Investigation of glass-forming ability,deformation and corrosion behavior of Ni-free Ti-based BMG alloys designed for application as dental implants

We developed new Ti-based bulk metallic glassy (BMG) alloys in Ti–Zr–Pd–Cu–Sn system without Ni element for application as biomaterials. These BMG alloys have a high potential to be applied as metallic biomaterials in various forms, such as melt-spun ribbons and cylindrical rods with a diameter of 4 mm. We also investigated of new Ti-based BMG alloys with higher glass-forming ability (GFA) for medical market as dental implants. These Ti-based BMG alloys do not contain Ni, Al and Be elements which are well known to be harmful for human body. In particular, a rod sample of the Ti_44.1Zr_9.8Pd_9.8Cu_30.38Sn_3.92Nb₂ BMG alloy with a diameter of 3 mm produced by copper mold casting exhibits a compressive strength of 1990 MPa and a Young's modulus of 99 GPa. In addition, the Ti_44.1Zr_9.8Pd_9.8Cu_30.38Sn_3.92Nb₂ BMG shows a large supercooled liquid region of 62 K and a reduced glass-transition temperature, T_rg( = T_g / T_m) of 0.61. The high thermal stability of the supercooled liquid allowed the fabrication of cylindrical rod specimens up to 5 mm in diameter. Thus the studied alloy exhibits high glass-forming ability (GFA) and a large size enough to be used for dental implants. The Ti_44.1Zr_9.8Pd_9.8Cu_30.38Sn_3.92Nb₂ BMG alloy also has a high corrosion resistance and is passivated at the lower passive current density of approximately 10^? 2 A m^? 2, 10^? 3 A m^? 2 and 10^? 2 A m^? 2, in 1 mass% lactic acid, PBS (phosphate-buffered saline without calcium and magnesium salts solution) and HBSS (Hank's balance salt solution without calcium, magnesium and phenol red), respectively, at 310 K, which are lower than those of pure Titanium and Ti–6Al–4V alloy.     

Effect of in situ synthesized TiB whisker on microstructure and mechanical properties of carbon–carbon composite and TiBw/Ti–6Al–4V composite joint

Carbon–carbon composite (C–C composite) and TiB whiskers reinforced Ti–6Al–4V composite (TiB_w/Ti–6Al–4V composite) were brazed by Cu–Ni + TiB₂ composite filler. TiB₂ powders have reacted with Ti which diffused from TiB_w/Ti–6Al–4V composite, leading to formation of TiB whiskers in the brazing layer. The effects of TiB₂ addition, brazing temperature, and holding time on microstructure and shear strength of the brazed joints were investigated. The results indicate that in situ synthesized TiB whiskers uniformly distributed in the joints, which not only provided reinforcing effects, but also lowered residual thermal stress of the joints. As for each brazing temperature or holding time, the joint shear strength brazed with Cu–Ni alloy was lower than that of the joints brazed with Cu–Ni + TiB₂ alloy powder. The maximum shear strengths of the joints brazed with Cu–Ni + TiB₂ alloy powder was 18.5 MPa with the brazing temperature of 1223 K for 10 min, which was 56% higher than that of the joints brazed with Cu–Ni alloy powder.     

Dissimilar joining of Ti3Al-based alloy to Ni-based superalloy by arc welding technology using gradient filler alloys

In this study, Ti–Al–Nb, Ti–Ni–Nb and Ni–Cr–Nb system alloys were designed and incorporated in order to construct a gradient structure at the surface of the joined Ti₃Al base material. And the Ti₃Al-based alloy and Ni-based superalloy were successfully joined together using gas tungsten arc (GTA) welding technology. The microstructure evolution, mechanical properties and fractured behaviors of the joints were investigated. The gradient structure remarkably decreased the formation tendency of brittle phases within the joints compared with a single filler alloy and thus improved the joint strength effectively. The average room-temperature tensile strength of the Ti₃Al/In718 dissimilar joint reached 353 MPa, and the strength value at 873 K was 245 MPa. At the Ti–Ni–Nb/Ni–Cr–Nb interface, some Ni₃(Nb, Ti) + (Nb, Ti)Cr₂ and TiNi₃ phases were detected in the Ti–Ni–Nb matrix. It was believed that their presence decreased the room-temperature strength of the Ti–Ni–Nb alloy but improved its high-temperature strength.     

