The Effect of Heat Treatment on the Tribological Properties and Room Temperature Corrosion Behavior of Fe–Cr–Al-Based OPH Alloy

The microstructure, mechanical, tribological, and corrosion properties of Fe–Cr–Al–Y-based oxide-precipitation-hardened (OPH) alloy at room temperature are presented. Two OPH alloys with a composition of 0.72Fe–0.15Cr–0.06Al–0.03Mo–0.01Ta–0.02Y₂O₃ and 0.03Y₂O₃ (wt.%) were prepared by mechanical alloying with different milling times. After consolidation by hot rolling, the alloys presented a very fine microstructure with a grain size of approximately 180 nm. Such a structure is relatively brittle, and its mechanical properties are enhanced by heat treatment. Annealing was performed at three temperatures (1000 °C, 1100 °C, and 1200 °C), with a holding time from 1 to 20 h. Tensile testing, wear testing, and corrosion testing were performed to evaluate the effect of heat treatment on the behavior and microstructural properties. The grain size increased almost 10 times by heat treatment, which influenced the mechanical properties. The ultimate tensile strength increased up to 300% more compared to the initial state. On the other hand, heat treatment has a negative effect on corrosion and wear resistance.     

Additive Manufacturing of Magnetostrictive Fe–Co Alloys

Fe–Co alloys are attracting attention as magnetostrictive materials for energy harvesting and sensor applications. This work investigated the magnetostriction characteristics and crystal structure of additive-manufactured Fe–Co alloys using directed energy deposition. The additive-manufactured Fe–Co parts tended to exhibit better magnetostrictive performance than the hot-rolled Fe–Co alloy. The anisotropy energy ΔK₁ for the Fe–Co bulk, prepared under a power of 300 W (referred to as bulk−300 W), was larger than for the rolled sample. For the bulk−300 W sample in a particular plane, the piezomagnetic constant d was large, irrespective of the direction of the magnetic field. Elongated voids that formed during additive manufacturing changed the magnetostrictive behavior in a direction perpendicular to these voids. Magnetic property measurements showed that the coercivity decreased. Since sensors should be highly responsive, Fe–Co three-dimensional parts produced via additive manufacturing can be applied as force sensors.     

Application of the Sinter-HIP Method to Manufacture Cr–Mo–W–V–Co High-Speed Steel via Powder Metallurgy

1.2C–4Cr–4Mo–10W–3.5V–10Co–Fe high-speed steel (JIS SKH57; ISO HS10-4-3-10) is often manufactured via casting and forging. By applying powder metallurgy, the properties of the abovementioned material can be improved. In this study, the effects of sintering conditions on the formation of precipitates and pores are evaluated. Additionally, strength with and without hydrostatic pressure during sintering is evaluated via static bending and impact tests. Sintering via hot isostatic pressing (HIP) at 1463 K can effectively eliminate pores and prevent the coarsening of precipitates. Toughness and strength improved by 50% by applying HIP.     

Structure and Properties of Heat-Resistant Alloys NiAl–Cr–Co–X (X = La,Mo, Zr,Ta, Re) and Fabrication of Powders for Additive Manufacturing

The NiAl–Cr–Co–X alloys were produced by centrifugal self-propagating high-temperature synthesis (SHS) casting. The effects of dopants X = La, Mo, Zr, Ta, and Re on combustion, as well as the phase composition, structure, and properties of the resulting cast alloys, have been studied. The greatest improvement in overall properties was achieved when the alloys were co-doped with 15% Mo and 1.5% Re. By forming a ductile matrix, molybdenum enhanced strength characteristics up to the values σ_ucs = 1604 ± 80 MPa, σ_ys = 1520 ± 80 MPa, and ε_pd = 0.79%, while annealing at T = 1250 ℃ and t = 180 min improved strength characteristics to the following level: σ_ucs = 1800 ± 80 MPa, σ_ys = 1670 ± 80 MPa, and ε_pd = 1.58%. Rhenium modified the structure of the alloy and further improved its properties. The mechanical properties of the NiAl, ZrNi₅, Ni_0.92Ta_0.08, (Al,Ta)Ni₃, and Al(Re,Ni)₃ phases were determined by nanoindentation. The three-level hierarchical structure of the NiAl–Cr–Co+15%Mo alloy was identified. The optimal plasma treatment regime was identified, and narrow-fraction powders (fraction 8–27 µm) characterized by 95% degree of spheroidization and the content of nanosized fraction <5% were obtained.     

