Effect of Mo content on electrochemical behaviour of TiMo alloys for dental applications

Corrosion behaviour of the new TiMo alloys together with the currently used metallic biomaterials commercial pure titanium (Cp‐Ti) was investigated for dental applications. Ingots of composition Ti12Mo, Ti20Mo and Ti40Mo were synthesized by the cold crucible levitation melting (CCLM) technique. All the samples were examined using electrochemical techniques: open circuit potential, potentiodynamic polarization curves and electrochemical impedance spectroscopy (EIS) in two electrochemical media: artificial saliva and in commercial mouthwash solution with 450 ppm F^? (Astera^©, EU), at 25 °C. The passive behaviour for all the Ti samples is observed for artificial saliva and for commercial mouthwash solution. The results suggest a non‐predominant fluoride effect on the passive behaviours of titanium samples. The EIS technique was applied to study the nature of the passive film formed on all the samples at various potentials in artificial saliva and in commercial mouthwash solution. Equivalent circuits (EC) were used to modelling EIS data, in order to characterize samples surface and better understanding the effect of Mo addition on the Cp‐Ti. The TiMo alloys, with a dendritic arrangement, appear to possess superior corrosion resistance than the Cp‐Ti in both electrochemical media.     

Influence of fluoride concentration and pH on corrosion behavior of Ti‐6Al‐4V and Ti‐23Ta alloys in artificial saliva

Titanium alloys exhibit an excellent corrosion resistance in most aqueous media due to the formation of a stable oxide film and some of these alloys (particularly Ti‐6Al‐4V) were chosen for surgical and odontological implants for this resistance and their biocompatibility. Treatments with fluorides (F^?) are known as the main method to prevent plaque formation and dental caries. Toothpastes, mouthwashes and prophylactic gels can contain from 200 to 20 000 ppm F^? and can present neutral to acidic character, which can affect the corrosion behavior of titanium alloys devices present in the oral cavity. In this work, the behavior of Ti‐6Al‐4V and the new experimental Ti‐23Ta has been evaluated in artificial saliva of pH 2, 5 and 7 and different F^? concentrations (0, 1000, 5000 and 10 000 ppm), through open‐circuit potential measurements, potentiodynamic polarization and electrochemical impedance spectroscopy. A defined correlation between pH and F^? concentration settled the active or passive character of the materials. For both alloys, an active behavior was observed for pH 2 and 1000 to 10 000 ppm F^? and for pH 5 and 5000 and 10 000 ppm F^?. The passive behavior was observed for the other investigated conditions. The F^? concentration increase and pH decrease reduced the corrosion resistance of the alloys and decreased the stability of their passive film. The corrosion behavior of both alloys was very similar, but the Ti‐23Ta alloy generally presented slightly higher corrosion resistance.     

Corrosion behavior of Ti‐xNb‐13Zr alloys in Ringer's solution

Ti‐6Al‐4V alloy has been widely used in restorative surgery due to its high corrosion resistance and biocompatibility. Nevertheless, some studies showed that V and Al release in the organism might induce cytotoxic effects and neurological disorders, which led to the development of V‐free alloys and both V‐ and Al‐free alloys containing Nb, Zr, Ta, or Mo. Among these alloys, Ti‐13Nb‐13Zr alloy is promising due to its better biomechanical compatibility than Ti‐6Al‐4V. In this work, the corrosion behavior of Ti, Ti‐6Al‐4V, and Ti‐xNb‐13Zr alloys (x = 5, 13, and 20) was evaluated in Ringer's solution (pH 7.5) at 37 °C through open‐circuit potential measurements, potentiodynamic polarization, and electrochemical impedance spectroscopy. Spontaneous passivity was observed for all materials in this medium. Low corrosion current densities (in the order of 10^?7 A/cm²) and high impedance values (in the order of 10⁵ Ωcm² at low frequencies) indicated their high corrosion resistance. EIS results showed that the passivating films were constituted of an outer porous layer (very low resistance) and an inner compact layer (high resistance), the latter providing the corrosion resistance of the materials. There was evidence that the Ti‐xNb‐13Zr alloys were more corrosion resistant than both Ti and Ti‐6Al‐4V in Ringer's solution.     

