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.     

High cycle fatigue behaviour of Ti–6Al–4V alloy at elevated temperatures

High cycle fatigue behaviour of Ti–6Al–4V alloy was studied at 623 K and 723 K. Fatigue strength decreased at elevated temperatures compared with at ambient temperature. In the short life regime, fatigue strength was lower at 723 K than at 623 K, but in the long life regime it was nearly the same at both temperatures. At elevated temperatures, cracks were generated earlier at applied stresses below the fatigue limit at ambient temperature, indicating lowered crack initiation resistance. Small cracks grew faster at elevated temperatures than at ambient temperature, which became more noticeable with increasing temperature. After allowing for the elastic modulus, small cracks still grew faster at elevated temperatures.     

Corrosion behavior of Ti–6Al–4V alloy weldment in hydrochloric acid

The corrosion behavior of a thin sheet of Ti–6Al–4V alloy was investigated in hydrochloric acid solution after welding by gas tungsten arc welding. The resulting microstructure of the weld metal (WM) consisted of coarse prior β grains containing fine acicular α platelets. It was found that both base metal (BM) and WM exhibited active–passive behavior after surface activation in open circuit potential experiments. The corrosion resistance of the BM and WM was found to decrease with increasing the temperature and acid concentration. However, the WM exhibited higher corrosion rate than the BM in all examined conditions. These results were also corroborated by electrochemical impedance spectroscopy measurements. Furthermore, it was revealed that the activation energy of the corrosion process for the WM was lower as compared to the BM, which confirmed the inferior corrosion behavior of the WM.     

Effect of Sn addition on the corrosion behavior of Ti‐Ta alloy

In the present paper, the effect of Sn addition on phase constitution and corrosion behavior of Ti₆₅Ta_(35?x)Sn_x (x = 0, 1, 3, 5 at%) alloys has been investigated using X‐ray diffraction and electrochemical measurements. The results show that the β phase is stabilized when quenching after the addition of Sn into Ti₆₅Ta₃₅ alloy, with Ti₆₅Ta₃₀Sn₅ alloy consisting of single β phase at room temperature. The corrosion resistance is enhanced with increase in the Sn content. When the Sn content increases up to 5%, the addition of Sn results in a decrease of corrosion current density from 0.690 µA/cm² of the Ti₆₅Ta₃₅ alloy to 0.098 µA/cm², and corresponding passive current density decreased from 37.7 µA/cm² of the Ti₆₅Ta₃₅ alloy to 9.30 µA/cm².     

Electrochemical evaluation of Ti‐13Nb‐13Zr,Ti‐6Al‐4V and Ti‐6Al‐7Nb alloys for biomedical application by long‐term immersion tests

In this investigation the electrochemical behaviour of the Ti‐13Nb‐13Zr, Ti‐6Al‐4V and Ti‐6Al‐7Nb alloys, for application as implant materials was evaluated in Hanks' solution by electrochemical techniques. The alloys were immersed in this solution for 410 days and periodically they were tested by electrochemical impedance spectroscopy. At the end of this period, polarization curves of the three titanium alloys were obtained. The electrochemical impedance experimental results were interpreted using an equivalent electrical circuit that simulates a duplex structure oxide composed of an inner compact layer, here called barrier layer, and an outer and porous layer. The results indicated that all the alloys present a very high corrosion resistance in the electrolyte used, typical of passive alloys, and that the corrosion resistance is mainly due to the barrier layer. The passive like behaviour was maintained during the whole period of test.     

Oxidation behavior of ceramic coatings on Ti–6Al–4V by micro-plasma oxidation

Compound ceramic coatings prepared on Ti–6Al–4V alloy by pulsed bi-polar micro-plasma oxidation (MPO) in NaAlO₂ solution were oxidized under different temperature in air. The phase composition and surface morphology of the coatings before and after oxidation were investigated by X-ray diffractometry and scanning electron microscopy, respectively. Meantime, the weight gains and the high temperature oxidation characteristics of the coated samples were investigated. The results show that the coatings prepared by MPO were composed of a large amount of Al₂TiO₅ and a little -Al₂O₃ and rutile TiO₂. And the oxidation process of the coated samples included the decomposition of the Al₂TiO₅ in the coating, the oxidation of the substrate and the changes of the coating structure. After high temperature oxidation, the increase of -Al₂O₃ in the coating was due to the decomposition of Al₂TiO₅, whereas the increase of rutile TiO₂ in the coating was attributable to both the decomposition of Al₂TiO₅ and the oxidation of the Ti substrate. The main crystalline of the coatings became rutile TiO₂ after the oxidation of 1000 °C for 1 h. The decomposition of Al₂TiO₅ in the coating occurred at 900 and 1000 °C, and its half decomposition time was less than 1 h at 1000 °C. Increasing oxidation temperature or extending oxidation time, the weight gains of coated samples was increased to different extent. However, the weigh gains of the coated samples was much lower than that of the substrate, so the ceramic coatings improved the oxidation resistance of Ti alloy greatly under the experimental conditions.     