Microstructure,Mechanical Properties and Corrosion Behaviors of Al–Li–Cu–Mg–Ag–Zn Alloys

Combined with microstructure characterization and properties tests, the effects of Zn contents on the mechanical properties, corrosion behaviors, and microstructural evolution of extruded Al–Li–Cu–Mg–Ag alloys were investigated. The results show that the increase in Zn contents can accelerate hardening kinetics and improve the hardness of peak-aged alloys. The Zn-added alloys present non-recrystallization characteristics combined with partially small recrystallized grains along the grain boundaries, while the T1 phase with finer dimension and higher number density could explain the constantly increasing tensile strength. In addition, increasing Zn contents led to a lower corrosion current density and a shallower maximum intergranular corrosion depth, thus improving the corrosion resistance of the alloys. Zn addition, distributed in the central layer of T1 phases, not only facilitates the precipitation of more T1 phases but also reduces the corrosion potential difference between the T1 phase and the matrix. Therefore, adding 0.57 wt.% Zn to the alloy has an excellent combination of tensile strength and corrosion resistance. The properties induced by Zn under the T8 temper (solid solution treatment + water quenching + 5% pre-strain+ isothermal aging), however, are not as apparent as the T6 temper (solid solution treatment + water quenching + isothermal aging).     

Surface Roughness Analysis and Prediction with an Artificial Neural Network Model for Dry Milling of Co–Cr Biomedical Alloys

The aim of this paper is to conduct an experimental study in order to obtain a roughness (Ra) prediction model for dry end-milling (with an AlTiCrSiN PVD-coated tool) of the Co–28Cr–6Mo and Co–20Cr–15W–10Ni biomedical alloys, a model that can contribute to more quickly obtaining the desired surface quality and shortening the manufacturing process time. An experimental plan based on the central composite design method was adopted to determine the influence of the axial depth of cut, feed per tooth and cutting speed process parameters (input variables) on the Ra surface roughness (response variable) which was recorded after machining for both alloys. To develop the prediction models, statistical techniques were used first and three prediction equations were obtained for each alloy, the best results being achieved using response surface methodology. However, for obtaining a higher accuracy of prediction, ANN models were developed with the help of an application made in LabView for roughness (Ra) prediction. The primary results of this research consist of the Co–28Cr–6Mo and Co–20Cr–15W–10Ni prediction models and the developed application. The modeling results show that the ANN model can predict the surface roughness with high accuracy for the considered Co–Cr alloys.     

Effect of Ag on Properties,Microstructure, and Thermostability of Cu–Cr Alloy

Cu–Cr-based alloys exhibit excellent electrical conductivity and strength, but their poor thermal stability limits their application in industry. In this paper, Cu–0.2Cr (at. %) and Cu–0.2Cr–0.12Ag (at. %) alloys were prepared to study the effect of Ag on the properties, microstructure, and thermal stability of the Cu–Cr alloy. Microstructure and precipitation were observed by an optical microscope (OM) and a transmission–electron microscope (TEM). After cold-drawing by 99.9% and aging at 450 °C for 2 h, the peak hardness and electric conductivity of the Cu–Cr alloy were 120.3 HV and 99.5% IACS, respectively, and those of the Cu–Cr–Ag alloy were 135.8 HV and 98.3% IACS, respectively. The softening temperature of the Cu–Cr alloy was 500~525 °C, and that of the Cu–Cr–Ag alloy was about 550 °C. The creep strains of the Cu–Cr and Cu–Cr–Ag alloys at 40 MPa and 400 ℃ for 50 h were 0.18% and 0.05%, respectively. Ag elements improved the thermal stability of the Cu–Cr alloy. Recovery and recrystallization occurred before the coarsening of precipitates during the softening process. Ag atoms mainly improved the softening resistance of the alloy by delaying recrystallization, and mainly increased creep resistance by preventing the increase in mobile-dislocation density.     

