Galvanic corrosion of titanium-based dental implant materials

This paper describes an investigation of the corrosion behavior of Ti-based dental materials with Au, CrNi and CoCr in Ringer solution by the use of Tafel plots, Evans diagrams and EIS Nyguist diagrams. The galvanic potentials and currents obtained for various implant couples are as follows: For, Ti6Al4V/CrNi couple −0.030 V (Ag/AgCl (3 M NaCl)) and 7.94 μA cm⁻²; for Ti6Al4V/CoCr couple −0.020 V (Ag/AgCl (3 M NaCl)) and 7.08 μA cm⁻²; for Ti6Al4V/Au couple −0.020 V (Ag/AgCl (3 M NaCl)) and 5.62 μA cm⁻². The Ti6Al4V/Au couple was found to be the most suitable one against galvanic corrosion according to both the Tafel method and mixed potential theory. The corrosion behaviors of Ti6Al4V/CoCr and Ti6Al4V/CrNi couples were found to be similar.     

Corrosion behavior of TiN and TiN/Ti composite films on Ti6Al4V alloy in Hank’s solution

Surface films of TiN and TiN/Ti were deposited on Ti6Al4V alloy by arc ion plating (AIP). Open-circuit potential, potentiodynamic polarization tests and electrochemical impedance spectroscopy (EIS) were employed to investigate the corrosion performance of TiN and TiN/Ti films in Hank’s simulated body fluid at 37 °C and pH 7.4. Scanning electron microscopy (SEM) was used to study the surface morphology of the corroded samples after the potentiodynamic polarization tests. The results show that the TiN and the TiN/Ti films can provide effective protection for the Ti6Al4V substrate in Hank’s fluid, and the TiN/Ti composite film showed a corrosion resistance superior to that of the TiN film. The outer TiN layer of the composite film mainly acted as an efficient barrier to corrosion during short-term experiments. In contrast to the bare Ti6Al4V, no pitting was observed on the surface of the TiN and TiN/Ti films deposited on the bare alloy after potentiodynamic polarization.     

Voltammetric stability of anodic films on the Ti6Al4V alloy in chloride medium

The biocompatibility and mechanical integrity of Ti and Ti6Al4V alloy can be affected by corrosion processes. This paper presents studies on the stability of anodic oxide films on Ti6Al4V and Ti in chloride medium. The oxides were grown potentiodynamically up to 8.0 V in the phosphate buffer saline (PBS) solution (pH 6.8) at 25 and 37 °C. The morphology of the obtained anodic oxides and the type of corrosion that occurred were analyzed by SEM–EDS. The Ti6Al4V alloy presented less corrosion resistance than pure Ti. Elemental analyses showed that the decrease of the alloy corrosion resistance is due mainly to the corrosion of Al.     

Electrochemical and structural evaluation of functionally graded bioglass-apatite composites electrophoretically deposited onto Ti6Al4V alloy

Titanium and its alloys are widely used as materials for implants, owing to their corrosion resistance, mechanical properties and excellent biocompatibility. However, clinical experience has shown that they are susceptible to localised corrosion in the human body causing the release of metal ions into the tissues surrounding the implants. Several incidences of clinical failures of such devices have demanded the application of biocompatible and corrosion resistant coatings and surface modification of the alloys. Coating metallic implants with bioactive materials is necessary to establish good interfacial bonds between the metal substrate and the bone. Hence, this work aimed at developing a bioglass-apatite (BG-HAP) graded coating on Ti6Al4V titanium alloy through electrophoretic deposition (EPD) technique. The coatings were characterized for their properties such as structural, electrochemical and mechanical stability. The electrochemical corrosion parameters such as corrosion potential (E_corr) (open circuit potential) and corrosion current density (I_corr) evaluated in simulated body fluid (SBF) have shown significant shifts towards noble direction for the graded bioglass-apatite coated specimens in comparison with uncoated Ti6Al4V alloy. Electrochemical impedance spectroscopic investigations revealed higher polarisation resistance and lower capacitance values for the coated specimens, evidencing the stable nature of the formed coatings. The results obtained in the present work demonstrate the suitability of the electrophoretic technique for the preparation of graded coating on Ti6Al4V substrates.     