Effect of potential on the corrosion behavior of a new titanium alloy for dental implant applications in fluoride media

The effect of fluoride ion concentration and pH on the corrosion behavior of TCA (60 Ti 10 Ag 30 Cu), which is a new Ti alloy with low melting point, pure Titanium (Ti), and TAV (TiAl6V4) was examined using open circuit potential (OCP) and electrochemical impedance spectroscopy (EIS) at different potentials. Results show that the corrosion resistance of TCA and Ti decrease at anodic potentials compared with results obtained at OCP. At one potential the corrosion resistance decrease depends on NaF concentration and pH. TAV shows less resistance against corrosion in fluoride containing saliva. TCA has potentials more positive than Ti and TAV due to surface enrichment of Cu and Ag as Ti dissolves which accelerates the cathodic reaction. Fluoride ion may not hinder the growth of oxide layers on the surfaces of the electrodes. It will have influence on the properties of the oxide layer causing them to be not protective against corrosion in acid media containing fluoride ions.     

Crevice corrosion monitoring of titanium and its alloys using microelectrodes

Crevice corrosion of titanium and its alloys in 10% sodium chloride was investigated at 100°C with the aid of microelectrodes. Potential, pH and chloride ion concentration inside the crevice were monitored using an Ag/AgCl electrode, a tungsten microelectrode and a Ag/AgCl chloride ion selective microelectrode, respectively. The pH and Cl^? concentrations within the crevice were calculated from the standard potential‐pH and potential‐log[Cl^?] calibration curves. The effect of Mo on the crevice corrosion of titanium was also studied. The passivation behavior on the titanium and Ti‐15%Mo alloy was studied using electrochemical impedance studies. There was no apparent change in pH and Cl^? ion activity inside the crevice for the alloy at 100°C, whereas a marginal decrease in pH and increase in Cl^? ion concentration were observed for pure titanium. Thus pure titanium is susceptible to crevice corrosion in hot 10% NaCl solutions at 100°C. The chloride ion activity was found to be reduced for the alloy so that the pH inside the crevice increased. The corrosion reaction resistance (R_t) was found to increase with the addition of Mo as an alloying element. It also increases with externally applied anodic potential. Hence, Mo is an effective alloying element, which enhances the crevice corrosion resistance of titanium.     

Effect of Chloride and Fluoride on the Rate of Corrosion of dental amalgam alloys

The anodic behaviour of massive and dental amalgam alloys in artificial saliva containing different concentrations of Cl^? or F^? ions has been studied. Quantitative relations could be established between concentrations of these ions and the height of the peaks corresponding to anodic oxidation of Sn or Ag. Contrary to f^?, Cl^? ions from Ag complexes via AgCl which excess cl^?ions. The massive alloy is stable below 0.15 V. Calcium fluoride can be safely admixed with dental amalgam alloy without enhancing its corrosion.     

Ti35合金在含氟离子硝酸中电化学腐蚀行为

Ti35合金具有优良的耐腐蚀性能,可在沸腾状态下高浓度的氧化性酸介质中进行长期工作,是商业后处理较为理想的候选材料。本文采用电化学测试系统测试了Ti35合金在含有不同氟离子浓度的6M硝酸溶液中的开路电位(OCP)、极化曲线、电化学阻抗谱(EIS),探讨了氟离子对Ti35合金耐蚀性能的影响。结果表明：随着氟离子浓度的增加,合金耐蚀性下降,但总体而言合金仍具有良好的耐蚀性。影响合金耐蚀性转变的氟离子浓度临界值约为50ppm,进一步应用混合电位理论,解释合金耐蚀性转变的原因。     

Formation behavior of anodic TiO2 nanombes in fluoride containing electrolytes

TiO₂ nanotube layers can be formed with titanium in the electrolytes containing fluoride by electrochemical method. The role of fluoride ion, the crystallinity of the anodic oxide, and the chemical state were investigated. The results show the anodic film is composed of oxide and a little amount of hydroxide. The presence of F⁻ ions leads to chemical dissolution of Ti oxide layer and prevents hydroxide precipitation. Consequently, chemical dissolution rate increases with increasing the fluoride content in the range of 0–2% (in mass fraction) because F⁻ ions in electrolyte attack the interface and allow the ions of the electrolyte to easily penetrate into the interface. The as-anodized TiO₂ nanotubes exhibit an amorphous structure. Thermally treated nanotubes are composed of mixtures of the anatase and rutile phases.     