Investigations of Effects of Intermetallic Compound on the Mechanical Properties and Shape Memory Effect of Ti–Au–Ta Biomaterials

Owing to the world population aging, biomedical materials, such as shape memory alloys (SMAs) have attracted much attention. The biocompatible Ti–Au–Ta SMAs, which also possess high X–ray contrast for the applications like guidewire utilized in surgery, were studied in this work. The alloys were successfully prepared by physical metallurgy techniques and the phase constituents, microstructures, chemical compositions, shape memory effect (SME), and superelasticity (SE) of the Ti–Au–Ta SMAs were also examined. The functionalities, such as SME, were revealed by the introduction of the third element Ta; in addition, obvious improvements of the alloy performances of the ternary Ti–Au–Ta alloys were confirmed while compared with that of the binary Ti–Au alloy. The Ti₃Au intermetallic compound was both found crystallographically and metallographically in the Ti–4 at.% Au–30 at.% Ta alloy. The strength of the alloy was promoted by the precipitates of the Ti₃Au intermetallic compound. The effects of the Ti₃Au precipitates on the mechanical properties, SME, and SE were also investigated in this work. Slight shape recovery was found in the Ti–4 at.% Au–20 at.% Ta alloy during unloading of an externally applied stress.     

Biological Safety Evaluation and Surface Modification of Biocompatible Ti–15Zr–4Nb Alloy

We performed biological safety evaluation tests of three Ti–Zr alloys under accelerated extraction condition. We also conducted histopathological analysis of long-term implantation of pure V, Al, Ni, Zr, Nb, and Ta metals as well as Ni–Ti and high-V-containing Ti–15V–3Al–3Sn alloys in rats. The effect of the dental implant (screw) shape on morphometrical parameters was investigated using rabbits. Moreover, we examined the maximum pullout properties of grit-blasted Ti–Zr alloys after their implantation in rabbits. The biological safety evaluation tests of three Ti–Zr alloys (Ti–15Zr–4Nb, Ti–15Zr–4Nb–1Ta, and Ti–15Zr–4Nb–4Ta) showed no adverse (negative) effects of either normal or accelerated extraction. No bone was formed around the pure V and Ni implants. The Al, Zr, Nb, and Ni–Ti implants were surrounded by new bone. The new bone formed around Ti–Ni and high-V-containing Ti alloys tended to be thinner than that formed around Ti–Zr and Ti–6Al–4V alloys. The rate of bone formation on the threaded portion in the Ti–15Zr–4Nb–4Ta dental implant was the same as that on a smooth surface. The maximum pullout loads of the grit- and shot-blasted Ti–Zr alloys increased linearly with implantation period in rabbits. The pullout load of grit-blasted Ti–Zr alloy rods was higher than that of shot-blasted ones. The surface roughness (Ra) and area ratio of residual Al₂O₃ particles of the Ti–15Zr–4Nb alloy surface grit-blasted with Al₂O₃ particles were the same as those of the grit-blasted Alloclassic stem surface. It was clarified that the grit-blasted Ti–15Zr–4Nb alloy could be used for artificial hip joint stems.     

In Situ Observation of the Tensile Deformation and Fracture Behavior of Ti–5Al–5Mo–5V–1Cr–1Fe Alloy with Different Microstructures

The plastic deformation processes and fracture behavior of a Ti–5Al–5Mo–5V–1Cr–1Fe alloy with bimodal and lamellar microstructures were studied by room-temperature tensile tests with in situ scanning electron microscopy (SEM) observations. The results indicate that a bimodal microstructure has a lower strength but higher ductility than a lamellar microstructure. For the bimodal microstructure, parallel, deep slip bands (SBs) are first noticed in the primary α (α_p) phase lying at an angle of about 45° to the direction of the applied tension, while they are first observed in the coarse lath α (α_L) phase or its interface at grain boundaries (GBs) for the lamellar microstructure. The β matrix undergoes larger plastic deformation than the α_L phase in the bimodal microstructure before fracture. Microcracks are prone to nucleate at the α_p/β interface and interconnect, finally causing the fracture of the bimodal microstructure. The plastic deformation is mainly restricted to within the coarse α_L phase at GBs, which promotes the formation of microcracks and the intergranular fracture of the lamellar microstructure.     

Deformation Behavior,a Flow Stress Model Considering the Contribution of Strain and Processing Maps in the Isothermal Compression of a Near-α Ti–3.3Al–1.5Zr–1.2Mo–0.6Ni Titanium Alloy

In the present study, isothermal compression tests are conducted for a near-α Ti–3.3Al–1.5Zr–1.2Mo–0.6Ni titanium alloy at deformation temperatures ranging from 1073 K to 1293 K and strain rates ranging from 0.01 s⁻¹ to 10 s⁻¹ on a Gleeble-3500 thermomechanical compressor. The results show that, in the initial stage of the compression, the flow stress rapidly increases to a peak value because of elastic deformation, and then the alloy enters the plastic deformation stage and the flow stress slowly decreases with the increase in strain and tends to gradually stabilize. In the plastic deformation stage, the flow stress significantly decreases with the increase in the deformation temperature and the decrease in strain rate. A flow stress model considering the contribution of the strain is established, and the relative error between the calculated and the experimental values is 3.72%. The flow stress model has higher precision and can efficiently predict the flow behavior in the isothermal compression of the alloy. Furthermore, the processing map of the Ti–3.3Al–1.5Zr–1.2Mo–0.6Ni alloy is drawn. Based on the processing map, the influence of process parameters on power dissipation efficiency and stability parameters is analyzed, and the optimized hot working process parameters are pointed out.     