Synthesis and evaluation of TaC nanocrystalline coating with excellent wear resistance,corrosion resistance,and biocompatibility

To improve the mechanical properties, corrosion resistance, and biocompatibility of implanted titanium alloys, a TaC nanocrystalline coating was deposited on Ti–6Al–4V alloy using a double-cathode glow discharge method. The microstructure of the newly developed coating was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The coating exhibits a dense and uniform structure, composed of equiaxed TaC grains with an average grain size of 15.2 nm. The mechanical properties of the TaC-coated Ti–6Al–4V alloy were evaluated by a scratch tester, a nanoindentation tester, and a ball-on-disc tribometer. The average hardness of the TaC nanocrystalline coating is about 6 times higher than that of uncoated Ti–6Al–4V alloy and the specific wear rate of the coating is two orders of magnitude lower than that for Ti–6Al–4V at applied normal loads of 4.9 N under dry sliding condition. The electrochemical behavior of the TaC nanocrystalline coating after soaking in Ringer's solution for different periods was investigated by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). Furthermore, in vitro cytocompatibility of the coating was assessed using MC3T3-E1 mouse osteoblastic cells. The results showed that the TaC coating exhibits better corrosion resistance and biocompatibility as compared to uncoated Ti–6Al–4V alloy.     

In vitro corrosion and mineralization of novel Ti–Si–C alloy

The in vitro electrochemical behaviour of a new titanium based α-alloy (Ti–0.5 wt% Si–0.65 wt% C), fabricated via casting and rapid cooling route, was determined using linear, Tafel, potentiodynamic polarization tests and electrochemical impedance spectroscopy (EIS), complemented with ex situ SEM-EDS analysis to evaluate the corrosion mechanism. The experimental results revealed that silicon and carbon, in addition to titanium, resulted in the enhancement of mechanical properties. The polarization tests confirmed that Ti–Si–C alloy possessed excellent corrosion resistance (a low corrosion current density of 0.033 μA cm⁻²), comparable to cp Ti and better than Ti6Al4V in phosphate buffered saline (PBS). The mechanism of corrosion was identified as selective dissolution of titanium solid solution matrix. EIS studies indicated the formation of a stable, passive oxide film on the alloy. Further, in vitro bioactivity was evaluated using mineralization tests i.e. by immersing the pre-treated alloy in a concentrated simulated body fluid (10× SBF). Chemical and microstructural characterization of the mineral layer, formed during immersion, revealed the deposition of fine, porous micron-sized globules of a phase rich in calcium-phosphate (Ca-P). In summary, the bulk properties and excellent in vitro electrochemical and mineralization behaviour of the as-cast Ti–Si–C alloy reveal a high potential for its application as load bearing metallic implants.     

Controlled surface modification of Ti6Al4V using biomimetic mineralization via thermo-chemical route improves bioactivity

Ti alloy (Ti6Al4V) sheets were bio-activated by a two-step thermo-chemical treatment followed by biomimetic mineralization. The samples were then characterized by standard techniques and evaluated of their mechanical properties, electrochemical corrosion potential and biological performance. The intermediate layer corresponding to thermo-chemical treatment displayed anatase TiO₂ peaks and the final bio-mineralization resulted in a globular hydroxyapatite (HAP) layer. Thermo-chemical treatment yielded a two-fold increase (98.79% increment) in microhardness value, whereas, the biomimetically activated samples showed a very small decrease in the same owing to their ceramic behavior. The surface hydrophobicity of the bio-activated surface was found reduced significantly, might assist to facilitate improved cell adhesion. Electrochemical corrosion measurements exhibited an increase in corrosion potential and decrease in current density of the samples, suggested increased corrosion resistant. The surface coating on the Ti6Al4V sheet also demonstrated enhanced cytocompatibility as no toxic effect of the samples could be perceived to human keratinocyte cell line (HaCaT). Similarly, the samples showed higher hemocompatibility and enhanced bactericidal activity. Our study concluded that the surface coating of Ti6Al4V sheets significantly improved corrosion resistance and bioactivity of the substrates, which can be applied for various biomedical applications.     