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%.     

Corrosion behaviour of a new Ti‐6Al‐2Nb‐1Ta alloy in various solutions

A new Ti‐6Al‐2Nb‐1Ta alloy was obtained for to satisfy the mechanical and anticorrosion requirements in neutral corrosive environment. The corrosion behaviour of this new Ti‐6Al‐2Nb‐1Ta alloy in 0.1 M Na₂SO₄, 3% NaCl solutions and synthetic sea water was studied in this paper, using potentiodynamic and linear polarisation method, electrochemical impedance spectroscopy (EIS) and monitoring of the open circuit potentials. The structure of the alloy represents an α + β uniform structure with un‐oriented grains. From the potentiodynamic polarisation curves it resulted that the studied alloy is self‐passivated in all three solutions having a very good and very easy tendency to passivation. The most favourable values of the electrochemical parameters were registered in 0.1 M Na₂SO₄ solution due to its reduced corrosivity. EIS measurements proved the improvement of the passive layer resistance with the immersion time. An electric equivalent circuit with two time constants was fitted. The values of the polarisation resistances showed very good protective capacities which improved in time. The open circuit potentials have the general tendency to ennoble in time, suggesting the thickening of the passive films and the increase of their protective capacities.     

Effects of the Zr and Mo contents on the electrochemical corrosion behavior of Ti–22Nb alloy

Ti–22Nb–xZr and Ti–22Nb–xMo (x = 0, 2, 4, 6, in atom percent) were prepared by an arc melting method. The alloys were solution‐treated at 1073 K for 1.8 ks followed by quenching them into ice water, and the electrochemical corrosion behavior in a 0.9% NaCl solution at 25 °C and neutral pH range of the solution‐treated alloys was evaluated by using electrochemical impedance spectroscopy, polarization curves and an equivalent circuit analysis. It was found that the microstructure of the solution‐treated Ti–22Nb alloy mainly contains β phase with small amount of α″ phase, and the addition of Zr or Mo to a Ti–22Nb alloy is efficient to stabilize the β phase. The resulting impedance parameters and passive current densities indicated that the corrosion resistance of the Ti–22Nb alloy was promoted significantly with the addition of Zr and Mo.     

Influence of dual‐RRA temper on the exfoliation corrosion and electrochemical behavior of Al–Zn–Mg–Cu alloy

Influence of dual‐retrogression and reaging (dual‐RRA) temper on the exfoliation corrosion (EC) and electrochemical behavior of Al–Zn–Mg–Cu alloy has been investigated by means of transmission electron microscope, energy dispersive X‐ray spectroscopy, tensile test, polarization curve, and EIS. Dual‐RRA temper not only kept the strength similar to retrogression and reaging temper, but also improved EC resistance compared to T76 temper, being attributed to coarser and sparser grain boundary precipitates as well as higher Cu and lower Zn content. Obtained polarization curves and EIS are in good agreement with EC rating sequence.     

Influence of regulated modification of nitride layer by oxygen on the electrochemical behavior of Ti–6Al–4V alloy in the Ringer's solution

The corrosion behavior of oxynitrided Ti–6Al–4V alloy was investigated in the Ringer's solution (simulated body fluid) at a temperature of 37°C. The oxynitriding of the alloy was carried out by leaking controlled oxygen‐containing medium into the reaction chamber at the final stage of the nitride formation. It was determined that oxynitriding improved corrosion resistance of Ti–6Al–4V alloy as it provided lower corrosion current density by 1.3–1.5 times and higher corrosion potential. In this paper, we analyzed that the resistance of the double layer had increased with the increase of the oxygen content in titanium oxynitride. Its value was higher compared with untreated alloy, indicating higher corrosion resistance of the oxynitrided one.     

Influence of microstructural changes on corrosion behaviour of thermally aged Ti‐6Al‐7Nb alloy

Solution treatment and ageing (STA) is an effective strengthening method for α + β titanium alloys. This paper reports the effect of solution treatment and aging on the corrosion behaviour of Ti‐6Al‐7Nb alloy in a simulated body fluid (Ringer's solution). Ti‐6Al‐7Nb alloy is hot rolled in the α + β field and subjected to solution treatment above and below its beta transus temperature (1283 K). The solution treated specimens are water quenched (WQ), air‐cooled (AC), and furnace cooled (FC) at three different rates, and subsequently aged at 823 K for 4 h. Microstructural changes were examined using optical microscopy and phases developed were analyzed using XRD. The influence of microstructure on the corrosion performance of the alloys are discussed in detail based on the Open Circuit Potential (OCP), passive current density and area of repassivation loop values obtained from the cyclic polarization study in Ringer's solution. The passive current density was low (0.5 μA/cm²) for the specimen with duplex microstructure obtained for specimen solution treated at 1223 K, air‐cooled, and aged, in comparison with that for as‐rolled specimen (1.5 μA/cm²). The corrosion aspects resulting from various heat treatments are discussed in detail.     

