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.     

Effect of vitreous enamel coating on the oxidation behavior of Ti6Al4V and TiAl alloys at high temperatures

Vitreous enamel coating is a promising candidate as a high temperature protective coating for titanium (Ti)-based alloys due to its high thermo-chemical stability, compatibility, and matching thermal expansion coefficient to the substrates. Vitreous enamel coating is economically attractive because of its low cost and easy handling. The oxidation behavior of Ti6Al4V (at 700°C) and Ti–48Al (at 800–900°C), with and without the vitreous enamel coating exposed to air, are investigated in this article. The results show that the vitreous enamel coating could markedly protect the substrate (Ti6Al4V and Ti48Al) from oxidation at elevated temperatures. In comparison, the TiAlCr coating might not provide long-term protection for the Ti6Al4V alloys due to the heavy interfacial interdiffusion at high temperatures, although a protective Al₂O₃ scale could form at the initial oxidation stage. The vitreous enamel coating remains intact, uniform, compact, and adhesive to the substrate, however, with undetectable interfacial reaction after oxidation. It is also worth noting that some new phases form in the coating during oxidation at 900°C, although the protectiveness of the coating seems to be unaffected.     

A novel potential ceramic material for melting Ti6Al4V alloy: A solid solution of BaZrO3 and CaZrO3

Vacuum induction melting technology is a promising low-cost method for producing high-quality titanium alloy. The key challenge lies in the development of ceramic crucibles with excellent chemical stability for titanium alloy corrosion. In this work, (Ba_1−x,Ca_x)ZrO₃ ceramic was designed and synthesised via pressureless sintering of a mixture of BaZrO₃ and CaZrO₃ powders. X-ray diffraction and scanning electron microscopy analyses showed that a new phase, Ba_0.8Ca_0.2ZrO₃, was formed after heat treatment at 1700 °C. Vacuum induction melting experiments of the Ti6Al4V alloy were carried out using a Ba_0.8Ca_0.2ZrO₃ crucible. Compared with the original BaZrO₃ crucible and CaZrO₃ crucible, the erosion layer of the Ba_0.8Ca_0.2ZrO₃ crucible was significantly reduced by approximately 85∼92.5%. The interface between the crucible and the alloy was clearly visible, and there was no obvious element diffusion between the alloy and the material. This shows that Ba_0.8Ca_0.2ZrO₃ is highly promising as a crucible material for melting Ti6Al4V alloys.     

Preparation,scratch adhesion and anti-corrosion performance of TiO2-MgO-BHA coating on Ti6Al4V implant by plasma electrolytic oxidation technique

Bovine hydroxyapatite (BHA) (from cortical bone), was selected as the main electrolyte for plasma electrolytic oxidation (PEO) on Ti6Al4V implant. The prepared PEO coatings were examined by X-ray diffraction, field emission scanning electron microscope and energy-dispersive X-ray spectroscopy. The surface roughness, adhesion strength, wettability, surface energy and corrosion behaviour of the film were also investigated. The results show that the oxide layer (26 μm) formation on the Ti6Al4V was rough and porous. The micro-pores were filled with anatase TiO₂, cubic MgO and hexagonal BHA particles. The porous structures and the compound particles were mainly composed of Mg, O, Ca, P, Ti, Na and Al. Unlike previous coatings produced from calcium and phosphorus inorganic solutions, the coating formation from a newly developed bovine bone-derived HA electrolyte revealed an additional MgO phase in the coating layer. Moreover, higher amount of single phase hexagonal crystalline BHA phase with a Ca/P ratio of 1.1 was achieved with a single PEO process. A film-to-substrate adhesion strength of 1862.24 mN and scratch hardness of about 4.1 GPa was achieved from this method. The TiO₂/MgO/BHA film exhibited better wettability, higher surface energy and superior corrosion resistance compared to the bare Ti6Al4V substrate.     

Predicting wear mechanisms of ultra-hard tooling in machining Ti6Al4V by diffusion couples and simulation

Conventional cemented carbide is recommended for machining Ti6Al4V. However, polycrystalline diamond (PCD) and polycrystalline cubic boron nitride (pcBN) also show promise. Demands for higher productivity accelerate diffusional dissolution and chemically driven wear mechanisms in these tool materials. This study investigates active wear mechanisms by studying the interactions between Ti6Al4V and PCD, pcBN, and cemented carbide tools in diffusion couples at temperatures from 900° to 1300°C. All tool materials suffered from diffusion to varying degrees, and different chemical reactions occurred. Titanium carbide with minor vanadium alloying (Ti,V)C reaction products act as diffusion barriers when using PCD and cemented carbide, while the reaction products acting as diffusion barrier in pcBN is (Ti,V)B₂. The presence of Mo and W in binder sites of pcBN reduces diffusional dissolution of cBN. Diffusion simulations agreed well with microscopy investigations and were enabled by the known temperature and pressure conditions of the static diffusion couples.     

