Corrosion behaviour of Ti-6Al-7Nb and Ti-6Al-4V ELI alloys in the simulated body fluid solution by electrochemical impedance spectroscopy

The corrosion behaviour of Ti-6Al-7Nb and Ti-6Al-4V ELI (extra low interstitial) was investigated as a function of immersion hours in simulated body fluid (SBF) condition, utilizing potentiodynamic polarisation and electrochemical impedance spectroscopy (EIS) techniques. Polarisation experiments were conducted after 0, 120, 240 and 360 h of immersion in SBF solution. From the polarisation curves, very low current densities were obtained for Ti-6Al-7Nb alloy compared to Ti-6Al-4V ELI, indicating a formation of stable passive layer. Impedance spectra were represented in the form of Bode plots and it was fitted using a non-linear least square (NLLS) fitting procedure, in which it exhibited a two time constant system suggesting the formation of two layers. The surface morphology of the titanium alloys have been characterized by SEM and EDAX measurements.     

Cold compaction study of Armstrong Process® Ti-6Al-4V powders

The Armstrong Process® developed by Cristal US, Inc./International Titanium Powder, is an innovative, low-cost technology for producing Ti and Ti alloy powders in a one-step, continuous process. In this work, Armstrong Ti-6Al-4V powders were characterized and the cold compaction behavior of the powders were investigated in detail. As-received as well as milled powders were uniaxially die-pressed at designated pressures up to 690 MPa to form disk samples with different aspect ratios. Samples with high aspect ratio exhibited non-uniform density along the pressing axis and the density distribution was consistent with the result predicted by finite element analysis. The model developed from the linear regression analysis on the experimental density data can be used to predict density of compacts with different aspect ratios. In the studied pressure range, an empirical powder compaction equation was applied to linearize the green density — pressure relationship. Cold compaction parameters were obtained for the as-received and milled Armstrong Ti-6Al-4V powders.     

The Durability of Adhesively-bonded Ti-6Al-4V

The durability of chromic acid-anodized Ti-6Al-4V alloy, adhesively-bonded with FM-5 supported polyimide adhesive has been studied. The performance tests compared titanium samples that had been thermally treated and bonded, and samples that were bonded and thermally treated. Following the thermal treatment, the durability was examined (1) by immersing wedge-type specimens in boiling water and measuring the crack growth and (2) by measuring the lap shear strength for single lap specimens. In the wedge tests, failure occurs within the adhesive for specimens treated at temperatures below 371°C for less than one hour. For treatments at higher temperatures and for longer periods of time, failure occurs within the anodic oxide. From the lap shear tests, the principal finding is that the lap strength decreases with increasing treatment time at constant temperature and with increasing temperature at a fixed time. For the lap specimens, failure occurs to a greater extent within the oxide as the treatment time and temperature increase. Surface analysis results indicate the formation of an aluminum fluoride species. It is reasoned that the formation of fluorine-containing materials weakens the oxide and promotes failure within the anodic oxide.     

The Durability of Adhesively-bonded Ti-6Al-4V

The durability of chromic acid-anodized Ti-6Al-4V alloy, adhesively-bonded with FM-5 supported polyimide adhesive has been studied. The performance tests compared titanium samples that had been thermally treated and bonded, and samples that were bonded and thermally treated. Following the thermal treatment, the durability was examined (1) by immersing wedge-type specimens in boiling water and measuring the crack growth and (2) by measuring the lap shear strength for single lap specimens. In the wedge tests, failure occurs within the adhesive for specimens treated at temperatures below 371°C for less than one hour. For treatments at higher temperatures and for longer periods of time, failure occurs within the anodic oxide. From the lap shear tests, the principal finding is that the lap strength decreases with increasing treatment time at constant temperature and with increasing temperature at a fixed time. For the lap specimens, failure occurs to a greater extent within the oxide as the treatment time and temperature increase. Surface analysis results indicate the formation of an aluminum fluoride species. It is reasoned that the formation of fluorine-containing materials weakens the oxide and promotes failure within the anodic oxide.     

