness up to 873 HV1 kg.Further investigations showed the corrosion performance of multiphase samples in 3.5% NaCl solution was inferior to that of wrought NiTi alloy. In contrast, the corrosion resistance of multiphase samples in 0.1 M H₂SO₄ solution was comparable to that of wrought NiTi alloy.     

Comparative study on the corrosion behavior of Ti-Nb and TMA alloys for dental application in various artificial solutions

The corrosion behavior of Ti-Nb dental alloy in artificial saliva with and without the addition of lactic acid and sodium fluoride was investigated by electrochemical techniques, with the commercial Titanium-molybdenum alloy (TMA) as a comparison. The chemical composition, microstructure and constitutional phase were characterized via energy dispersive spectrometry, optical microscope and X-ray diffraction, meanwhile the open circuit potential, electrochemical impedance spectroscopy and potentiodynamic polarization measurements were carried out to study the corrosion resistance of experimental alloys, with the corroded surface being further characterized by scanning electron microscopy and X-ray photoelectron spectroscopy. It was found that the corrosion behavior of Ti-Nb alloy was similar to those TMA alloy samples in both artificial and acidified saliva solutions, whereas statistical analysis of the electrochemical impedance spectroscopy and polarization parameters showed Ti-Nb alloy exhibited better corrosion resistance in fluoridated saliva and fluoridated acidified saliva. SEM observation indicated that TMA alloy corroded heavily than Ti-Nb alloy in fluoride containing saliva. XPS surface analysis suggested that Nb₂O₅ played an important role in anti-corrosion from the attack of fluoride ion. Based on the above finding, Ti-Nb alloy is believed to be suitable for the usage in certain fluoride treated dental works with excellent corrosion resistance in fluoride-containing oral media.