Understanding the protective role of a gradient titanium oxide ceramic layer on Ti6Al4V against corrosion via analyses of Mott-Schottky curve and electron work function (EWF)

Thermal oxidation (TO) process was employed to generate a gradient titanium oxide ceramic layer for improving corrosion performance and service safety of Ti6Al4V alloy. The semiconductor characteristic of the TO layer was evaluated in CO₂-saturated simulated oilfield brine. The generated TO layer with a thickness of about 20 μm was dense and continuous without cracks or spalling characteristics. The TO layer mainly comprised of an oxide ceramic layer (rutile TiO₂ ceramic phase, minor anatase one, and Al₂O₃) and an oxygen diffusion layer. The conducted electrochemical analysis suggested that the corrosion resistance of Ti6Al4V alloy was improved using TO surface strengthening process. It was demonstrated that the TO layer with semiconductor characteristics showed a transition from n-type (donor) to p-type (acceptor) with the increasing applied electric potential. The electron work function of the TO layer was higher than that of Ti6Al4V alloy with a naturally formed passive film. The improvement in corrosion properties was attributed to the excellent chemical stability and semiconductor properties of the metal oxide ceramic phases (TiO₂, Al₂O₃) in the TO layer.     

A study of the potentials achieved during mechanical abrasion and the repassivation rate of titanium and Ti6Al4V in inorganic buffer solutions and bovine serum

Titanium alloys in orthopaedic implants are susceptible to mechanical disruption of the passive film (fretting corrosion). To study this effect, open-circuit potential (ocp) measurements before, during and after mechanical disruption of the passive film in a tribo-electrochemical cell on commercial pure titanium and Ti6Al4V alloy in inorganic buffer solutions in the pH range from 2.0 to 12.0 and calf bovine serum at pH 4.0 and 7.0 are reported. Additionally, the effect of pH, electrolyte and sample composition on the repassivation rate has been investigated. The potentials achieved during the abrasion of Ti6Al4V are the same as those characterizing pure titanium, which indicates that the corrosion current of both materials in the active state is due to the oxidation of titanium. However, commercial pure titanium displays a tendency to repassivate faster than Ti6Al4V in inorganic buffer solutions thanks to the lower critical current density and the higher catalytic activity towards the hydrogen evolution reaction observed on the pure metal in comparison with the alloy.Proteinaceous solutions like bovine serum, significantly slow down the anodic dissolution and the cathodic reactions both on titanium and the alloy. However, the repassivation rate of the Ti6Al4V is not affected by serum, while that of cp titanium significantly decreases both at pH 4.0 and 7.0.     

In vitro cytotoxicity,corrosion and antibacterial efficiencies of Zn doped hydroxyapatite coated Ti based implant materials

Ti6Al4V alloy is successfully used as implant material in dental and orthopedic surgeries for years due to its much better compatibility, lower density, corrosion resistance, etc. compared to the other metals. Meantime, modification of the surface of these alloys is needed to enhance material-tissue interaction and osteointegration between the implant and the bone. In this study, Ti6Al4V alloy surfaces were modified by application of RF magnetron sputtering technique and coated with zinc (Zn) doped hydroxyapatite (HAp). The obtained coating was very stable with highly crystalline structure, demonstrated enhanced corrosion resistance, osteointegration and antimicrobial effectiveness against Escherichia coli (E. coli) bacteria.     

Tantalum carbide coating on Ti‐6Al‐4V by electron beam physical vapor deposition method: Study of corrosion and biocompatibility behavior

This study aimed to improve the corrosion resistance and biocompatibility of titanium alloy (Ti‐6Al‐4V) by tantalum carbide (TaC) deposition through electron beam physical vapor deposition (EB‐PVD) method. The physical and chemical characteristics of the coated surface are comprehensively evaluated. The corrosion resistance and ion release are assessed. Cytocompatibility assay and cell morphology observation are performed to assess toxicity and cell interaction, respectively. The TaC‐coated Ti‐6Al‐4V exhibits more resistance to corrosion and ion release. It provides a surface, which is appropriate for cell adhesion, an expansion as well as better biocompatible performance. So, it could improve osseointegration Ti‐alloy implants in clinical applications.     

电流密度对Ti 6Al 4V微弧氧化膜形貌和性能的影响

采用NaAlO2-Na3PO4-NaF溶液体系,研究了电流密度对Ti 6Al 4V合金微弧氧化膜厚度、生长速率、表面形貌、粗糙度、组成相以及氧化膜耐蚀性、耐磨性等影响.结果表明,(1)在试验的电流密度范围内,氧化膜的厚度随电流密度的增大呈线性增大,但氧化膜的粗糙度却几乎呈指数增大,表面质量变差;(2)在质量分数为3.5%的NaCl溶液中显示了比Ti 6Al 4V钛合金更好的耐蚀性;(3)在干摩擦条件下,氧化膜的摩擦系数高于基体的,氧化膜的磨损机制为脆性断裂.     