Martian regolith—Ti6Al4V composites via additive manufacturing

In order to investigate the in-space in situ resource utilization, directed energy deposition (DED)-based additive manufacturing (AM) has been utilized to process Martian regolith—Ti6Al4V (Ti64) composites. Here we investigated the processability of depositing 5, 10, and 100 wt% of Martian regolith premixed with Ti6Al4V using laser-based DED, analyzing the printed structure via X-ray diffraction, Vicker's microhardness, scanning electron microscopic imaging, and wear characteristics utilizing an abrasive water jet cutter to simulate abrasive environments on the Martian surface. The results indicate that the surface roughness and hardness of the composites increase with respect to the Martian regolith’ weight percentage due to in situ ceramic reinforcement. For instance, i5-wt% addition of Martian regolith increased the Vicker's microhardness from 366 ± 6 HV_0.2 for as-printed Ti64 to 730 ± 27 HV_0.2 while maintaining similar abrasive wear performance as Ti6Al4V. The results point toward laser-based AM for fabricating Ti64—Martian regolith composites with comparable properties. The study also reveals promising results in limiting the mass burden for future space missions, resulting in cheaper and easier launches.     

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.     

Interfacial structures and strengthening mechanisms of in situ synthesized TiC reinforced Ti6Al4V composites by selective laser melting

The in-situ nanoscale TiC particles reinforced Ti6Al4V composites was prepared by selective laser melting (SLM) from the mixture of Ti6Al4V alloy powders and graphene powders, the microstructure and interface bonding of the composites were studied. The composites were mainly composed of α, α' martensite and α+β structures. More TiC were formed in the overlapping regions than that in the molten pool, the solidification rate in overlapping regions was slow, which was beneficial to TiC nucleation and growth. The TiC and Ti matrix displayed following orientation relationships: axis [0 0 1]_β-Ti∥[-1 -1 1]_TiC∥[0 -1 1 0 ]_α-Ti, lattice plane (2 2 2)_TiC //(0 0 0 2)_α-Ti, lattice plane (1 1 1)_TiC//(0 0 0 2)_α-Ti, lattice plane (1 1 1)_TiC//(1 0 -1 0)_α-Ti. The TiC and Ti matrix have a small degree (6.2%) of mismatch between (1 1 1)_TiC and (0 0 0 2)_α-Ti, and the semi-coherent interface was occurred. TiC preferentially nucleated and grew up along its (1 1 1) plane. The situ synthesized TiC was added into the Ti6Al4V alloy, refined the grains, and increased the microhardness of the alloy. The microhardness of the composites was 13.6% higher than that of Ti6Al4V alloy. The TiC effectively pinned the dislocations and grain boundaries were responsible for the enhanced mechanical properties of the composites.     

Influence of annealing temperature on microstructure evolution of TiAlSiN coating and its tribological behavior against Ti6Al4V alloys

TiAlSiN multicomponent coating, owing to its high hardness and excellent high temperature resistance, was widely used in the cutting field of difficult-to-cut materials such as titanium alloys. For machining titanium alloys, high temperature is easy to gather on the tool chips and deteriorate the cutting tools. Moreover, high temperature will also promote the microstructure evolution and make the wear mechanism more complex. In this paper, TiAlSiN coatings were deposited on cemented carbides and annealed at 400 °C, 600 °C and 800 °C respectively for 60 min in air, followed by reciprocating friction tests against Ti6Al4V counterparts. AFM, SEM, EDS and XPS were applied to investigate the microstructure evolution and tribological behavior of TiAlSiN coating after high temperature annealing. The results demonstrated that the oxidation resistance of TiN phase in TiAlSiN coating was worse than Si₃N₄ and AlN phases. These nitrides can be oxidized to TiO₂, SiO_x and AlO_x under 600 °C, and the depth of oxide layer was increased with the rising annealing temperature, resulting in the coarsened microstructure. The wear mechanisms of as-deposited TiAlSiN coating were oxidation wear and adhesion wear. With the rising annealing temperature, abrasive wear was gradually enhanced. For the TiAlSiN coating annealed at 800 °C, abrasive wear became the dominant wear mechanism.     

