Ti-6Al-7Nb alloys have been widely used in the medical field, particularly in artificial hip joints, spinal fixators, and dental implants, owing to their light weight, low toxicity, and superior corrosion resistance. Grain refinement through a severe plastic deformation process under high pressure, such as high-pressure torsion (HPT) or high-pressure sliding, is widely employed for strengthening metallic materials. This overview presents the recent advances in the effect of HPT on the mechanical properties of the Ti-6Al-7Nb alloy. This alloy was grain-refined through HPT under applied pressures of 2 and 6 GPa, and the results revealed that the alloy subjected to HPT processing at 6 GPa exhibited a higher strength. To inhibit the decrease in the total elongation of the alloy, the number of revolutions in the HPT process was set to moderate. The tensile properties achieved after HPT processing were found to be dependent on the initial microstructure before the HPT treatment. Furthermore, an alloy with a bimodal equiaxed and acicular structure was subjected to grain refinement via the HPT process. The results revealed that fragmentation of the acicular structure during HPT further increased the strength. Moreover, the HPT-processed Ti-6Al-7Nb alloy exhibited superplasticity. It was thus confirmed that grain refinement by HPT is an effective method for strengthening the Ti-6Al-7Nb alloy, which is advantageous for medical applications.

Metals that are used to reconstruct skeletal structures often interfere with magnetic resonance imaging (MRI) owing to differences in magnetic susceptibility; consequently, metals with lower magnetic susceptibilities need to be developed for use in implant devices. Herein, we investigated the corrosion properties of the Zr-14Nb-5Ta-1Mo alloy, which exhibits low magnetic susceptibility and excellent mechanical properties. The pitting potential of Zr-14Nb-5Ta-1Mo was higher than that of pure Zr. The passive current density of Zr-14Nb-5Ta-1Mo also higher than that of pure Zr, which is ascribable to slow reconstruction of the initial passive film associated with the presence of Nb and Ta. XPS revealed that the passive film is enriched with Nb and Ta. Therefore, while the Zr-14Nb-5Ta-1Mo alloy exhibited a high initial passive current density in simulated body fluid, it formed a stable passive film that suppressed localized corrosion. Zr-14Nb-5Ta-1Mo is therefore a prospective implant-material alloy candidate.

Ultrafine-grained and heterostructured materials are currently of high interest due to their superior mechanical and functional properties. Severe plastic deformation (SPD) is one of the most effective methods to produce such materials with unique microstructure-property relationships. In this review paper, after summarizing the recent progress in developing various SPD methods for processing bulk, surface and powder of materials, the main structural and microstructural features of SPD-processed materials are explained including lattice defects, grain boundaries and phase transformations. The properties and potential applications of SPD-processed materials are then reviewed in detail including tensile properties, creep, superplasticity, hydrogen embrittlement resistance, electrical conductivity, magnetic properties, optical properties, solar energy harvesting, photocatalysis, electrocatalysis, hydrolysis, hydrogen storage, hydrogen production, CO2 conversion, corrosion resistance and biocompatibility. It is shown that achieving such properties is not currently limited to pure metals and conventional metallic alloys, and a wide range of materials are processed by SPD, including high-entropy alloys, glasses, semiconductors, ceramics and polymers. It is particularly emphasized that SPD has moved from a simple metal processing tool to a powerful means for the discovery and synthesis of new superfunctional metallic and nonmetallic materials. The article ends by declaring that the borders of SPD have been extended from materials science and it has become an interdisciplinary tool to address scientific questions such as the mechanism of geological and astronomical phenomena and the origin of life.