Corrosion resistance of pulsed laser-treated Ti-6Al-4V implant in simulated biofluids

A commercial Ti-6Al-4V alloy was treated with a pulsed-wave Nd:YAG laser under various process conditions to obtain surface oxide layer for corrosion resistance. The corrosion behaviors of bare and laser-treated Ti-6Al-4V alloy exposed to three different simulated biofluids (SBFs), namely, (1) NaCl solution, (2) Hank's solution, and (3) Cigada solution, were studied by using the electrochemical techniques like open circuit potential (OCP), Tafel analysis, and electrochemical impedance spectroscopy (EIS). The Tafel analysis showed that the laser-treated Ti-6Al-4V specimens were more corrosion resistant than the bare specimens in any of the above SBFs. The various electrical equivalent circuit models were applied to fit the EIS results to further understand corrosion mechanisms due to different surface layers formed on the alloy surface before and after the laser treatment. Optical and AFM imaging techniques were used to evaluate the topographic and morphologic features of the alloy exposed to such SBFs. The corrosion behavior of the laser-treated surfaces was explained by the melting and solid-state oxidation processes, the morphology of the surface oxide, and the underlying alloy microstructure. It is realized during the present investigation that better corrosion resistance and surface stability can be achieved by oxide growth in solid-state, under a pulsed laser condition.     

Corrosion behaviour of Ti-6Al-4V in phosphoric acid

Ti-6A1-4V shows distinct active-passive behaviour in phosphoric acid over a wide concentration range. The cathodic polarization curves are similar over a wide range of acid concentration and temperatures. The alloy undergoes active dissolution and turns passive in the negative potential region followed by a wide range of passivity at all acid concentrations at different temperatures. Increasing acid concentration up to 11 M results in an increase in critical current density (i _cr). The passive current density (i _p) increases up to an acid concentration of 9 M while at 13 M i _cr and i _p decrease appreciably. A significant increase in both i _cr and i _p occurs with increase in solution temperature. The passive specimen remained stable for a long time when exposed to phosphoric acid under open circuit conditions.     

Ti-6Al-4V在氯离子环境中的耐蚀性研究

针对腐蚀性环境油气田开发实际,利用高温高压釜,研究Ti-6Al-4V在盐酸溴化锌加重溶液中的失重腐蚀速率,并利用体式显微镜及扫描电镜对试样进行腐蚀形貌观察和腐蚀膜成份分析,试验结果表明:在本文试验条件下,Ti-6Al-4V的腐蚀速率为0.1089mm/a;Ti-6Al-4V蚀坑较浅且呈开放式,未被腐蚀产物所覆盖;腐蚀膜中含有一定量Cl元素,表明Cl-是参与腐蚀反应的主要元素。     

Surface Preparation of Ti-6Al-4V for High-Temperature Adhesive Bonding

The role of surface preparation in high-temperature bond durability is investigated for Ti-6Al-4V adherends. Four surface preparations, including a newly-introduced treatment, plasma-sprayed Ti-6Al-4V coatings, are evaluated using a simple tensile test and a wedge/crack-propagation test. At temperatures approaching 300°C, the oxide-metal interface of oxide preparations becomes unstable. Such exposure results in a weakening of the oxide and, hence, bond failure at low tensile strength. The plasma-sprayed coating is a microscopically-rough metallic film with only a thin, native oxide. The plasma-sprayed adherend remains strong over prolonged, high-temperature exposures, and the micro-roughness is important for crack arrest in the wedge test.     

Surface Preparation of Ti-6Al-4V for High-Temperature Adhesive Bonding

The role of surface preparation in high-temperature bond durability is investigated for Ti-6Al-4V adherends. Four surface preparations, including a newly-introduced treatment, plasma-sprayed Ti-6Al-4V coatings, are evaluated using a simple tensile test and a wedge/crack-propagation test. At temperatures approaching 300°C, the oxide-metal interface of oxide preparations becomes unstable. Such exposure results in a weakening of the oxide and, hence, bond failure at low tensile strength. The plasma-sprayed coating is a microscopically-rough metallic film with only a thin, native oxide. The plasma-sprayed adherend remains strong over prolonged, high-temperature exposures, and the micro-roughness is important for crack arrest in the wedge test.     

Adhesion Tensile Testing of Environmentally Exposed Ti-6Al-4V Adherends

The structural and bonding properties of Ti-6Al-4V adherends, prepared by chromic acid anodization (CAA), were studied as a function of exposure in high-temperature environments such as vacuum, air, boiling and pressurized water, and steam. Subsequent to the environmental exposure, bonds were produced and the adhesive tensile strengths measured. Long-term exposure to high temperature, dry environments did not cause structural changes to the adherend oxide but did result in poor bond strength. The failure mode in these cases was within the oxide, which was apparently weakened by the exposure. The water-and steam-exposed oxides underwent a transition from amorphous to crystalline TiO₂ (with an accompanying change in oxide morphology); however, bond strength was maintained for moderate exposures at T ≤ 250°C. For exposure at T = 300°C, the bond strength was degraded severely. The latter result can be explained by a lack of porosity in the transformed oxide. SEM and XPS measurements were made on debonded surfaces to determine the loci of failure.     