Ti6Al4V钛合金表面蓝色微弧氧化膜的制备及性能

利用微弧氧化技术在Ti6Al4V钛合金表面制备出蓝色微弧氧化膜。对微弧氧化膜的微观形貌和元素组成进行了分析,并对微弧氧化膜的显微硬度进行了测试。结果表明:微弧氧化膜表面光整,呈均匀深蓝色,其主要由Ti、Mn、O和C四种元素组成,还含有少量的V、Al和Si元素;微弧氧化膜的表面粗糙度约为0.159μm,与钛合金的表面粗糙度相近;微弧氧化膜的显微硬度为5 437.4 MPa,显著高于钛合金的显微硬度。     

Non-destructive measurement of residual stress distribution as a function of depth in sapphire/Ti6Al4V brazing joint via Raman spectra

The residual stress distribution as a function of depth in a sapphire/Ti6Al4V brazing joint is non-destructively measured using Raman Spectra for the first time. A modified method that is suitable for brazing joints is developed to deconvolute the actual residual stress value in each depth from the measured averaged stress value. The measured in-plane residual stress is compressive and increases non-linearly from the surface to the interface. While the out-of-plane residual stress is compressive; it increases from the surface to the interface and peaks at a distance of 150?µm from the sample surface. Then the stress begins to decrease and becomes tensile stress, which increases to the interface. This method can also be applied to other brazing/ diffusion bonding joint with a transparent substrate.     

Investigation of brazing of Ba(Zn0.33Ta0.67)O3 ceramic with Ti6Al4V alloy

Feasibility of brazing Barium Zinc Tantalate (BZT) ceramics with Ti6Al4V alloy using active and non-active brazing alloy was investigated in the present study for high power RF window application. BZT ceramics were brazed successfully with Ti6Al4V alloy under high vacuum with active brazing alloy (Ticusil® (4.5%Ti) and Cusil-ABA® (1.5%Ti) at 850 °C and non-active brazing alloy (BAg8) at 830 °C. Micrographs at the interface of non-active brazed joints are free of interfacial micro-defects, and exhibit excellent physical contact and good metallurgical bonding with high diffusivity when compared to active-brazed joints. Ceramic-filler interfacial layer thickness is high for samples containing non-active filler (~25 µm) compared to the samples containing active filler materials (~9 µm and ~5 µm). The average shear strength of BZT ceramics brazed with non-active brazing alloy BAg8 is higher (~45.5 MPa) in comparison with active brazing alloys (~33 MPa and ~31 MPa). Fracture surface reveals that the failure is on ceramics side only indicating that the strength of non-active brazed joint is more compared to ceramics.     

Brazing ZTA ceramic and Ti6Al4V alloy directly in air: Excellent oxidation resistance at 800 °C

The Ag-2mol.% CuO braze is adopted to successfully join the zirconia toughened alumina ceramic to the surface aluminized Ti6Al4V directly in air. Fine interfaces are formed between the reactive air brazing braze and the matrix on both sides. Nano-scale diffusion layers are observed at the Ag/ZTA interface. Too low brazing temperatures (≤970 °C) result in the insufficient wettability of Ag–CuO on ceramic, while excessively high temperatures (1030–1090 °C) lead to the over-oxidation of coated Ti6Al4V. A balance is achieved at 1000 °C, at which joints reach the highest shear strength (～56.8 MPa). The oxidation tests at 800 °C for 120 h prove that joints possess excellent oxidation resistance.     

Cutting performance and wear mechanism of TiB2-B4C ceramic cutting tools in high speed turning of Ti6Al4V alloy

TiB₂–20vol%B₄C (TB20) and TiB₂–80vol%B₄C (TB80) ceramic cutting tool materials were prepared by hot pressing, and then tested in turning of Ti6Al4V alloy with various cutting parameters. The tool life and wear mechanism of TB20 and TB80 were studied and compared with a commercial grade tungsten carbide tool (WO). The results of turning showed that effective cutting length of TB20 was about one third longer than that of TB80 and WO. Among the three tools, the increment of cutting temperature measured for TB20 was the lowest as flank wear increased from 0 to 600?µm. Analysis showed that dominant wear mechanism was adhesive wear in all of the three tools tested, while chipping was also observed in TB80 and temperature deterioration in WO. In addition, the TB20 exhibited a much better integrity of cutting edge after flank wear reaching 600?µm, due to its higher toughness than TB80 and higher thermal resistance than WO, respectively. The adhesive layers of work-piece material on the rake and flank faces of both TB20 and TB80 were much thinner than that of WO, which suggested a lower adhesive wear rate in TiB₂-B₄C cutting tools. The high wear resistance of TiB₂-B₄C cutting tools is attributed to higher thermal resistance, higher hardness, and lower chemical affinity with titanium as compared with tungsten carbides, which makes them very promising materials for high speed machining of titanium alloys.     