Microstructure evolution and mechanical properties of GH984G alloy with different Ti/Al ratios during long-term thermal exposure

GH984G alloy is a low cost Ni–Fe based wrought superalloy designed for 700 °C advanced ultra-supercritical (A-USC) coal-fired power plants. In this paper, the microstructure evolution and tensile properties of GH984G alloy with different Ti/Al ratios during thermal exposure at different high temperatures are investigated. Detailed microstructure analysis reveals that the Microstructure of alloys with different Ti/Al ratios are similar after standard heat treatment, and the primary precipitates are γ′, MC, M₂₃C₆ and M₂B. However, η phase precipitates at grain boundary in the alloy with high Ti/Al ratio after thermal exposure at 750 °C for 570 h. By contrast, the microstructure stability of the alloy with lower Ti/Al ratio is excellent. There is no detrimental phase even if after thermal exposure at 750 °C for 5000 h in the alloy with lower Ti/Al ratio. γ′ coarsening plays a great role on the tensile strength, and the critical size range of γ′ could be defined as approximately 27–40 nm. The influence of η phase on tensile strength has close relationship with its volume fraction, the high volume fraction results in the decrease of tensile strength. The tensile strength of the alloy with lower Ti/Al ratio is obviously higher than the alloy with higher Ti/Al ratio and the yield strength has no obvious decrease during long-term thermal exposure at 700 °C. It is demonstrated that the thermal stability of microstructure and mechanical properties of GH984G alloy can be improved by moderately decreasing Ti/Al ratio to satisfy the requirement of A-USC plants.     

Study of Al–Ti/Si bi-layer as the recording media for write-once HD-DVD optical disks

Optimum structure for HD-DVD optical disks containing Al–Ti/Si bi-layer recording system was identified by reflectivity simulation and dynamic test of disk samples. For the disk sample with optimized structure, the maximum partial response signal-to-noise ratio (PRSNR) of 19.1 dB, minimum simulated bit error rate (sbER) of 1.7 × 10^?7 and modulation >0.6 were achieved at the writing power (P_w) = 11.2 mW. Transmission electron microscopy (TEM) revealed that the polycrystalline granular clusters constitute the recording marks. Subsequent analyses evidenced that element mixing/alloy reactions occur in between Si and Al–Ti layers and the formation of Al_3.21Si_0.47 crystalline phase is responsible for the signal recording in the disk samples.     

Transient liquid phase (TLP) bonding of Al7075 to Ti–6Al–4V alloy

TLP diffusion bonding of two dissimilar aerospace alloys, Ti–6Al–4V and Al7075, was carried out at 500 °C using 22 μm thick Cu interlayers for various bonding times. Joint formation was attributed to the solid-state diffusion of Cu into the Ti alloy and Al7075 alloy followed by eutectic formation and isothermal solidification along the Cu/Al7075 interface. Examination of the joint region using SEM, EDS and XPS showed the formation of eutectic phases such as, ?(Al₂Cu), T(Al₂Mg₃Zn₃) and Al₁₃Fe along grain boundaries within the Al7075 matrix. At the Cu/Ti alloy bond interface a solid-state bond formed resulting in a Cu₃Ti₂ phase formation along this interface. The joint region homogenized with increasing bonding time and gave the highest bond strength of 19.5 MPa after a bonding time of 30 min.     