In orthopedics, occasionally, different types of metals are used in applications in which they are in contact with each other. However, few studies have electrochemically investigated the galvanic corrosion of orthopedic implants formed of different metals. In this study, galvanic corrosion of Ti-6Al-4V ELI alloy, Co-Cr-Mo alloy, and 316L type stainless steel, which are used in orthopedics, and a newly developed Zr-1Mo alloy as a low-magnetic susceptibility material was evaluated in saline. Coupling of the Ti-6Al-4V ELI and Co-Cr-Mo alloys did not exhibit localized corrosion and maintained highly stable passive films. Coupling of the 316L type stainless steel and Co-Cr-Mo alloy, temporary localized corrosion occurred. Similarly, coupling of the Zr-1Mo and Co-Cr-Mo alloys, temporary localized corrosion occurred. However, both of 316L type stainless steel and Zr-1Mo alloy were finally repassivated spontaneously with the immersion time. The degree of the localized corrosion of the Zr-1Mo alloy was smaller than that of 316L type stainless steel. No galvanic current was observed when the Ti-6Al-4V ELI and Co-Cr-Mo alloys were coupled. A slight galvanic current flowed when 316L type stainless steel or the Zr-1Mo alloy was coupled with the other alloys; however, the galvanic current with the Zr-1Mo alloy coupling recovered to zero after a certain period owing to repassivation. No metal ions were detected from the couplings with Zr-1Mo

A customized micro-arc oxidation (MAO) treatment technique was developed to obtain antibacterial properties with no toxicity on Ti surfaces. A two-step MAO treatment was used to fabricate a specimen containing both Ag and Zn in its surface oxide layer, and the optimal incorporation conditions were determined. Surface characterization by EDS was performed followed by the antibacterial properties against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) and osteogenic cell compatibility evaluations. In addition, metal ion release tests were performed to evaluate the contents of Ag and Zn and the ion release behavior in order to simulate practical usage. MAO-treated specimens prepared using proper concentrations of Ag and Zn (0.5Ag-5Zn: 0.5 mM AgNO3 and 5.0 mM ZnCl, respectively) exhibited excellent antibacterial properties against E. coli and S. aureus and no toxicity to MC3T3-E1 in antibacterial and cytotoxic evaluations, respectively. The antibacterial property of 0.5Ag-5Zn against S. aureus was sustained even after two months of immersion in physiological saline, simulating the in vivo environment.

Titanium (Ti) is always covered by thin passive films. Thus, valence band (VB) spectra, obtained using X-ray photoelectron spectroscopy (XPS), are superpositions of the VB spectra of passive films and that of the metallic Ti substrate. In this study, to obtain the VB spectra only of passive films, angular resolution (for eliminating the substrate Ti contribution) and argon ion sputtering (for removing passive films) were used along with XPS. The passive film on Ti was determined to consist of a very thin TiO2 layer with small amounts of Ti2O3, TiO, hydroxyl groups, and water with a thickness of 5.9 nm. The VB spectra of Ti were deconvoluted into four peak components: a peak at similar to 1 eV, attributed to the Ti metal substrate; a broad peak in the 3-10 eV range, mainly attributed to O 2p (similar to 6 eV) and O 2p-Ti 3d hybridized states (similar to 8 eV), owing to the pi (non-bonding) and sigma (bonding) orbitals in the passive oxide film; and a peak at similar to 13 eV, attributed to the 3 sigma orbital of O 2p as OH- or H2O. The VB region spectrum between approximately 3 and 14 eV from Ti is originating from the passive film on Ti. In particular, characterization of VB spectrum obtained with a takeoff angle of less than 24 degrees is effective to obtain VB spectrum only from the passive film on Ti. The property as n-type semiconductor of the passive film on Ti is probably higher than that of rutile TiO2 ceramics.

The cytocompatibility and osteoconductivity of the Zr-14Nb-5Ta-1Mo alloy were investigated using a mouse osteoblastic cell line (MC3T3-E1) to promote the application of this newly developed alloy in dental/medical treatment. The initial cell-attached morphology was visualized by fluorescent staining, and cells cultured on the Zr alloy showed similar cell adhesion behavior to cells cultured on titanium (Ti). In our 5-day proliferation investigation, similar cell numbers were obtained with both Zr alloy and Ti. These results indicate that the cytocompatibility of Zr alloy is similar to that of Ti. In addition, the similar results in the evaluation of alkaline phosphatase (ALP) activity and staining of deposited calcium using alizarin red S with both Zr alloy and Ti indicated that the osteoconductivity of the Zr alloy is similar to that of Ti. Our results prove the good cytocompatibility and osteoconductivity of the Zr-14Nb-5Ta-1Mo alloy, enabling its promotion for use in dental/medical applications.