Ti-6Al-4V钛合金脉冲阳极氧化工艺

研究了Ti-6Al-4V钛合金脉冲阳极氧化工艺,并对影响阳极氧化膜厚度的主要因素(如温度、电流密度、时间等)进行了研究,得到了满足膜厚要求的工艺参数。将优化得出的工艺参数应用于零件的仿形试件生产,得到厚度均匀的阳极氧化膜,并对其表面形貌、成分等进行了分析。     

Microstructures and mechanical properties of wear-resistant titanium oxide coatings deposited on Ti-6Al-4V alloy using laser cladding

In this work, a freeze-dried TiO₂ nano-sized powder was used as the coating material and single tracks of TiO_x coating were cladded on Ti-6Al-4V substrates using a diode laser. The microstructure, chemical composition, and mechanical properties of the coatings were characterized and their relationships were explored. Coatings with structural and compositional gradients formed under a laser energy density (LED) of 20 kJ/m, while coatings with a relatively homogeneous microstructure were obtained using a LED of 30 kJ/m. The microstructure evolution was controlled by the molten pool lifetime and the intensity of convective flow during laser processing. The elastic modulus of the graded coating showed a decreasing trend from the top coating surface to the interface while that of the homogeneous coating remained constant. Our results also demonstrated that the hardness and wear resistance of the oxide coatings were up to four and ten times higher than that of the substrate.     

Gas nitriding and subsequent oxidation of Ti-6Al-4V alloys

Ti-6Al-4V alloys consisting of α-Ti grains and intergranular β-Ti islands were nitrided at 850°C for 1 to 12 h under a nitrogen pressure of 1 Pa. With increasing nitriding time, the Ti-N compound layer became thicker, and the α-Ti diffusion zone containing dissolved nitrogen became wider. In the Ti-N compound layer, the initially formed Ti₂N became TiN as the nitriding progressed. The nitride layers were oxidized to rutile-TiO₂ after oxidation at 700°C for 10 h in air.     

Dip Coating of Calcium Hydroxyapatite on Ti-6Al-4V Substrates

Ti-6Al-4V alloy is the most commonly used metallic material in the manufacture of orthopedic implants. The main inorganic phase of human bone is calcium hydroxyapatite (Ca₁₀(PO₄)₆(OH)₂, HA). To achieve better biocompatibility with bone, metal implants made of Ti-6Al-4V are often coated with bioceramics. Dip-coating techniques scarcely are used to apply HA onto metallic implants. New dipping-solution recipes to be used for HA coatings are described in this work. Scanning electron microscopy and X-ray diffractometry have been used for sample characterization.     

Corrosion resistance of anodic oxides on the Ti-50Zr and Ti-13Nb-13Zr alloys

Electrochemical analyses on the biocompatible alloys Ti-50Zr and Ti-13Nb-13Zr, as-cast and heat-treated, in distinct electrolytes (simulating or not physiological media: pH 7, Ringer, PBS, phosphate buffer and Na₂SO₄ solutions; pH 1, H₂SO₄, HNO₃, CH₃SO₃H, HClO₄ and H₃PO₄ solutions) are reported. Analyses of the open-circuit potential values indicated that either as-cast or heat-treated samples of both alloys present the same tendency to spontaneously form an oxide film on their surfaces and that the oxide grown in the Na₂SO₄ solution presents better protection characteristics than those formed in the phosphate buffer, Ringer and PBS solutions, in this order. Cyclic voltammograms obtained in the Ringer and PBS solutions showed that the Ti-13Nb-13Zr alloy does not transpassivate up to potentials of 8 V (versus SCE), while the Ti-50Zr alloy presents corrosion at potentials lower than 2 V (versus SCE), indicating that this alloy is less resistant to corrosion in solutions simulating physiological conditions. The obtained pit potential values showed that the heat treatment has very little influence on the corrosion behavior of the alloys. Finally, both alloys did not present transpassivation at potentials up to 8 V (versus SCE) in the H₂SO₄, HNO₃, CH₃SO₃H and H₃PO₄ solutions; however, when immersed in the HClO₄ solution the Ti-50Zr alloy underwent pit corrosion while the Ti-13Nb-13Zr alloy remained corrosion resistant in this potential range.     

Factors Affecting the Durability of Ti-6Al-4V/Epoxy Bonds

Factors influencing the durability of Ti-6Al-4V/epoxy interphases were studied by determining chemical and physical properties of Ti-6Al-4V adherend surfaces and by characterizing the strength and durability of Ti-6Al-4V/epoxy bonds.