Electrochemical impedance spectroscopic studies of titanium and its alloys in saline medium

The influence of potential on electrochemical behaviour of pure Ti, Ti‐6Al‐7Nb, and Ti‐6Al‐4V ELI alloy under saline conditions were investigated by electrochemical impedance spectroscopy (EIS). All measurements were carried out in saline solution (0.9% NaCl) at different impressed potentials (corrosion potential (E_corr), 0 mV (SCE) and + 500 mV (SCE)) for 1 h. The experimental results were compared with those obtained by potentiodynamic polarization curves. The corrosion current densities obtained for the titanium alloys showed lower values than for pure Ti, indicating the formation of a stable passive film with time. Electrochemical impedance spectroscopic studies indicated that the resistance of the passive film increased with the impressed potential. The impedance spectra were fitted using a non‐linear least square (NLLS) fitting procedure. The magnitude of the corrosion resistance of titanium alloys under saline solution was compared and results are presented.     

Electrochemical stability and surface analysis in evaluation fluoride effect on new bioalloy Ti7Al3V2Mo2Fe used in dentistry

The aim of this study is focused on the effect of fluoride concentration on the corrosion behavior of Ti7Al3V2Mo2Fe alloys uncoated/coated in artificial saliva. Ti7Al3V2Mo2Fe alloys were covered by chemical methods with hydroxyapatite to enhance the osteointegration of implants materials. The stability of Ti7Al3V2Mo2Fe alloys uncoated/coated in artificial saliva with/without fluoride ions was studied by electrochemical techniques (open circuit potential, cyclic voltammetry, and linear polarization). On the covered samples, dissolution test in simulated body fluids and wettability test were performed. Investigations regarding the sample surface modifications were made by atomic force microscopy and Fourier transform infrared spectroscopy. The results show that the corrosion resistance of Ti7Al3V2Mo2Fe in solution containing fluoride decreases in comparison with that in a solution not containing fluoride. Significant changes appear at a concentration larger than 0.05 M. The coating has a positive effect on corrosion resistance of metallic substrate in the fluoride presence acting as a semi‐mechanical barrier.     

纯Ti和Ti-Pd合金在有、无添加H2O2的磷酸盐缓冲溶液中的耐腐蚀性能（英文）

采用动电位和电化学阻抗谱技术研究了纯Ti(2级)和Ti-Pd合金(7级)的耐腐蚀性能。实验温度为36.6℃,实验溶液包括模拟的健康人体条件的pH7.4的PBS溶液和添加了H2O2(0.015mol/L)的pH5.2的炎症状态的PBS溶液。Ti-Pd合金(7级Ti),在含H2O2的PBS溶液中,其耐腐蚀性能比纯Ti的好(较低的腐蚀电流密度),表明其是一种很好的骨科植入材料。     

Electrochemical characteristics of titanium based biomaterials in artificial saliva

In the last decade, new titanium alloys have been developed in different areas of dentistry, such as Ti6Al7Nb, Ti6Al2Nb1Ta1Nb, and Ti5Al2.5Fe. The aim of this study was to compare the Ti6Al7Nb, Ti6Al2Nb1Ta1Nb, Ti5Al2.5Fe, and Ti6Al4V alloys with the commercial titanium, regarding the corrosion resistance in artificial saliva. In the electrochemical estimations the polarization data are converted into instantaneous corrosion rate values (I_corr). The passivation properties were comparable for the four alloys. The EIS spectra are best fitted using an equivalent circuit (EC), which corresponds to the model of a two‐layer structure for the passive film. High impedance values (in the order of 10⁶ Ω cm²) were obtained from medium to low frequencies for all materials suggesting high corrosion resistance in artificial saliva. The electrochemical and corrosion behavior of Ti6Al4V is not affected on substituting vanadium with niobium, iron, molybdenum, and tantalum.     