In situ corrosion monitoring of Ti–6Al–4V alloy in H2SO4/HCl mixed solution using electrochemical AFM

Electrochemical atomic force microscope (ECAFM) was employed for in situ observation of corrosion of solution annealed and furnace cooled Ti–6Al–4V titanium alloy in 0.5 mol l⁻¹ H₂SO₄ + 1 mol l⁻¹ HCl mixed solution. A scanning electron microscope (SEM) equipped with an energy dispersive spectrometer (EDS) was also used for microstructure examination and chemical composition analysis. For solution annealed followed by furnace-cooled Ti–6Al–4V titanium alloy, selective corrosion of α phase and galvanic effect at α/β interface could be clearly observed at open circuit potential under ECAFM. A higher dissolution rate was also found in α phase than β phase on the bare Ti–6Al–4V titanium alloy. The effect of potential on the corrosion behavior was also explored. Negligible corrosion was found after potentiostatic etching at −0.5 and −0.85 V_Pt for 120 min. However, selective dissolution of α phase with respect to β phase occurred when the potential was controlled at −0.9 V_Pt. The polarity inversion during potentiostatic etching at −0.9 V_Pt was also found and discussed in this study.     

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.     

Electrochemical corrosion behavior of magnesium and titanium alloys in simulated body fluid

The electrochemical behavior of AZ91D and Ti–6Al–4V alloys was investigated in simulated body fluid (SBF) at 37 °C. The aim of the present study was to evaluate their corrosion performance through the analysis of corrosion resistance variation with time, using electrochemical impedance spectroscopy (EIS) tests and corrosion current density using potentiodynamic polarization measurements. Very low current density was obtained for Ti–6Al–4V alloy compared to that of AZ91D alloy, indicating a typical passive behavior for Ti alloy. EIS results exhibited high corrosion resistance indicating a highly stable film on titanium alloy compared to magnesium alloy in SBF.     

The investigation of the tribocorrosion properties of DLC coatings deposited on Ti6Al4V alloys by CFUBMS

Various machine components produced from titanium alloys used in various industries are subject to a combination of electrochemical and mechanical effects. The science of surface transformations resulting from the interaction of mechanical loading and chemical reactions that occur between elements of a tribosystem exposed to corrosive environments is described as tribocorrosion. This research focuses on the tribocorrosion behaviour of Ti6Al4V alloys after coated by using closed field unbalance magnetron sputtering (CFUBMS). The structural analyses of the coatings were performed using Raman spectroscopy and scanning electron microscopy (SEM). Tribocorrosion experiments were performed in a pin-on-disc tribotester under electrochemical polarisation in NaCl 1 wt.% solution. This study shows that the Ti-DLC coating is protecting the Ti6Al4V alloy and having good performance in corrosion and tribocorrosion conditions. The OCP values for Ti6Al4V substrate and Ti-DLC protective coatings during tribocorrosion tests were measured as −560 V and −330 V, respectively. These results showed that Ti-DLC protective coating on Ti6Al4V substrates increased the tribocorrosion resistance by acting as a barrier layer.     

In vitro biocompatibility of a nanocrystalline β-Ta2O5 coating for orthopaedic implants

To improve the durability and bioactivity of Ti–6Al–4V alloy used for medical implants, the β-Ta₂O₅ nano-crystalline coatings were introduced using double cathode glow discharge technique. The coating microstructure was characterized using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (HRTEM). The coating exhibits an assembly of near-equiaxed grains, locally aligned normal to the coating surface. The β-Ta₂O₅ coating exhibits strong adhesion to substrate and a strong resistance to deformation and cracking under applied loads. Cells culture tests showed that the coating is more beneficial to the adhesion and proliferation of NIH-3T3 cells as compared to the uncoated alloy. In-vitro bioactivity was evaluated by immersion of the coating in simulated body fluids (SBF) for different periods up to 14 days at 37 °C. The results indicated that bioactivity of Ti–6Al–4V was dramatically improved after the deposition of β-Ta₂O₅, since the coating has a higher apatite forming ability than the Ti–6Al–4V substrate. Finally, the electrochemical behavior of the β-Ta₂O₅ coating after soaking in SBF at 37 °C for 0, 3, 7, and 14 days was studied through potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). EIS measurements also confirm that the presence of a hydroxyapatite layer on the coating becomes thicker and denser during soaking in SBF. Moreover, the coating exhibits better corrosion resistance than the bare alloy. Hence, the β-Ta₂O₅ coating is a promising candidate coating for protection of orthopedic implants with enhanced bioactivity and corrosion resistance.     

