Untersuchungen über das Korrosionsverhalten von Zirkoniumlegierungen I. Verhalten gegenüber wäßrigen Medien

Investigations into the corrosion behaviour of zirconium alloys I. Behaviour in the presence of aqueous media Extensive corrosion research covering 5O Zr alloys have shown that the good corrosion resistance of pure Zr cannot be improved to any greater extent by alloying. Pur Zr as well as most of its alloys have a high corrosion resistance; even in boiling mineral acids (20% H₂SO₄, HNO₃, and HCl) the corrosion rate is below 0.5 g/m²·d and no attack can be recognized in neutral salt solutions. The metal also resists attack by boiling 2O% KOH. Strong attack, however, it caused bv Fe-III-chloride. The metals do not resist attack by HF, while neutral KF attacks but little, however produces pitting. The effect of alloying additions is due to the structure produces by them: pure grain boundaries or very fine heterogeneous structures show good corrosion resistance. Ti, Hf, Sn and small amounts of Nb have little influence, Mo, W, larger amounts Nb and small pt and Re additions give rise to Local cells, while Fe, Cr and Ni have practically no influence.     

Untersuchungen über das Korrosionsverhalten von Zirkoniumlegierungen II. Verhalten bei Wasserdampfkorrosion

Investigation into the corrosion behaviour of zirconium alloys. 11. Behaviour under steam corrosion conditions An investigation into the corrosion behaviour of about 50 Zr alloys in high pressure high temperature steam (240 atm, 400°C) and hot air (4OO°C) has revealed a clear correlation between the behaviour in the two media. Alloys characterized by lower scaling susceptibility are also less susceptible to corrosion in steam, while, on the other hand, thicker scale layers tend to reduce hydrogen embrittlement. From the alloying additions studied Sn, Fe, Cr and Ni have a clearly favourable influence and W may have a similar effect. Ti has an outspoken negative influence on the behaviour in steam (spalling off of the scale) and Si, too, is deleterious because the SiO₂ being formed is soluble in steam, so that the scale layers retain their penetrability. Mo cannot be recommended either, while Nb is favourable in particular because of its grain refining effect. The favourable effect of Cu additions has been confirmed. Alloys with Fe, Cr and Ni and single types with Mo, Nb and Cu are superior to pure Zr with respect to steam resistance and are in part superior to Zircaloy 2 with respect to their mechanical strength.     

Beitrag zum physikalischen und korrosionschemischen Verhalten von IVa-Metallegierungen

The physical and corrosion-chemical behaviour of IVa metal alloys The stability of titanium in respect of non-oxidant acids can be considerably increased by alloying it with Zr, Hf, Nb, Mo or Re. In the case of Zr, Hf, Nb and Ta, a decisive improvement of the corrosion behaviour can only be attained if the At-percentage of these metals in the alloys exceeds 50 pC. In the case of molybdenum, a content from 20 pC upwards has already a markedly passivating effect. But the improvement in corrosion properties must be bought at the price of poorer machinability. A particularly effective alloying metal, even in small quantities, is Rhenium. An excellent corrosion resistance and, at the same time, good machinability can be attained with ternary Ti-Mo-Ta alloys (with Mo + Ta accounting for some 20 At-pC) and with a Ti-12Mo-1Re alloy. The alloying of titanium with Zr, Hf, V, Cr or Mo is apt to cause, in some cases, a considerable deterioration in the scaling resistance of titanium. Improvements can be obtained by using small quantities of Nb, W and particularly Ta. Ti-Ta alloys with Ta contents up to 10 At-pC still have a good scaling resistance at 900° C.     

Untersuchung über das Korrosionsverhalten von Zirkoniumlegierungen. IV. Das Lochfraßverhalten Zirkoniumlegierungen

Investigation into corrosion behaviour of zirconium alloys. IV-Pitting behaviour of zirconium alloys Electrochemical investigations into the resistance of a number of Zr-alloys in different solutions against pitting corrosion have shown that additions of Va- and VIa-group metals and in particular Ti improve the resistance of pure Zr. Metals forming local elements decrease pitting corrosion resistance. Minor amounts of Fe, Ni and Cr have practically no influence. The pitting corrosion resistance of Zr and its alloys decreases with increasing concentration of chloride ions in the solutions. Additions of SO₄-ions retard the beginning of the pitting but do not shift the pitting corrosion potential. NO₃-ions on the other hand produce a real inhibition. Newly developed methods for the quick determination of the pitting corrosion potential were very useful for the described investigations.     

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.     

Corrosion behavior of Zr–Nb–Cr cladding alloys

Zr-Nb-Cr alloys were used to evaluate the effects of alloying elements Nb and Cr on corrosion behavior of zirconium alloys. The microstructures of both Zr substrates and oxide films formed on zirconium alloys were characterized. Corrosion tests reveal that the corro- sion resistance of ZrxNb0.1Cr （x = 0.2, 0.5, 0.8, 1.1; wt%） alloys is first improved and then decreased with the increase of the Nb content. The best corrosion resistance can be obtained when the Nb concentration in the Zr matrix is nearly at the equilibrium solution, which is closely responsible for the formation of columnar oxide grains with protective characteristics. The Cr addition degrades the corrosion resistance of the Zrl.lNb alloy, which is ascribed to Zr（Cr,Fe,Nb）2 precipitates with a much larger size than β-Nb.     