Behavior of Dental/Implant Alloys in Commercial Mouthwash Solution Studied by Electrochemical Techniques

This study investigates the electrochemical behavior of the various dental materials: Paliag (Ag-Pd based), Wiron 99 (Ni-Cr based), Cp-Ti (commercial pure titanium), and experimental Ti12Mo5Ta alloy in commercial mouthwash solution with 500 ppm F^? (Oral B^®) and compares it with the behavior of the same dental materials in artificial saliva. Linear potentiodynamic polarization (LPP) and electrochemical impedance spectroscopy (EIS) are the electrochemical procedures of investigation. The passivation of all dental samples in artificial saliva and mouthwash solution occurred spontaneously at open circuit potential. The corrosion current density of all tested dental materials in mouthwash solution were low (1-2 μA/cm²). The results suggest a non-predominant fluoride effect on the passive layer formed on all samples at open circuit potential. No passivation could be established with Paliag alloy when polarized in mouthwash solution. The EIS results confirm that all dental sample exhibit passivity in mouthwash solution at open circuit potential (polarization resistance was around 5 × 10⁵ Ω cm²). For Paliag alloy after LPP in mouthwash solution the protectiveness passive layer was no more present. The corrosion resistances of four dental materials in mouthwash solution are in the following order: Ti12Mo5Ta > Cp-Ti > Wiron 99 > Paliag.     

TA16和TA17钛合金在高温高压水中的腐蚀行为研究

研究了TA16和TA17钛合金在高温高压中性水质中的电化学行为、均匀腐蚀行为和应力腐蚀行为.结合SEM和XPS分析技术,分析了腐蚀后合金表面形貌和氧化膜的组成.研究结果表明:在高温高压中性水质中,两种钛合金具有很好的耐腐蚀性能,TA16钛合金的钝化性能、抗均匀腐蚀和抗应力腐蚀性能均优于TA17合金,腐蚀后两种钛合金表面生成了表层由TiO2组成、内层由TiO2、Ti2 O3和TiO组成的致密氧化膜.     

Corrosion inhibition of Ti‐6Al‐4V alloy in sulfuric and hydrochloric acid solutions using inorganic passivators

The effect of iodate (IO₃^?), metavanadata (VO₃^?) and molybdate (MoO₄^2?) anions on the passivation of Ti‐6Al‐4V alloy in sulfuric and hydrochloric acid solutions was studied using open‐circuit potential measurements, polarization techniques and electrochemical impedance spectroscopy (EIS). The alloy surface was examined by scanning electron microscopy (SEM). It was found that an optimum concentration of the passivator is essential for the corrosion inhibition process. Above this concentration the rate of alloy corrosion decreases as the concentration of the passivating ion increases. Scanning electron micrographs have shown that the flawed regions present in the alloy surface were repaired in the presence of the passivator anion. The optimum concentration of each anion and its corrosion inhibition efficiency for titanium and Ti‐6Al‐4V alloy have been determined. It turned out that the corrosion inhibition efficiencies of IO₃^?, VO₃^? and MoO₄^2? anions for the corrosion of Ti and Ti‐6Al‐4V in both hydrochloric and sulphuric acid solutions exceed 98%.     

Effect of nitrogen ion implantation dose on torsional fretting wear behavior of titanium and its alloy

Various doses of nitrogen ions were implanted into the surface of pure titanium, Ti6Al7Nb and Ti6Al4V, by plasma immersion ion implantation. Torsional fretting wear tests involving flat specimens of no-treated and treated titanium, as well as its alloys, against a ZrO₂ ball contact were performed on a torsional fretting wear test rig using a simulated physiological medium of serum solution. The treated surfaces were characterized, and the effect of implantation dose on torsional fretting behavior was discussed in detail. The results showed that the torsional fretting running and damage behavior of titanium and its alloys were strongly dependent on the dose of the implanted nitrogen ions and the angular displacement amplitude. The torsional fretting running boundary moved to smaller angular displacement amplitude, and the central light damage zone decreased, as the ion dose increased. The wear mechanisms of titanium and its alloys were oxidative wear, abrasive wear and delamination, with abrasive wear as the most common mechanism of the ion implantation layers.     