New observations on wear characteristics of solid Al2O3/Si3N4 ceramic tool in high speed milling of additive manufactured Ti6Al4V

Additive Manufacturing (AM) technologies applied to the titanium alloys have attracted attention from industries in recent years. Despite one of the main goals of AM is the reduction of manufacturing steps, semi-finish/finish machining operations are still required so as to obtain the desired geometrical tolerance and surface features. In this study, the solid end mill was manufactured by Al₂O₃/Si₃N₄ (Sialon) ceramic materials and employed in high-speed slot milling of Ti6Al4V alloy fabricated by the Direct Metal Laser Sintering (DMLS) AM technology to study the tool wear characteristics during processing. The Raman spectroscopic method was employed to characterize the molecular structures of Sialon ceramics for the manufacturing of the cutting tool. The morphologies and elemental maps of wear region of the ceramic tool were examined by scanning electron microscope and energy dispersive spectroscopy techniques. The results show that the adhesion wear and diffusion wear are the dominant wear mechanisms, and the chemical stability of Al₂O₃/Si₃N₄ (Sialon) ceramics fabricated as the solid ceramic tool to the attack of the atoms from additive manufactured Ti6Al4V is relatively weak under the atmosphere. The difference of thermal expansion coefficients of diffusion layer and tool substrate accelerates the initiation and propagation of thermal cracks formed on the diffusion interface. Moreover, fracturing and crater-like groves near the tool edge were finally formed due to the removal of adhered workpiece material.     

Effect of carburizing treatment on microstructural,mechanical and tribological performances of Cr doped DLC coating deposited on Ti6Al4V alloy

Cr doped diamond-like carbon (DLC) coating was deposited on the carburized Ti6Al4V alloy (TA) by magnetron sputtering (MS). The physical and chemical characteristics of Cr doped DLC coating were obtained using scanning electron microscope, energy dispersive spectroscope, Raman spectrometer, X-ray photoelectron spectroscopy and Fourier transform infrared, and the mechanical property and adhesion force were analyzed by nanoindenter and scratch tester. The effects of carburizing treatment on the coefficient of friction (COF) and wear mechanism of Cr doped DLC coatings were investigated on a ball-on-disk tribometer. The results show that the adhesion force and mechanical property of Cr doped DLC coating deposited on the carburized TA are higher than those deposited on the original TA. The average coefficients of friction (COFs) of Cr doped DLC coatings deposited on the original and carburized TAs under the dry-friction condition are 0.157 and 0.143, respectively, showing that the carburizing treatment has the obvious effect of friction reduction for the Cr doped DLC coating. The wear mechanism of Cr doped DLC coating deposited on the carburized TA is combined action of abrasive wear and adhesive wear, which are contributed to the enhancement of mechanical property of Cr doped DLC coating by carburization treatment. Furthermore, the average COFs of Cr doped DLC coatings deposited on the original and carburized TAs under the oil-lubrication condition are 0.152 and 0.131, respectively, which are superior to those under the dry-fiction condition. The carburizing treatment promotes the formation of self-repairing carbonyl of Cr doped DLC coating, and the oil-wet characteristic of Cr doped DLC coating with the aromatic aldehyde of CO as the functional group plays the main role of friction reduction.     

The effect of bioactive glass nanoparticles on corrosion barrier performance and bioactivity of zinc oxide coatings electrodeposited on Ti6Al4V substrate

Zinc oxide coatings were electrodeposited on Ti6Al4V substrates from a nitrate bath with and without 1 wt% BG nanoparticles at ?1.2 and ?1.4 V_Ag/AgCl, where the former voltage created a spherical morphology, the latter developed a flower-like one. The spherical morphology was modified through the incorporation of BG nanoparticles, where surface roughness, wettability, and adhesion strength of the coating were enhanced. The coatings with spherical morphology also revealed complete barrier property after immersion in PBS solution. However, fully adverse effects were found for the coatings deposited at ?1.4 V_Ag/AgCl. This indicates that morphology is the most important factor determining the properties of ZnO and ZnO-BG coatings. The highest corrosion barrier performance was achieved for the ZnO-BG composite coating with spherical morphology. Although the composite coating with flower-like morphology did not provide complete barrier property at short immersion times, it earned that at longer times due to the plugging supported by the BG nanoparticles. The bioactivity tests in SBF at long times showed that the formation of Ca-P deposits on the surface of the composite coatings was noticeably improved.     