Observations on chip formation and acoustic emission in machining Ti–6Al–4V alloy

Orthogonal cutting tests were undertaken to investigate the mechanisms of chip formation for a Ti–6Al–4V alloy and to assess the influences of such on acoustic emission (AE). Within the range of conditions employed (cutting speed, v_c=0.25–3.0 m/s, feed, f=20–100 μm), saw-tooth chips were produced. A transition from aperiodic to periodic saw-tooth chip formation occurring with increases in cutting speed and/or feed. Examination of chips formed shortly after the instant of tool engagement, where the undeformed chip thickness is slightly greater than the minimum undeformed chip thickness, revealed a continuous chip characterised by the presence of fine lamellae on its free surface. In agreement with the consensus that shear localisation in machining Ti and its alloys is due to the occurrence of a thermo-plastic instability, the underside of saw-tooth segments formed at relatively high cutting speeds, exhibiting evidence of ductile fracture. Chips formed at lower cutting speeds suggest that cleavage is the mechanism of catastrophic failure, at least within the upper region of the primary shear zone. An additional characteristic of machining Ti–6Al–4V alloy at high cutting speeds is the occurrence of welding between the chip and the tool. Fracture of such welds appears to be the dominant source of AE. The results are discussed with reference to the machining of hardened steels, another class of materials from which saw-tooth chips are produced.     

In vitro corrosion behaviour of Ti‐5Al‐2Nb‐1Ta alloy in Hanks solution

Electrochemical polarization and impedance spectroscopic (EIS) techniques were used to investigate the corrosion behavior of Ti‐5Al‐2Nb‐1Ta alloy in Hanks solution at different immersion periods (0 h, 120 h, 240 h and 360 h). The impedance spectra are fitted using a non‐linear least square (NLLS) fitting procedure. The EIS spectra exhibited a two time constant system, suggesting the formation of two layers on the metal surface. The surface morphology of the alloy has been characterized by SEM and EDAX measurements.     

Mechanical and corrosion behaviour of a Ti‐Al‐Nb alloy after deformation at elevated temperatures

The mechanical properties of Ti6Al7Nb alloy deformed and heat treated at elevated temperatures were correlated with its microstructure and corrosion behaviour in Ringer (of different pH values: 2.49, 6.9 and 8.9) and Ringer–Brown solutions. Microstructural analysis revealed a Widmanstatten structure for the alloys deformed at 1100 °C (β field) and structure with α grains at 930 °C (α + β field). The thermo‐mechanical processing improved the electrochemical behaviour of Ti6Al7Nb alloys, especially their passive state. Open circuit potential variations in time reflected more compact, stable, resistant passive films on the surface of the treated alloys. Open circuit potential gradients simulating the non‐uniformities of pH along the implant surface have very low values that cannot generate galvanic corrosion. Corrosion rates and ion release are very much reduced. Impedance spectra were fitted with a two time‐constants equivalent circuit for some alloys and with three time‐constants equivalent circuit for other alloys.     

Influence of temperature and chloride ion concentration on the corrosion behaviour of Mg–4Al–3Ca–0.5RE alloy

The influence of temperature and chloride ion concentration on the corrosion behaviour of Mg?4Al?3Ca?0.5RE alloys were studied in this paper. Corrosion rates of the alloys were measured by weight loss test and electrochemical measurement. The results revealed that a shorter incubation period to the onset of corrosion, a more negative corrosion potential, and a higher corrosion rate was correlated with a higher temperature in 3% NaCl solution and a higher chloride ion concentration at 30°C. The corrosion behaviour of the alloys was affected by surface film and the corrosion mainly occurred at the breaks or defects in surface films.     

Exfoliation corrosion and electrochemical impedance spectroscopy of an Al‐Li alloy in EXCO solution

The exfoliation corrosion and electrochemical impedance spectroscopy (EIS) of an Al‐2.8%Cu‐1.5%Li‐0.3%Mg‐0.3%Zn‐0.3%Mn‐0.15%Zr alloy with various aging states in EXCO solution were investigated. The equilibrium precipitates at grain boundaries are anodic to the alloy base at their adjacent periphery. With prolonging aging time, the amount and the size of the equilibrium precipitates at grain boundaries are increased, resulting in an enhanced susceptibility to exfoliation corrosion. At the beginning of immersion in EXCO solution, the EIS plot of the alloys is composed of a capacitive arc in the high frequency range and an inductive loop in the low frequency range. As immersion time is increased, two capacitive arcs appear in the high‐mediate and mediate‐low frequency ranges respectively and the appearance time of two capacitive arcs could be an indication of the speed of localized corrosion development in EXCO solution. The longer appearance time of two capacitive arcs of the under‐aged alloy indicates its slower localized corrosion development.