Calcium carbonate (CC)-hydroxyapatite (HAP) porous microparticles have gained a lot of popularity as a promising material for clinical applications. The objective of this study is to evaluate the effects of CC-HAP microparticles on osteoblast-like cells to be used as a bone-regeneration biomaterial. In this study, the different concentrations of conditioned media were used to compare the effects of released ions from CC-HAP microparticles. The material’s characteristics demonstrated that the immersion in cell culture medium did not change the crystal phases of CC-HAP. The decrease of calcium ions in cell culture medium is due to the dissolution-precipitation reactions on the material surfaces, which made more crystalline surfaces. The atomic absorption spectroscopy measurement demonstrated that the dissolution-precipitation reactions on the material surfaces in cell culture medium happened in 3 days and were stable between 3 to 5 days. The conditioned media immersed in cell culture medium for 4 days were used for further experiments. Cell evaluations demonstrated that excessive adding of CC -HAP could inhibit cell behaviors such as cell adhesion, proliferation, and differentiation. The cell adhesion indicated by the number of vinculin-positive focal adhesions per cell decreased with the increase of the CC-HAP concentrations. The cells cultured with CC-HAP proliferated at a lower rate than the control without CC-HAP. One of the reasons for the inhibition of cell proliferation was thought to be less formation of focal adhesions with higher concentrations of CC-HAP. The excessive adding of CC-HAP had an inhibitory effect on osteoblast differentiation. The results of this study revealed that the conditioned media prepared by immersion of CC-HAP porous microparticles in cell culture media had effects on the behaviors of osteoblast-like cells such as cell adhesion, proliferation, and differentiation.

Ti-6Al-7Nb alloy with and without heat treatment was processed by high-pressure torsion (HPT), and subsequently its microstructures and mechanical properties were investigated. Herein, the development of the microstructure by HPT processing significantly depended on the initial microstructures even though their minimum grain size was approximately equal and less than 100 nm. The needle-like structure was fragmented into several grains by HPT processing with a small number of revolutions, and grain refinement was more easily achieved than the equiaxed structure. The Ti-6Al-7Nb alloy with a duplex microstructure comprising equiaxed and needle-like structures was obtained with an adequate balance of tensile strength (1280 MPa) and elongation to fracture (22%). The results show that the combination of the initial duplex microstructure of equiaxed a grain, needle-like structure of the aA phase, and the resultant inhomogeneous microstructure obtained by HPT processing through a moderate number of revolutions is effective in achieving a better balance of mechanical properties in the Ti-6Al-7Nb alloy.

For the elucidation of the mechanism of calcium phosphate formation on commercially pure titanium (CP Ti) in the human body, rutile TiO2 single crystal plates with (001), (110), and (111) facets, namely, TiO2(001), TiO2(110), and TiO2(111), and polycrystalline plates (TiO2(poly)) were immersed in a simulated body fluid, Hanks' solution (Hanks), for 100-105 s, and the adsorption of calcium and phosphate ions was precisely characterized employing X-ray photoelectron spectroscopy (XPS). Previously published CP Ti data were used for comparison. Prior to immersion in Hanks, oxygen content was more than twice as high as that of titanium due to the existence of hydroxyl groups and water on the oxides. After immersion in Hanks, the composition and chemical state of the TiO2 substrates remained unchanged. Among the electrolytes contained in Hanks, only calcium and phosphate ions were adsorbed by and incorporated onto TiO2 surfaces. Adsorption of calcium ions onto rutile did not exhibit any systematic increase of calcium with immersion time except TiO2(poly). Adsorption of phosphate ions was initially constant, followed by an increase with the logarithm of immersion time. The adsorption rate of phosphate ions decreased in the following order: TiO2(001), TiO2(poly), TiO2(111), CP Ti, and TiO2(110). The coordination number and band gap of each crystal facet of rutile is important for the adsorption and incorporation of phosphate ions. Regular calcium phosphate formation on CP Ti is possibly enabled by the surface oxide film, which consists chiefly of amorphous TiO2. However, calcium phosphate formation kinetics on CP Ti differed from those on the TiO2 crystalline phase. These findings may further the understanding of CP Ti hard tissue compatibility.