Composition and processing effects on the electrochemical characteristics of biomedical titanium alloys

The electrochemical behaviour of the Ti–13Nb–13Zr and Ti–6Al–4V ELI alloys with martensitic microstructures was investigated by polarization and electrochemical impedance spectroscopy (EIS) in Ringer’s solution. The impedance spectra were interpreted by a two time-constants equivalent circuit. Both investigated alloys showed high corrosion resistance, but the thin and uniform passive film on the Ti–6Al–4V ELI alloy surface was more protective. The inner barrier and outer porous layer were highly resistant and capacitive. However, thicker and more porous passive film on the Ti–13Nb–13Zr alloy surface may be beneficial for osteointegration. The suitable thermomechanical processing improved the corrosion resistance of Ti–13Nb–13Zr alloy.     

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.     

Relationship between phase composition and corrosion resistanceof Ni-Ti-Nb based shape memory alloys

1　ＩＮＴＲＯＤＵＣＴＩＯＮＮｉ Ｔｉ Ｎｂａｌｌｏｙｓ ,ｏｎａｃｃｏｕｎｔｏｆｔｈｅｉｒｓｈａｐｅｍｅｍ ｏｒｙａｎｄ ｐｈａｓｅｔｒａｎｓｆｏｒｍａｔｉｏｎｈｙｓｔｅｒｉｓｉｓ ,ｈａｖｅｂｅｅｎｐａｉｄａｔｔｅｎｔｉｏｎｂｙｒｅｓｅａｒｃｈｅｒｓｆｏｒｍａｎｙｙｅａｒｓａｎｄｐｒｏ ｐｏｓｅｄｆｏｒｖａｒｉｏｕｓａｐｐｌｉｃａｔｉｏｎｓ[1～ 5] .Ｔｈｅｒｅｓｕｌｔｓｓｈｏｗｔｈａｔｔｈｅｐｈａｓｅｔｒａｎｓｆｏｒｍａｔｉｏｎｈｙｓｔｅｒｉｓｉｓｄｕｅｔｏ β ＮｂｐａｒｔｉｃｌｅｓｉｎＮｉ Ｔｉｍａｔ…     

钛生物医学材料耐蚀性能研究进展

综述了钛生物医学材料在体液中的耐蚀性能.主要阐述了局部腐蚀、磨损腐蚀、腐蚀疲劳和应力腐蚀破裂等4种腐蚀形式.进而展望了目前钛生物材料的研究动向及应用前景.     

Stability of the passive state of Zr–Nb crystalline alloys

Stability of the passive state was assessed for pure Zr and four Zr–Nb alloys (2.5, 5.0, 10.0, 25.0 at.% Nb) after 24 h exposure to naturally aerated 3.5% NaCl solution (pH = 6). Open circuit potential values indicated that all the Zr–Nb alloys studied and the pure Zr undergo spontaneous passivation due to spontaneously formed oxide film passivating the metallic surface. It also indicated that the addition of increasing Nb contents to pure Zr seems to improve the protection characteristics of its spontaneous oxides. Potentiodynamic polarization curves showed an increase of the breakdown potential and the extent of the passive range following an increased niobium amount in the alloy. This leads to the conclusion that a progressive increase of niobium content positively affects the localized corrosion behaviour of the Zr–Nb alloys by enhancing the electrochemical stability of the passive film. Electrochemical impedance spectroscopy (EIS) studies showed high impedance values for all the samples, and its increase on increased niobium content in the alloy indicated an improvement in the corrosion resistance of the spontaneous oxide film. The fit obtained suggests a single passive film present on the metal surface, with resistance improving with the increase of niobium amount in the alloy. All these electrochemical results show the beneficial effect of increasing niobium contents on the passive state stability of the Zr–Nb alloys.     

Comparison between corrosion behaviour of implant alloys Ti6Al7Nb and Ti6Al4Zr in artificial saliva

The present paper investigates two different titanium alloys: Ti6Al7Nb – a well‐established implant biomaterial and Ti6Al4Zr – a relatively new titanium alloy. Roughness is evaluated with atomic force microscopy (AFM) and the hydrophilic/hydrophobic balance by contact angle measurements. Furthermore, an extensive characterization was done in order to evaluate and compare the electrochemical behaviour for both titanium alloys in artificial Fusayama and Afnor saliva, at different immersion times, and consisted of Tafel plots, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Also, metals ions release was measured using inductively coupled plasma mass spectrometry (ICP‐MS). In both studied artificial saliva, Ti6Al4Zr alloy presents a better electrochemical behaviour according to corrosion rates from both electrochemical techniques and ICP‐MS.     