Surface treatment of new type aluminum lithium alloy and fatigue crack behaviors of this alloy plate bonded with Ti–6Al–4V alloy strap

Samples consisting of new aluminum lithium alloy (Al–Li alloy) plate developed by the Aluminum Company of America and Ti–6Al–4V alloy (Ti alloy) plate were investigated. Plate of 400 mm × 140 mm × 2 mm with single edge notch was anodized in phosphoric solution and Ti alloy plate of 200 mm × 20 (40) mm × 2 mm was anodized in alkali solution. Patterns of two alloys were studied at original/anodized condition. And then, aluminum alloy and Ti alloy plates were assembled into a sample with FM 94 film adhesive. Fatigue crack behaviors of the sample were investigated under condition of nominal stress σ = 36 MPa and 54 MPa, stress ratio of 0.1. Testing results show that anodization treatment modifies alloys surface topography. Ti alloy bonding to Al–Li alloy plate effectively retards crack growth than that of Al–Li alloy plate. Fatigue life of sample bonded with Ti alloy strap improves about 62.5% than that of non-strap plate.     

The effect of different methods to add nitrogen to titanium alloys on the properties of titanium nitride clad layers

In this investigation, titanium nitride (TiN) reinforcements are synthesized in situ on the surface of Ti–6Al–4V substrates with gas tungsten arc welding (GTAW) process by different methods to add nitrogen, nitrogen gas or TiN powder, to titanium alloys. The results showed that if nitrogen gas was added to titanium alloys, the TiN phase would be formed. But if TiN powder was added to titanium alloys, TiN + TiN_x dual phases would be presented. The results of the dry sliding wear test revealed that the wear performance of the Ti–6Al–4V alloy specimen coated with TiN or TiN + TiN_x clad layers were much better than that of the pure Ti–6Al–4V alloy specimen. Furthermore, the evolution of the microstructure during cooling was elucidated and the relationship among the wear behavior of the clad layer, microstructures, and microhardness was determined.     

Bond strength of Ti–5Cr based alloys to dental porcelain with Mo addition

Porcelain fused to metal crown (PFM) is widely used in dental restoration for its esthetics. Due to its excellent corrosion resistance, biocompatibility and mechanical properties, commercially pure titanium (c.p. Ti) and Ti–6Al–4V alloy have dramatically improved dental implants and prosthesis, despite the insufficient bond strength of titanium to porcelain. This study investigated the bond strength of new Ti–5Cr–xMo (x = 1–11 wt.%) alloys and low-fusing dental porcelain (Duceratin Plus, DeguDent Gmbh, Germany), and c.p. Ti and Ti–6Al–4V alloy were compared. The results show that Ti–5Cr–9Mo alloy has the highest bond strength (37.67 MPa), a result that is higher than that of c.p. Ti (30.72 MPa) and Ti–6Al–4V (30.01 MPa).     

Microstructural and mechanical properties of jointed ZrO2/Ti–6Al–4V alloy using Ti33Zr17Cu50 amorphous brazing filler

Ceramic ZrO₂ and metallic Ti–6Al–4V alloy are jointed by using a Ti₃₃Zr₁₇Cu₅₀ (at.%) amorphous alloy as a solder at 1123–1273 K in a high vacuum. It is demonstrated that the microstructure and mechanical properties are significantly influenced by the brazing temperature, the heat time and the cooling rate. The brazing seam jointing ZrO₂ with Ti–6Al–4V is composed of ZrO₂/Cu₂Ti₄O, (Ti,Zr)₂Cu/TiO, Ti₂O/CuTi₂, (Ti,Zr)₂Cu/CuTi₂/Ti–6Al–4V alloys and compounds, of which the increasing thickness weakens the shear strength as the brazing temperature, the heat time the cooling rate increase. The maximum shear strength of the brazing joints reaches 162 MPa with the optimal technical parameters: the brazing temperature of 1173 K, the heat time of 10 min and the cooling rate of 5 K/min. The fracture of the joint occurs in the brittle seam layer nearby the side of ZrO₂.     