Recently, biofilm formation caused by bacterial adhesion and colonization has been recognized as the major cause of failure in orthopedic and dental implant surgeries. In this study, a customized micro-arc oxidation (MAO) treatment technique was developed to obtain desirable antibacterial properties on Ti surfaces. The two-step MAO treatment was applied in the fabrication of specimens with Ag and with/without Zn in their surface oxide layer. In order to simulate practical usage, surface analyses and immersion tests were performed to evaluate the incorporation of Ag and Zn into the resulting oxide layer and ion release behavior, respectively. Additionally, the antibacterial properties of the specimens after long-term immersion in physiological saline were evaluated using Gram-negative facultative anaerobic bacteria. The MAO-treated specimens containing Ag and Zn exhibited excellent antibacterial properties against Escherichia coli, which were sustained even after 6 months of immersion in physiological saline to simulate practical usage. Moreover, the Ag ions released from the surface oxide indicate the antibacterial properties of the specimen in the early stage, while the release of the corrosion products of Zn demonstrates its antibacterial properties in the later stage.

An electrochemical surface treatment was developed to visualize the corrosion-inducing inclusions of Zr in chloride environments. Pure Zr and Zr alloy (Zr-0.5O-0.5C) were evaluated in this study. The electrochemical surface treatment consisted of repeated galvanostatic anodic polarization and potentiostatic cathodic polarization. After the electrochemical surface treatment, only one brittle and non-conductive shell of Zr oxide was observed at the corrosion initiation site on the tested surface. The corrosion-inducing inclusions were found inside the corrosion pit under the optimum polarization conditions. At the corrosion initiation site on pure Zr, the area inside the corrosion pit contained larger amounts of O, C, and Si than the surrounding matrix. In the case of the Zr-0.5O-0.5C alloy, relatively larger inclusions were observed after the treatment. Extremely large amounts of Si, together with O and C, were present in the inclusions. The inclusions that induced localized corrosion on the pure Zr and Zr-0.5O-0.5C specimens were found to be precipitated, involving the specific aggregation of Si. The surface treatment developed in this study is expected to be utilized as a powerful tool to elucidate the localized corrosion mechanism of Zr in chloride environments.

Improvement of corrosion resistance of austenitic 316L stainless steel via laser powder bed fusion (LPBF) is currently a prominent research topic; however, the effects of crystallographic texture and the related grain boundary density on the corrosion resistance of LPBF-fabricated parts have not been elucidated. For biomedical applications, crystallographic texture control from a single crystalline-like to randomly oriented polycrystalline microstructure is highly attractive for optimizing the mechanical properties (particularly the Young’s modulus) of implants. An investigation of the impacts of crystallographic planes and grain boundaries exposed to the biological environment on corrosion behavior is necessary. 316L stainless steels with different crystallographic textures and grain boundary densities were successfully fabricated via LPBF. The corrosion resistances of the LPBF-fabricated specimens were comprehensively assessed by anodic polarization, dissolution, and crevice corrosion repassivation tests. The LPBF-fabricated specimens showed extremely high pitting potentials in the physiological saline compared with the commercially available counterparts, and importantly, excellent pitting corrosion resistance was observed irrespective of the crystallographic planes and grain boundary density exposed. Moreover, the LPBF-fabricated specimens did not show metastable pitting corrosion even in an accelerated test using an acid solution. The repassivation behavior of the specimens was not affected by LPBF. Such a drastic improvement in the corrosion resistances of the LPBF-fabricated specimens might be attributed to suppression of inclusion coarsening owing to the rapid cooling rate during solidification in LPBF. By using LPBF, the desired crystallographic texture can be introduced based on the desired mechanical properties without concern for corrosiveness.