Corrosion resistant Ti alloy for sulphuric acid medium: Suitability of Ti–Mo alloys

The corrosion resistance of Ti–Mo (5, 10, 15 and 25 wt% molybdenum) alloys in 5–25% sulphuric acid was evaluated. The Ti–Mo alloys offered a better corrosion resistance than commercially pure titanium (CP‐Ti). The higher impedance values, higher phase angle maximum, ability to reach the phase angle maximum at relatively lower frequencies, ability to exhibit a constant phase angle maximum over a wider range of frequencies, higher phase angle values at 0.01 Hz, have confirmed the formation of a stable passive oxide film on Ti–Mo alloys. The study recommends the use of Ti–Mo alloys, particularly Ti–25Mo alloy, as a suitable material of construction for sulphuric acid medium.     

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.     

Electrochemical corrosion behavior of biomedical Ti–22Nb and Ti–22Nb–6Zr alloys in saline medium

The aims of this study were to investigate the effects of Zr addition and potentiodynamic polarization on the microstructure and corrosion resistance of Ti–22Nb and Ti–22Nb–6Zr alloy samples. The corrosion tests were carried out in 0.9% NaCl at 37 °C and neutral pH value, utilizing the OCP, potentiodynamic polarization, and electrochemical impedance spectroscopy (EIS) techniques. The results of XRD and optical microscopy indicated that the addition of Zr stabilized the β phase, which plays a crucial role in the corrosion resistance improvement of the Ti–22Nb–6Zr alloy. From the polarization curves, it can be seen that the alloys exhibited a wide passive region without the breakdown of the passive films and also low corrosion current densities. In addition, the values of the corrosion current densities and passive current densities decreased with the addition of 6 at% Zr into the Ti–22Nb alloy. The EIS results of these two alloy samples after 1‐h immersion in 0.9% NaCl solution, and being fitted by R_S(Q_PR_P) model, suggested that the corrosion resistance of the passive films improved with the addition of Zr and only a single passive film formed on the surfaces. However, two time constants were observed for the Ti–22Nb and Ti–22Nb–6Zr alloy samples after potentiodynamic polarization, the spectra of which can be fitted using the R_s(Q_o(R_o(Q_bR_b))) model. In addition, the corrosion resistance of the two alloy samples was reinforced significantly because of polarization when compared to the immersed samples. All these observations suggested a nobler electrochemical behavior of the titanium alloys with the addition of Zr element and after polarization.     

Ti13Nb13Zr 合金离子氮化层的摩擦磨损性能研究

目的提高医用钛合金的耐磨损性能。方法应用等离子渗氮技术在Ti13Nb13Zr基材上制备改性层,并对改性层组织、成分及硬度进行测试。利用往复磨损试验机研究改性层在干摩擦条件下的摩擦磨损性能,并与未处理的基材进行对比。结果 Ti13Nb13Zr合金表面经渗氮后形成致密均匀的改性层,硬度高达1110HV0.025,改性层的磨损体积约为基材的1/23。结论等离子渗氮技术有效地改善了Ti13Nb13Zr合金的摩擦磨损性能。     

Electrochemical corrosion of novel beta titanium alloys

Electrochemical corrosion behaviors of novel beta titanium alloys, Ti−30Ta−10Nb−10Zr, Ti−40Ta−10Nb−10Zr and Ti−40Ta−10Nb−4Sn were characterized in naturally aerated Hank's solution at 37°C compared with currently used biomedical titanium alloys. Ti−30Ta−10Nb−10Zr and Ti−40Ta−10Nb−10Zr exhibited comparable corrosion resistance to CP Ti or Ti−6Al−4V, while the corrosion resistance of Ti−40Ta−10Nb−4Sn was greatly inferior to the other alloys. An EIS data analysis confirmed that the resistance of passive film for Ti−30Ta−10Nb−10Zr and Ti−40Ta−10Nb−10Zr was comparable to CP Ti or Ti−6Al−4V. Ti−30Ta−10Nb−10Zr and Ti−40Ta−10Nb−10Zr alloys are promising metallic biomaterials for the future, owing to their very low elastic modulus and good corrosion resistance capabilities.     

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.     

Einflüsse von Mo,V, Nb,Ti, Zr und deren Karbiden auf die Korrosion und Wasserstoffaufnahme von Eisen in H2S-haltigen Lösungen

Effects of Mo, V, Nb, Ti, Zr and their carbides on the corrosion and hydrogen uptake of iron in H₂S-solutions Effects of the transition metals Mo, V, Nb, Ti, Zr and their carbides as well as of phosphorous on the corrosion and hydrogen uptake of iron in acid to weakly acid NaCl solutions with and without H₂S are discussed. Investigations were carried out on binary, ternary and quaternary iron based alloys, using electrochemical and surface analytical methods. No specific effect of one of the alloying elements or the carbides on the corrosion or hydrogen uptake is observed. Due to the experimental conditions, sulphur and oxygen enriched surface scales form, by which the kinetics of the corrosion processes are determined. The alloying elements are enriched on the iron surface only as a carbide. Phosphorous is enriched as a phosphide at low pH and as a phosphate at higher pH. H₂S and phosphides increase the corrosion rate and hydrogen uptake. In pure iron or low strength iron alloys, at the very high H₂S affected hydrogen activities new lattice defects are induced permanently resulting in extremely high hydrogen concentrations.     

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.