Effects of Si addition on mechanical properties and superelasticity of Ti–7.5Nb–4Mo–2Sn shape memory alloy

Effects of 0–2.1 at.% Si additions on microstructure and mechanical properties of a Ni-free biomedical superelastic β-Ti alloy, Ti–7.5 at.%Nb–4 at.%Mo–2 at.% Sn (Ti–7.5Nb–4Mo–2Sn), were investigated. The alloys after annealing at 973 K mainly contain β and α″. As the concentration of Si is higher than 1 at.%, Ti₅Si₃ particles can be found in the alloys, and the number density of the particles increases with the increasing of silicon’s concentration. The addition of Si promotes the strength of the Ti–7.5Nb–4Mo–2Sn due to the Si solid solution strengthening effect and fine Ti₅Si₃ precipitates. However, as the Si concentration reaches 2.1%, the alloy exhibits a brittle fracture. The 0.5–1.6 at.% Si additions improve the superelasticity of the Ti–7.5Nb–4Mo–2Sn alloy by increasing the critical stress for inducing martensite (σ_SIM).     

Evaluation of wear characteristics of Al3Tip/Mg composite

The dry sliding wear tests were performed for a novel developed Al₃Ti_p/Mg composite under the ambient temperatures at 25–200 °C and the loads of 25–150 N. The wear rate of the composite increased with increasing the load, but reduced with increasing the ambient temperature. The Al₃Ti_p/Mg composite had relatively lower wear rates than AZ91D alloy under the loads of less than 100 N at 25 °C. At 200 °C, the Al₃Ti_p/Mg composite presented an absolutely higher wear resistance than AZ91D alloy, and the mild-severe wear transition was delayed. These were attributed to Al₃Ti particulates and the mechanical mixing layer formed on the worn surfaces, which hindered the plastic deformation and thermal softening of the matrix. The mechanical mixing layer contained MgO, Fe–Ti–O, Al₃Ti, Mg₁₇Al₁₂ and Mg and thickened with increasing the ambient temperature. The predominant wear mechanisms of the composite were oxidation wear and delamination wear.     

Mechanical properties of Ti–4.5Al–3V–2Mo–2Fe and possibility for healthcare applications

The mechanical properties of Ti–4.5Al–3V–2Mo–2Fe, a relatively low cost titanium alloy originally designed for structural applications (especially for aerospace applications), were investigated. The alloy was subjected to heat treatments with various solution treatment temperatures (annealing temperature) and cooling rates. The mechanical properties of the heat-treated alloys were then used in order to judge the prospects of practical usage of the alloy for healthcare equipment such as wheelchairs.The mechanical properties of Ti–4.5Al–3V–2Mo–2Fe are highly affected by either solution treatment or cooling rate, and they change as a result of the change in the microstructure. The alloy single annealed at temperature in the α + β field has very high fatigue ratio (0.80–0.85) and high specific strength (210–260 MPa/g cm^− 3) with a modest fracture toughness (J_IC = 25–35 kN/m). This balance of fatigue ratio and specific strength is better than that of the existing wheelchair materials.Thus, from the point of view of mechanical properties, Ti–4.5Al–3V–2Mo–2Fe has high potential to be used for healthcare applications.     

Experimental study of diffusion welding/bonding of titanium to copper

In the present study, Ti–6Al–4V alloy was bonded to electrolytic copper at various temperatures of 875, 890 and 900 °C and times of 15, 30 and 60 min through diffusion bonding. 3 MPa uniaxial load was applied during the diffusion bonding. Interface quality of the joints was assessed by microhardness and shear testing. Also, the bonding interfaces were analysed by means of optical microscopy, scanning electron microscopy and energy dispersive spectrometer. The bonding of Ti–6Al–4V to Cu was successfully achieved by diffusion bonding method. The maximum shear strength was found to be 2171 N for the specimen bonded at 890 °C for 60 min. The maximum hardness values were obtained from the area next to the interface in titanium side of the joint. The hardness values were found to decrease with increasing distance from the interface in titanium side while it remained constant in copper side. It was seen that the diffusion transition zone near the interface consists of various phases of βCu₄Ti, Cu₂Ti, Cu₃Ti₂, Cu₄Ti₃ and CuTi.     