An electrochemical surface treatment technique was developed in this study to improve the localized corrosion resistance of zirconium in a chloride ion environment. A combination of anodic and cathodic polarization cycles was applied to induce the selective dissolution of the inclusions that could potentially initiate the localized corrosion of zirconium. Shallow dips were observed on the specimen surface after the treatment, thereby indicating the dissolution of the inclusions. The electrochemical treatments via galvanostatic anodic polarization and potentiostatic cathodic polarization in concentrated phosphate-buffered saline resulted in a high pitting potential of greater than 2V in a simulated body fluid. This indicated that the devised technique realized a significant increase in the localized corrosion resistance of the treated Zr.

To clarify the mechanism of localized corrosion on zirconium in chloride environments, corrosion tests of zirconium and its alloys were performed using conventional and micron-scale measurement systems with surface areas of 0.35 cm(2) and less than 0.04 cm(2), respectively. The pitting potential significantly dropped by more than 1 V when zirconium was alloyed with over 10 mol% of tin. Zr4Sn and Zr5Sn3 intermetallics hindered the formation of passive films on the substrate. Additionally, tin was found on the surface of a commercially pure zirconium. From the micron-scale measurement results, the inclusion with the highest concentration of tin (at least 0.44 mol%) in the tested area was selected as the preferential initiation site for pitting corrosion. Thus, tin played an important role in determining the corrosion resistance of zirconium in chloride environments.

This study investigates the interaction between E. coli bacteria and various surface states of Cu. Pure Cu was oxidized at 298 K, 673 K, and 1273 K, and its surface chemical state was characterized using X-ray photoelectron spectroscopy. The oxidized specimens were immersed in both bacteria-free and bacteria-containing solutions, and the release of Cu ions from each specimen was evaluated. As a result, the specimens, which existed as mainly Cu-0 or Cu+ on the surface, exhibited the same corrosion behavior and promoted the elution of Cu ions due to the presence of E. coli in the immersion solution. In contrast, the release of Cu ions from the specimen that existed mainly as Cu2+ did not change in the presence of bacteria. According to the XPS analyses before and after immersion in bacteria-free and bacteria-containing solutions, the generation of Cu2+ on the surface was inhibited by the presence of E. coli, and promoted Cu ion elution. This study proposes that the specific corrosion behavior of Cu due to bacteria is beneficial for developing its antibacterial properties.

Recently, silver (Ag) and copper (Cu) have been incorporated into a titanium (Ti) surface to realize their antibacterial property. This study investigated both the durability of the antibacterial effect and the surface change of the Ag- and Cu-incorporated porous titanium dioxide (TiO2) layer. Ag- and Cu-incorporated TiO2 layers were formed by micro-arc oxidation (MAO) treatment using the electrolyte with Ag and Cu ions. Ag- and Cu-incorporated specimens were incubated in saline during a period of 0–28 days. The changes in both the concentrations and chemical states of the Ag and Cu were characterized using X-ray photoelectron spectroscopy (XPS). The durability of the antibacterial effects against Escherichia coli (E. coli) were evaluated by the international organization for standardization (ISO) method. As a result, the Ag- and Cu-incorporated porous TiO2 layers were formed on a Ti surface by MAO. The chemical state of Ag changed from Ag2O to metallic Ag, whilst that of Cu did not change by incubation in saline for up to 28 days. Cu existed as a stable Cu2O compound in the TiO2 layer during the 28 days of incubation in saline. The concentrations of Ag and Cu were dramatically decreased by incubation for up to 7 days, and remained a slight amount until 28 days. The antibacterial effect of Ag-incorporated specimens diminished, and that of Cu was maintained even after incubation in saline. Our study suggests the importance of the time-transient effects of Ag and Cu on develop their antibacterial effects.