Influence of Dissolving Fe–Nb–B–Dy Alloys in Zirconium on Phase Structure,Microstructure and Magnetic Properties

This paper refers to the structural and magnetic properties of [(Fe₈₀Nb₆B₁₄)_0.88Dy_0.12]_1−xZr_x (x = 0; 0.01; 0.02; 0.05; 0.1; 0.2; 0.3; 0.5) alloys obtained by the vacuum mold suction casting method. The analysis of the phase contribution indicated a change in the compositions of the alloys. For x < 0.05, occurrence of the dominant Dy₂Fe₁₄B phase was observed, while a further increase in the Zr content led to the increasing contribution of the Fe–Zr compounds and, simultaneously, separation of crystalline Dy. The dilution of (Fe₈₀Nb₆B₁₄)_0.88Dy_0.12 in Zr strongly influenced the magnetization processes of the examined alloys. Generally, with the increasing x parameter, we observed a decrease in coercivity; however, the unexpected increase in magnetic saturation and remanence for x = 0.2 and x = 0.3 was shown and discussed.     

Magnetic-Property Assessment on Dy–Nd–Fe–B Permanent Magnet by Thermodynamic Calculation and Micromagnetic Simulation

Heavy rare-earth (HRE) elements are important for the preparation of high-coercivity permanent magnets. A further understanding of the thermodynamic properties of HRE phases, and the magnetization reversal mechanism of magnets are still critical issues to obtain magnets that can achieve better performance. In this work, the Nd–Dy–Fe–B multicomponent system is investigated via the calculation of the phase diagram (CALPHAD) method and micromagnetic simulation. The phase composition of magnets with various ratios of Nd and Dy is assessed using critically optimized thermodynamic data. γ-Fe and Nd₂Fe₁₇ phases are suppressed when partial Nd is substituted with Dy (<9.3%), which, in turn, renders the formation of Nd₂Fe₁₄B phase favorable. The influence of the magnetic properties of grain boundaries (GBs) on magnetization reversal is detected by the micromagnetic simulations with the 3D polyhedral grains model. Coercivity was enhanced with both 3 nm nonmagnetic and the hard-magnetic GBs for the pinning effect besides the GBs. Moreover, the nucleation and propagation of reversed domains in core-shell grains are investigated, which suggests that the magnetic structure of grains can also influence the magnetization reversal of magnets. This study provides a theoretical route for a high-efficiency application of the Dy element, realizing a deterministic enhancement of the coercivity in Nd–Fe–B-based magnets.     

Some Aspects of Oxidation and Reduction Processes in Ti–Al and Ti–Al–Nb Systems

The oxidation of titanium and titanium aluminides has attracted the attention of scientists for many years because of their high-temperature application. The most popular method to investigate oxidation behavior is the measurement of alloy mass changes during exposure to elevated-temperature under isothermal or thermal cycling conditions. However, the thermogravimetric method is not enough to establish an oxidation mechanism. In this paper, the temperature-programmed oxidation (TPOx) and reduction (TPR) were applied for the Ti–Al and Ti–Al–Nb systems, which was a new experimental concept which revealed interesting phenomena. Although oxidation of titanium alloys is well-described in the literature, not many papers present at the same time reduction of oxidized alloys. The results presented in the paper concentrated on the first stages of oxidation, which are scarcely described in the literature, but are important to understand the oxidation mechanism. Comparison between powder and bulk samples with similar compositions revealed essential differences in the oxidation mechanism.     