A biomimetic bilayer coating on laser-textured Ti6Al4V alloy with excellent surface wettability and biotribological properties for artificial joints

Titanium alloys with excellent mechanical properties and biocompatibility are widely used in surgical implants. However, due to its poor tribological properties, it is difficult to be used in joint bearing interfaces. Herein, mimicking the soft/hard hierarchical structure of articular cartilage/subchondral bone and the unique lubrication mechanisms of articular cartilage, a biomimetic bilayer coating consisting of a TiO₂ layer and a hydrogel layer was fabricated on laser-textured Ti6Al4V alloy by laser surface texturing, thermal oxidation and ultraviolet radiation techniques. Meanwhile, a zwitterionic polymer (SBMA) was introduced into the hydrogel layer to provide hydration lubrication. The experimental results demonstrated that the introduction of SBMA greatly improved the hydrophilicity and compressive modulus of the hydrogel layer. Compared with Ti6Al4V, the Ti6Al4V-hydrogel bearing interface exhibited a lower friction coefficient (0.06) and better wear resistance when lubricated in deionized water. More importantly, this Ti6Al4V-hydrogel bearing interface could maintain stable and low friction coefficients when lubricated in different physiological solutions for a long-term friction (4 h), and the lowest friction coefficient (0.039) was measured in phosphate buffer (PBS) solution. The outstanding biotribological performance was mainly attributed to the biphasic and hydration lubrication mechanisms of the hydrogel layer. This study provides new insights into the development of Ti6Al4V bearing interfaces for artificial joints.     

Heparin Enriched-WPI Coating on Ti6Al4V Increases Hydrophilicity and Improves Proliferation and Differentiation of Human Bone Marrow Stromal Cells

Titanium alloy (Ti6Al4V) is one of the most prominent biomaterials for bone contact because of its ability to bear mechanical loading and resist corrosion. The success of Ti6Al4V implants depends on bone formation on the implant surface. Hence, implant coatings which promote adhesion, proliferation and differentiation of bone-forming cells are desirable. One coating strategy is by adsorption of biomacromolecules. In this study, Ti6Al4V substrates produced by additive manufacturing (AM) were coated with whey protein isolate (WPI) fibrils, obtained at pH 2, and heparin or tinzaparin (a low molecular weight heparin LMWH) in order to improve the proliferation and differentiation of bone-forming cells. WPI fibrils proved to be an excellent support for the growth of human bone marrow stromal cells (hBMSC). Indeed, WPI fibrils were resistant to sterilization and were stable during storage. This WPI-heparin-enriched coating, especially the LMWH, enhanced the differentiation of hBMSC by increasing tissue non-specific alkaline phosphatase (TNAP) activity. Finally, the coating increased the hydrophilicity of the material. The results confirmed that WPI fibrils are an excellent biomaterial which can be used for biomedical coatings, as they are easily modifiable and resistant to heat treatments. Indeed, the already known positive effect on osteogenic integration of WPI-only coated substrates has been further enhanced by a simple adsorption procedure.     

Potential dependent selective dissolution of Ti–6Al–4V and laser treated Ti–6Al–4V in acid/chloride media

The corrosion properties of Ti–6Al–4V and laser surface melted (LSM) Ti–6Al–4V samples were investigated in 0.05 M H₂SO₄/0.05 M NaCl solution. Laser surface treatment was found to increase the corrosion potential and decrease the corrosion rates of the alloy. The current–potential profile of the LSM was found to be generally noisy below 0.5 V, indicating an unstable surface, which undergoes continuous dissolution and repassivation. However, above 0.5 V the LSM specimen exhibited higher corrosion current compared to the untreated alloy. Inductively coupled plasma (ICP) analysis of metals in solution was carried out after controlled potential electrolysis. Generally, the aluminium percentage was found to be the highest in solution compared to titanium and vanadium. The aluminium percentage in solution reached 94% compared to titanium and vanadium upon polarization in the passive region at 1.01 V. SEM showed that some local and shallow pitting to occur in both the untreated and LSM alloy. EDS results showed that aluminium composition of the electrolysed alloy surface is lower than the original material composition, and decreased from 6% in the original alloy to 0.18% after two hours of electrolysis of the LSM specimen.