Anodic Behavior of a Titanium–Aluminum Hybrid Electrode: Formation of Hydroxide-Oxide Compounds

The electrochemical behavior of a titanium–aluminum hybrid electrode in aqueous solutions of electrolytes containing halide ions (F^– and Cl^–) was studied. The effects of current density, solution composition, and ratio of the working surface area of titanium and aluminum on the anodic dissolution rate of a Ti?Al hybrid electrode and its electrochemical characteristics were revealed. The joint anodic dissolution of aluminum and titanium in the aqueous media under study made it possible to obtain precursors of the highly disperse oxide system Al₂O₃–TiO₂. Data of X-ray and electron-microscopic analysis confirmed the results obtained.     

CP-Ti在含氟离子硝酸中电化学腐蚀行为

采用开路电位(OCP)、动电位极化曲线(PPC)、电化学阻抗谱(EIS) 3种电化学测试手段对工业纯钛(CP-Ti)在含氟离子硝酸溶液中的电化学腐蚀行为进行研究。结果表明:随着硝酸溶液中氟离子浓度的增加,CP-Ti耐蚀性变差;影响CP-Ti耐蚀性转变的临界氟离子浓度为1. 25 mmol/L;氟离子与CP-Ti表面的氧化膜发生反应,致使均匀、致密的氧化膜溶解转变为多孔膜,降低了CP-Ti的耐蚀性。     

Evaluating electrochemical behaviour of recrystallized titanium alloys in Ringer's solution

By anodic potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) techniques, the effect of recrystallization on the corrosion and electrochemical behaviour of Ti12Mo and Ti12Mo5Ta alloys was studied. Aerated Ringer's solution was employed as electrolyte solution at 37 °C. The pH was 6.9 and adjusted to 2.5 simulating the disease state. The results show excellent corrosion resistance for recrystallized Ti12Mo and Ti12Mo5Ta alloys, corroborated by high values of polarization resistance and low values of passive current density. Recrystallized structure rendered the Ti12Mo and Ti12Mo5Ta alloys extremely corrosion resistant.     

Bestimmung der Abtragungsraten von Zirconium,Tantal und der Legierung Tantal-40Niob in fluoridhaltiger azeotroper Salpetersäure mit Hilfe der Radiotracer-Methode

The radiotracer technique as a means to investigate the corrosion of zirconium, tantalum, and a Ta-40Nb alloy in fluoride containing azeotropic nitric acid Zirconium and tantalum as well as the tantalum 40% niobium alloy are of considerable technical importance due to their high corrosion resistance against numerous corrosive media. With respect to corrosion testing in analytically pure azeotropic nitric acid in the temperature range between 20 and 121°C, corrosion rates were determined for zirconium: 7 · 10^?6 to 5 · 10^?4 mm/y, for tantalum: 10^?8 to 4 · 10^?6 mm/y, and for the Ta-40Nb alloy: 2 · 10^?7 to 8 · 10^?6 mm/y [1]. These corrosion rates will be markedly increased by adding small amounts of fluorides or by fluoride impurities. The radiotracer method after neutron activation was applied to determine the corrosion rates in azeotropic fluoride containing nitric acid. Even minute additions of fluorides strongly affect the corrosion resistance of zirconium. In the range between 0.15 and 10 ppm F^? and at a temperature of 108°C, corrosion rates between 5.3 · 10^?3 and 3.1 mm/y were measured. It was impossible to establish a limit for the fluoride concentration, below which the corrosion rate of zirconium will not be adversely influenced. The corrosion rates of tantalum and the Ta-40Nb alloy are considerably increasing above a fluoride concentration of 10 ppm. The highest corrosion rates measured were between 8.4 · 10^?3 mm/y at 50°C/280 ppm F^? and 1.4 · 10^?2 mm/y at 110°C/320 ppm F^?. Within the range of this investigation, the corrosion resistance of tantalum was higher than that of the Ta-40Nb alloy by one order of magnitude. The corrosion resistance of zirconium and tantalum was not influenced by any treatment of the samples before testing.