Thermomechanical Processing of a Near-α Ti Matrix Composite Reinforced by TiBw

To further improve the mechanical properties of the as-cast 7.5 vol.% TiB_w/Ti–6Al–2.5Sn–4Zr–0.7Mo–0.3Si composite, multi-directional forging (MDF) and subsequent heat treatments were carried out to adjust TiB whiskers (TiB_w) and matrix characteristics. The effect of various microstructures on the tensile properties and fracture toughness of the composites was analyzed in this paper. After MDF, the TiB_w are broken into short rods with a low aspect ratio and display a random distribution. Moreover, distinct microstructures were obtained after thermomechanical processing and different heat treatments. Both room-temperature and high-temperature tensile strength and ductility are improved after thermomechanical processing. By increasing the solution-treatment temperature, the microstructures transform from equiaxed to fully lamellar. A simultaneous improvement of the room-temperature and high-temperature properties is associated with the microstructural changes. In addition, the fracture toughness exhibits an increasing trend as the volume fraction of equiaxial α phases decreases. The lamellar microstructure demonstrates excellent fracture toughness due to deflection of the crack propagation path.     

Bulk TiB2-Based Ceramic Composites with Improved Mechanical Property Using Fe–Ni–Ti–Al as a Sintering Aid

The densification behavior, microstructure and mechanical properties of bulk TiB₂-based ceramic composites, fabricated using the spark plasma sintering (SPS) technique with elements of (Fe–Ni–Ti–Al) sinter-aid were investigated. Comparing the change of shrinkage displacement of pure TiB₂ and TiB₂–5 wt% (Fe–Ni–Ti–Al), the addition of elements Fe–Ni–Ti–Al into TiB₂ can facilitate sintering of the TiB₂ ceramics. As the sintering temperature exceeds 1300 °C, the relative density does not significantly change. Alumina particles and austenite (Fe–Ni–Ti) metallic binder distributed homogeneously in the grain boundary of TiB₂ can inhibit the growth of the TiB₂ grains when the sintering temperature is below 1300 °C. The density and particle size of TiB₂ greatly influence the mechanical behavior of TiB₂–5 wt% (Fe–Ni–Ti–Al) composites. The specimen sintered at 1300 has the highest microhardness of 21.1 ± 0.1 GPa with an elastic modulus of 461.4 GPa. The content of secondary borides (M₂B, being M = Fe, Ni), which are more brittle than TiB₂ particles, can also influence the fracture toughness. The specimen sintered at 1500 °C has the highest fracture toughness of 6.16 ± 0.30 MPa·m^1/2 with the smallest M₂B phase. The results obtained provide insight into fabrication of ceramic composites with improved mechanical property.     

Formation and Thermal Stability of the ω-Phase in Ti–Nb and Ti–Mo Alloys Subjected to HPT

This paper discusses the features of ω-phase formation and its thermal stability depending on the phase composition, alloying element and the grain size of the initial microstructure of Ti–Nb and Ti–Mo alloys subjected to high-pressure torsion (HPT) deformation. In the case of two-phase Ti–3wt.% Nb and Ti–20wt.% Nb alloys with different volume fractions of α- and β-phases, a complete β→ω phase transformation and partial α→ω transformation were found. The dependence of the α→ω transformation on the concentration of the alloying element was determined: the greater content of Nb in the α-phase, the lower the amount of ω-phase that was formed from it. In the case of single-phase Ti–Mo alloys, it was found that the amount of ω-phase formed from the coarse-grained β-phase of the Ti–18wt.% Mo alloy was less than the amount of the ω-phase formed from the fine α′-martensite of the Ti–2wt.% Mo alloy. This was despite the fact that the ω-phase is easier to form from the β-phase than from the α- or α′-phase. It is possible that the grain size of the microstructure also affected the phase transformation, namely, the fine martensitic plates more easily gain deformation and overcome the critical shear stresses necessary for the phase transformation. It was also found that the thermal stability of the ω-phase in the Ti–Nb and Ti–Mo alloys increased with the increasing concentration of Nb or Mo.     

Dissimilar Brazing of Ti–15Mo–5Zr–3Al and Commercially Pure Titanium Using Ti–Cu–Ni Foil

Dissimilar brazing of Ti–15Mo–5Zr–3Al (Ti-1553) to commercially pure titanium (CP-Ti) using Ti–15Cu–15Ni foil was performed in this work. The microstructures in different sites of the brazed joint showed distinct morphologies, which resulted from the distributions of Mo, Cu, and Ni. In the brazed zone adhered to the Ti-1553 substrate, the partitioning of Mo from the Ti-1553 into the molten braze caused the formation of stabilized β-Ti without Ti₂Cu/Ti₂Ni precipitates. In the CP-Ti side, the brazed joint displayed a predominantly lamellar structure, composed of the elongated primary α-Ti and β-transformed eutectoid. The decrease in the Mo concentration in the brazed zone caused the eutectoid transformation of β-Ti to Ti₂Cu + α-Ti in that zone. The diffusion of Cu and Ni from the molten braze into the CP-Ti accounted for the precipitation of Ti₂Cu/Ti₂Ni in the transformed zone therein. The variation in the shear strength of the joints was related to the amount and distribution of brittle Ti₂Ni compounds. Prolonging the brazing time, the wider transformed zone, consisting of coarse elongated CP-Ti interspersed with sparse Ti₂Ni precipitates, was responsible for the improved shear strength of the joint.     