Nanostructured β-phase Ti–31.0Fe–9.0Sn and sub-μm structured Ti–39.3Nb–13.3Zr–10.7Ta alloys for biomedical applications: Microstructure benefits on the mechanical and corrosion performances

Nanostructured Ti–31.0Fe–9.0Sn and sub-micrometer structured Ti–39.3Nb–13.3Zr–10.7Ta (wt.%) β-type alloys, exhibiting different microstructures and dissimilar mechanical properties, have been prepared by copper mold casting. The microstructure, mechanical behavior and corrosion resistance, in simulated body fluid, of both alloys have been investigated and compared to those of commercial Ti–6Al–4V. Nanoindentation experiments reveal that the Ti–31.0Fe–9.0Sn rods exhibit very large hardness (H ≈ 9 GPa) and high Young's modulus. Conversely, the Ti–39.3Nb–13.3Zr–10.7Ta alloy is mechanically softer but it is interesting for biomedical application because of its rather low Young's modulus (E ≈ 71 GPa). Concerning the corrosion performance, Ti–35Nb–7Zr–5Ta shows a corrosion behavior comparable to Ti–Al6–V4, with no potential breakdown up to 0.4 V vs. Ag|AgCl. On the contrary, the Ti–31.0Fe–9.0Sn alloy exhibits a more anodic corrosion potential, but the value is still less negative than for pure elemental Fe and Ti. From all these properties and because of the absence of toxic elements in the compositions, the Ti–39.3Nb–13.3Zr–10.7Ta and Ti–31.0Fe–9.0Sn alloys are attractive for use as metallic biomaterials.     

Corrosion behavior of biomedical Ti–24Nb–4Zr–8Sn alloy in different simulated body solutions

Corrosion behavior of a multifunctional biomedical titanium alloy Ti–24Nb–4Zr–8Sn (wt.%) in 0.9% NaCl, Hank's solution and artificial saliva at 37 °C was investigated using open circuit potential, impedance spectroscopy and potentiodynamic polarization techniques, and some results were compared with pure titanium and Ti–6Al–4V alloy. The results showed that the alloy exhibited good corrosion resistance due to the formation of a protective passive film consisting mainly of TiO₂ and Nb₂O₅, and a little of ZrO₂ and SnO₂. Ca ions were detected in the passive film as the alloy immersed in Hank′s and artificial saliva solutions and they have negative effect on corrosion resistance. The EIS results indicated that either a duplex film with an inner barrier layer and an outer porous layer or a single passive layer was formed on the surface, and they all transformed into stable bilayer structure as the immersion time increased up to 24 h. The polarization curves demonstrated that the alloy had a wider passive region than pure titanium and Ti–6Al–4V alloy and its corrosion current density (less than 0.1 μA/cm²) is comparable to that of pure titanium.     

Phase transformation in Ti–48Al–6Nb porous alloys and its influence on pore properties

Ti–48Al–6Nb porous alloys were synthesized by the powder metallurgy (PM) method, and the associated phase transformation and pore parameter were investigated in order to reveal the pore-formation mechanism. The present results indicate that the Nb–Al and Ti–Al phase transformations contribute to the pore-formation. It was found that the five-step phase transformations for the Ti–48Al–6Nb porous alloys occur as follows: (1) Ti + Al → TiAl₃ at 600–700 °C; (2) Nb + Al → NbAl₃ at 700–900 °C; (3) TiAl₃ + Ti → TiAl at 900–1100 °C; (4) TiAl + Ti → Ti₃Al/TiAl at 1100–1350 °C; (5) NbAl₃ + Nb → Nb₂Al and the Ti₃Al turns to the major phase at 1350 °C. These phase transformations made the pore-diameter increasing continuously from 1.71 μm to 12.10 μm and also made the pore volume distributing widely. At the second step of 700–900 °C, the Nb–Al phase transformation leads to 5% more volume expansion compared to the Ti–Al based porous alloys. Meanwhile, the porosity and total pore area initially increase and then decrease at this step, but they increase intensely at the final step, which is needed as a catalytic carrier.     