Ti-6Al-4V adherend surfaces were oxidized either by chemical etch or anodization. Four principal pretreatments were studied: chromic acid anodization (CAA), sodium hydroxide anodization (SHA), phosphate fluoride acid etch (P/F) and TURCO basic etch (TURCO). The oxides were characterized by SEM, STEM, profilometry, contact angles and XPS.

All adhesive bonding was carried out using a structural epoxy, FM-300U. Both lap shear and wedge test samples were tested in hot, wet environments. The results lead to the conclusion that the interfacial area between the adhesive and adherend is the primary factor affecting bond durability.     

Ti-6Al-4V合金表面激光熔覆NiCrBSi＋5%BN涂层组织和性能

Ti-6Al-4V合金具有比强度高、耐蚀性能好等优点,在航天、航空、石油和化工等新科技工业部门广泛使用。在表面激光熔覆金属-陶瓷复合涂层是改善钛合金性能的重要方式,利用XRD、SEM和EDS等分析手段对NiCrBSi＋5%（质量分数）BN熔覆层的微观组织进行分析。利用HV-1000型显微维氏硬度计测试激光熔覆试样的硬度。     

Laser Assisted Nitriding of Ti-6Al-4V Alloy: Metallurgical and Electrochemical Properties

The surface properties of Ti-6Al-4V alloy, such as wear resistance, are inadequate for many applications. To improve the surface properties of the alloy, many techniques have been considered. One of the promising techniques is to form a nitride layer on the surface of the workpiece by a laser beam. In the present study, laser assisted nitriding of the Ti-6Al-4V alloy surface is carried out under a nitrogen gas flow environment. A CO₂ laser is used to irradiate the Ti-6Al-4V alloy surface while nitrogen is introduced co-axially with the laser beam onto the workpiece surface. The resulting surface cross section is examined metallurgically. SEM and XRD were carried out for material characterization. The study is extended to include the electrochemical response of the resulting surfaces. The surface morphology of the electrochemically treated workpieces are examined. It is found that in the laser treated region dendritic structures occur and TiN forms in the surface vicinity. The density of pit formation at the surface of the treated region reduces considerably.     

Effect of transition layer on the performance of hydroxyapatite/titanium nitride coating developed on Ti-6Al-4V alloy by magnetron sputtering

A gradient transition multilayer hydroxyapatite/titanium nitride (HA/TiN) coating was prepared on the Ti-6Al-4V alloy by magnetron sputtering. The composition, surface topography, microstructure, adhesion strength and electrochemical properties of the as-deposited coatings were characterized by SEM/EDS, AFM, XRD, FT-IR and electrochemical workstation. The experimental results showed that the single TiN coating deposited at a partial pressure of nitrogen (N₂) of 0.08?Pa had the best internal stress and tribological performance, and its volume loss was only 0.89% of that of Ti-6Al-4V alloy. The introduction of the TiN transition layer greatly improved the wear resistance of the Ti-6Al-4V alloy, and the adhesion strength of the HA layer to the substrate increased from 6.50?±?0.5?N to 11.70?±?1.2?N, an increase of 56%. The HA/TiN coating surface consisted of uniform hemispherical particles with dense structure and invisible defects (micro-cracks and pores). For the HA surface layer, the crystal structure and active hydroxyl (-OH) group was restored after heat treatment. Potentiodynamic polarization experiments indicated that the HA/TiN coating achieved the lowest corrosion current density and the most positive corrosion potential compared to the single TiN layer and Ti-6Al-4V alloy. In summary, it can be conclude that the gradient transition layer can well improve the mechanical properties and electrochemical behavior of the titanium alloy, and largely ensuring the stability of the surface bioactive coating.     

Evaluation of Ti-6Al-4V surface treatments for use with a polyphenylquinoxaline adhesive

Three surface treatments for Ti-6Al-4V adherends were evaluated using a thermoplastic polymer monoether polyphenylquinoxaline, MEPPQ, which had been shown in previous studies to have good potential as a high temperature adhesive for aerospace applications. Initial results based on long term thermal exposure at 232°C (450°F) using the phosphate-fluoride (PF) and chromic acid anodized (CAA) treatments with MEPPQ adhesive were not encouraging. A significant improvement in strength retention and a change in failure mode (cohesive) at 232°C (450°F) was found for the sodium hydroxide anodization (SHA) treated specimens when compared to the PF and CAA treated specimens. Although an improvement in long term thermal durability was obtained with the SHA treatment of Ti-6Al-4V, a change in failure mode from cohesive to adhesive was noted for the RT tests after 12 months exposure at 232°C (450°F). Such a change is indicative of a degradation of the adhesive-adherend interface. An improved surface treatment with better long term durability is still required for aerospace applications.