Al2O3/Cu-Sn-Ti+B钎料/Ti-6Al-4V合金连接的微观结构及力学性能

在Cu-21Sn-12Ti钎料中添加不同质量分数的B粉制备Cu-Sn-Ti＋B复合钎料,然后在钎焊温度910℃保温10 min条件下钎焊Al2O3与Ti-6Al-4V合金。研究了原位生成TiB对Al2O3/Ti-6Al-4V合金接头微观结构及力学性能的影响。接头中原位生成的TiB呈晶须状均匀分布在Ti2Cu上,当采用TiB体积分数低于40%的钎料钎焊Al2O3与Ti-6Al-4V合金时,均可获得连接良好且界面致密的钎焊接头。随接头中TiB的体积分数增加,Ⅱ区中的Ti2（Cu,Al）含量增加,并逐渐变得连续,TiB的分布区Ⅲ范围增宽,Ti-6Al-4V合金向钎料中的溶解量增加。接头的室温抗剪强度随TiB的体积分数增加先上升后下降,当接头中TiB体积分数增至20%时,接头抗剪强度达最大,为70.1MPa。     

Interfacial microstructure and mechanical properties of ultrasonic-assisted brazing joints between Ti–6Al–4V and ZrO2

Ultrasonic-assisted brazing (28.8 kHz, 180 W) was introduced to achieve high-quality joints between Ti–6Al–4V alloy and ZrO₂ ceramic with Al-5wt.%Si brazing filler in air. The interfacial microstructure of intermetallic compounds (IMCs) and the phase constitution of joints ultrasonic-assisted brazed at 700 °C for different ultrasonic time were investigated in detail using a scanning electron microscope equipped with an energy-dispersive X-ray spectrometer and X-ray diffractometer. When the ultrasonic time was 20s, the average shear strength of the joint reached a maximum value of 90.68MPa and two important types of IMCs Ti(Al,Si)₃ and Ti₇Al₅Si₁₂ formed at the interface between the Ti–6Al–4V and the filler. Ultrasonic played a vital role in the formation of Si segregation regions at the interface near the Ti–6Al–4V and in the centre of the joint. A change in the Ti molar fraction, resulting from the cavitation effect of ultrasonic on the surface of Ti–6Al–4V, increased the chemical potential gradient of Si across the joint. Meanwhile, driven by the ultrasonic standing wave field in the liquid Al-5wt.%Si filler, Si atoms moved to the ultrasonic antinode-plane spontaneously. Ultrasonic-assisted brazing proved to be an effective method of joining Ti–6Al–4V and ZrO₂ with Al-5wt.%Si filler.     

Investigation of Ti3AlC2 formation mechanism through diffusional reaction between carbon and Mo-modified Ti6Al4V

Carbon and Mo-coated Ti6Al4V alloy diffusion couple was used to investigate Mo-modified diffusion reaction between carbon and Ti6Al4V. Randomly dispersed carbide particles were observed in Ti6Al4V alloy after 900℃ exposure. Carbide particles were found evolving from defective TiC_x (x<1) to mixture of TiC_x and defective Ti₃AlC₂. Although Mo atoms were hardly detected in particles, their dilution effect along Ti alloy grain boundary (GB) is beneficial to carbon diffusion and carbide formation along GB. Based on high-resolution TEM (HRTEM) imaging, high density stacking faults (SFs) and nanotwins were observed in TiC_x particles which explain Raman activation of defects in TiC. Formation of SFs and nanotwins in TiC_x is attributed to carbon vacancies, which inversely promotes incoherent twin boundary (ITB) formation. Transformation from TiC_x to Ti₃AlC₂ is considered driven by Al indiffusion along ITBs. Intergrowth of TiC_x in defective Ti₃AlC₂ is the compromise to low Al concentration in Ti6Al4V.