Microstructures and wear properties of YPSZ/CeO2 reinforced composites deposited by laser cladding

In this study, the influence of YPSZ/CeO₂ on the surface performance of the laser-cladded composites was firstly researched. Laser cladding of the Fe₃Al/Co42B + YPSZ/CeO₂ pre-placed powders on Ti–6Al–4V alloy can form the composite coating, which increased the wear resistance of the substrate. With addition of 20 wt.%TiC, the longevity of the molten pool decreased, leading to the decreasing of the growth time of the precipitates and the content of CoTi, TiNi, AlNi, Ti₃Al and TiB phases. The addition of 20 wt.%TiC did not improve the tribological properties of the Fe₃Al/Co42B + YPSZ/CeO₂ laser-cladded composite coating.     

Interfacial structure and fracture behavior of 6061 Al and MAO-6061 Al direct active soldered with Sn–Ag–Ti active solder

Micro-arc oxidation (MAO), a novel coating method capable of depositing compact, ultra-hard ceramic composite coatings on Al and its alloys, is applied to heat sink surfaces. A micro-porous Al₂O₃ layer was synthesized on 6061 Al-Alloy (MAO–Al) using the MAO technique. The microstructure, shear strength and fracture of Al/Al, MAO–Al/MAO–Al, and Al/MAO–Al joints were determined after direct active soldering in air with the Sn3.5Ag4Ti(Ce) active solder at 250 °C for 30 s. During active soldering, Al dissolves into SAT solder to form a coarse Al–Ag–Sn solid solution around the solder. Also, the active element Ti concentrates to and reacts with the MAO–Al layer to form both Ti-oxidized (e.g., TiO and TiO₂) or rich-Ti(Al,Sn)₃, and subsequently Ag₃Sn nanoparticles are adsorbed at the solder/MAO–Al interfaces. The shear-tested bonding strengths were 15.3 ± 1.38 MPa for Al/Al, 10.45 ± 1.53 MPa for MAO–Al/Al, and 8.25 ± 1.53 MPa for MAO–Al/MAO–Al joints. In the Al/Al specimen, the fracture occurred in Al–Ag–Sn compounds of the active matrix after shear testing. In the MAO–Al/MAO–Al and MAO–Al/Al specimens, the fracture occurred in the MAO–Al/active solder interface.     

Influence of sol–gel derived Al2O3 film on the oxidation behavior of a Ti3Al based alloy

Al₂O₃ thin films were deposited on a Ti₃Al based alloy (Ti–24Al–14Nb–3V–0.5Mo–0.3Si) by sol–gel processing. Isothermal oxidation at temperatures of 900–1000 °C and cyclic oxidation at 800–900 °C were performed to test their effect on the oxidation behavior of the alloy. Results of the oxidation tests show that the oxidation parabolic rate constants of the alloy were reduced due to the applied thin film. This beneficial effect became weaker after longer oxidation time at 1000 °C. TiO₂ and Al₂O₃ were the main phases formed on the alloy. The thin film could promote the growth of Al₂O₃, causing an increase of the Al₂O₃ content in the composite oxides, sequentially decreased the oxidation rate. Nb/Al enriched as a layer in the alloy adjacent to the oxide/alloy interface in both the coated and uncoated alloy. The coated thin film decreased the thickness of the Nb/Al enrichment layer by reducing the scale growth rate.