Comparisons of Dy Utilization Efficiency by DyHx Grain Boundary Addition and Surface Diffusion Methods in Nd-Y-Fe-B Sintered Magnet

Using the heavy rare earth Dy element to improve coercivity is the most common solution for hindering the reduction in magnetic properties in the Nd–Fe–B magnet, and the effective utilization of Dy has become the focus of research in industrial society. In this work, we investigated the influence of DyH_x addition and diffusion methods on the microstructure, magnetic performance, and thermal stability of the Nd–Y–Fe–B magnet with a Y-rich core structure. The coercivity of the DyH_x addition magnet increases from 9.45 kOe to 15.51 kOe when adding 1.6 wt.% DyH_x, while the DyH_x diffusion magnet increases to 15.15 kOe. According to the analysis of the microstructure and elemental distribution, both Dy-rich shells were basically formed due to the diffusion process of Dy atoms. The Dy-rich shell in the DyH_x addition magnet was similar with the original core–shell structure in the Nd–Y–Fe–B magnet. However, the distinct dual-shell structure consisting of a thinner Dy-rich shell and a Y-lean shell was constructed in the DyH_x diffused magnet, contributing to the superior coercivity increment and Dy utilization efficiency. Furthermore, the remanence of the DyH_x diffused magnet is up to 12.90 kG, which is better than that of the DyH_x addition magnet (12.59 kG), due to fewer Dy atoms entering the 2:14:1 matrix grain to cause the antiferromagnetic coupling with Fe atoms. Additionally, the thermal stability of the DyH_x diffusion magnet is also better than that of the DyH_x addition magnet, owing to the elevated coercivity at room temperature, which expands the application range of the Nd–Y–Fe–B magnet to a certain extent.     

Exfoliation Resistance,Microstructure, and Oxide Formation Mechanisms of the White Oxide Layer on CP Ti and Ti–Nb–Ta–Zr Alloys

We found that specific biomedical Ti and its alloys, such as CP Ti, Ti–29Nb–13Ta–4.6Zr, and Ti–36Nb–2Ta–3Zr–0.3O, form a bright white oxide layer after a particular oxidation heat treatment. In this paper, the interfacial microstructure of the oxide layer on Ti–29Nb–13Ta–4.6Zr and the exfoliation resistance of commercially pure (CP) Ti, Ti–29Nb–13Ta–4.6Zr, and Ti–36Nb–2Ta–3Zr–0.3O were investigated. The alloys investigated were oxidized at 1273 or 1323 K for 0.3–3.6 ks in an air furnace. The exfoliation stress of the oxide layer was high in Ti–29Nb–13Ta–4.6Zr and Ti–36Nb–2Ta–3Zr–0.3O, and the maximum exfoliation stress was as high as 70 MPa, which is almost the same as the stress exhibited by epoxy adhesives, whereas the exfoliation stress of the oxide layer on CP Ti was less than 7 MPa, regardless of duration time. The nanoindentation hardness and frictional coefficients of the oxide layer on Ti–29Nb–13Ta–4.6Zr suggested that the oxide layer was hard and robust enough for artificial tooth coating. The cross-sectional transmission electron microscopic observations of the microstructure of oxidized Ti–29Nb–13Ta–4.6Zr revealed that a continuous oxide layer formed on the surface of the alloys. The Au marker method revealed that both in- and out-diffusion occur during oxidation in Ti–29Nb–13Ta–4.6Zr and Ti–36Nb–2Ta–3Zr–0.3O, whereas only out-diffusion governs oxidation in CP Ti. The obtained results indicate that the high exfoliation resistance of the oxide layer on Ti–29Nb–13Ta–4.6Zr and Ti-36Nb-2Ta-3Zr-0.3O are attributed to their dense microstructures composing of fine particles, and a composition-graded interfacial microstructure. On the basis of the results of our microstructural observations, the oxide formation mechanism of the Ti–Nb–Ta–Zr alloy is discussed.