β-Ti alloys have long been investigated and applied in the biomedical field due to their exceptional mechanical properties, ductility, and corrosion resistance. Metastable β-Ti alloys have garnered interest in the realm of biomaterials owing to their notably low elastic modulus. Nevertheless, the inherent correlation between a low elastic modulus and relatively reduced strength persists, even in the case of metastable β-Ti alloys. Enhancing the strength of alloys contributes to improving their fatigue resistance, thereby preventing an implant material from failure in clinical usage. Recently, a series of biomedical high-entropy and medium-entropy alloys, composed of biocompatible elements such as Ti, Zr, Nb, Ta, and Mo, have been developed. Leveraging the contributions of the four core effects of high-entropy alloys, both biomedical high-entropy and medium-entropy alloys exhibit excellent mechanical strength, corrosion resistance, and biocompatibility, albeit accompanied by an elevated elastic modulus. To satisfy the demands of biomedical implants, researchers have sought to synthesize the strengths of high-entropy alloys and metastable β-Ti alloys, culminating in the development of metastable high-entropy/medium-entropy alloys that manifest both high strength and a low elastic modulus. Consequently, the design principles for new-generation biomedical medium-entropy alloys and conventional metastable β-Ti alloys can be converged. This review focuses on the design from β-Ti alloys to the novel metastable medium-entropy alloys for biomedical applications.

Hydroxyapatite (HA) is a major component of the inorganic minerals in the hard tissues of humans and has been widely used as a biomedical ceramic material in orthopedic and dentistry applications. Because human bone contains several impurities, including carbonates, chlorides, fluorides, magnesium, and strontium, human bone minerals differ from stoichiometric HA. Additionally, natural bone is composed of nano-sized HA, and the nanoscale particles exhibit a high level of biological activity. In this paper, HA is prepared via the hydrothermal process because its reaction conditions are easy to control and it has been shown to be quite feasible for large-scale production. Therefore, the hydrothermal process is an effective and convenient method for the preparation of HA. Furthermore, eggshell is adopted as a source of calcium, and mulberry leaf extract is selectively added to synthesize HA. The eggshell accounts for 11% of the total weight of a whole egg, and it consists of calcium carbonate, calcium phosphate, magnesium carbonate, and organic matter. Eggshell contains a variety of trace elements, such as magnesium and strontium, making the composition of the synthesized HA similar to that of the human skeleton. These trace elements exert considerable benefits for bone growth. Moreover, the use of eggshell as a raw material can permit the recycling of biowaste and a reduction in process costs. The purpose of this study is to prepare HA powder via the hydrothermal method and to explore the effects of hydrothermal conditions on the structure and properties of the synthesized HA. The room-temperature precipitation method is used for the control group. Furthermore, the results of an immersion test in simulated body fluid confirm that the as-prepared HA exhibits good apatite-forming bioactivity, which is an essential requirement for artificial materials to bond to living bones in the living body and promote bone regeneration. In particular, it is confirmed that the HA synthesized with the addition of the mulberry leaf extract exhibits good in vitro biocompatibility. The morphology, crystallite size, and composition of the carbonated nano-HA obtained herein are similar to those of natural bones. The carbonated nano-HA appears to be an excellent material for bioresorbable bone substitutes or drug delivery. Therefore, the nano-HA powder prepared in this study has great potential in biomedical applications.

Commercially pure titanium (c.p. Ti) is often used in biomedical implants, but its surface cannot usually combine with the living bone. A coating of hydroxyapatite (HA) on the surface of titanium implants provides excellent mechanical properties and has good biological activity and biocompatibility. For optimal osteocompatibility, the structure, size, and composition of HA crystals should be closer to those of biological apatite. Our results show that the surface of c.p. Ti was entirely covered by rod-like HA nanoparticles after alkali treatment and subsequent hydrothermal treatment at 150 °C for 48 h. Nano-sized apatite aggregates began to nucleate on HA-coated c.p. Ti surfaces after immersion in simulated body fluid (SBF) for 6 h, while no obvious precipitation was found on the uncoated sample. Higher apatite-forming ability (bioactivity) could be acquired by the samples after HA coating. The HA coating featured bone-like nanostructure, high crystallinity, and carbonate substitution. It can be expected that HA coatings synthesized from eggshells on c.p. Ti through a hydrothermal reaction could be used in dental implant applications in the future.

Nano-hydroxyapatite (nHA) demonstrates favorable biological activity, cell adhesion, cell proliferation, and osteoconductivity, making it highly valuable in biomedicine. It is extensively used as a bone substitute and in bone transplantation within the dental and orthopedic fields. This study employed oyster shells as a calcium source to synthesize nHA at 150 °C with various hydrothermal reaction durations (10 min, 1 h, 6 h, and 12 h). As a control, HA synthesized via a wet precipitation method for 1 h at room temperature was utilized. Subsequent material analyses, including XRD, FE-SEM, FTIR, and ICP-MS, were conducted, followed by comprehensive evaluations of the bioactivity, cell attachment, cell proliferation, and sintering properties of the synthesized nHA. The results indicated that nHA synthesized through the hydrothermal reaction produced nanoscale crystals, with the aspect ratio of nHA particles increasing with the duration of hydrothermal treatment. Notably, rod-like nHA particles became prominent with hydrothermal durations exceeding 6 h. nHA particles derived from oyster shells contained carbonate and trace elements (Na, Mg, K, and Sr), similar to constituents found in human hard tissue such as bone and teeth. The immersion of nHA synthesized at 150 °C for 1 h (HT2) in simulated body fluid (SBF) for 28 d led to the formation of a bone-like apatite layer on the surface, indicating the excellent bioactivity of the synthesized nHA. The cell culture results revealed superior cell attachment and proliferation for nHA (HT2). Following the sequential formation and sintering at 1200 °C for 4 h, HT2 ceramics exhibited enhanced microhardness (5.65 GPa) and fracture toughness (1.23 MPa·m^0.5), surpassing those of human tooth enamel.

In this study, hydroxyapatite/chitosan (HA/CS) composite coatings were prepared by hydrothermal treatment on the surface of low-modulus Ti–25Nb–8Sn alloy to improve the surface bioactivity of the alloy. HA, the main mineral composition of the human skeleton, has excellent bioactivity and is often used as a surface coating on biometal implants. CS, a natural polymer with good antibacterial, hydrophilic and non-toxic characteristics, is often used as dermal regeneration templates, hemostatic agents and drug delivery systems. In this experiment, a natural crab shell was used as a raw material to prepare the HA/CS composite coating by alkali treatment and hydrothermal reaction at various temperatures. The microstructure, morphology and phase composition of the coating surfaces were analyzed by XRD, SEM, and FTIR, and the sample coated with HA/CS was soaked in simulated body fluid (SBF) to evaluate its bioactivity. The experimental results showed that the HA/CS composite coatings through hydrothermal treatment at various temperatures can be successfully fabricated on the surface of the Ti alloy. HA on the coating surface exhibited mainly spherical particles and contained A- and B-type carbonate. When the hydrothermal temperature was up to 200 °C, the spherical particles were approximately 20–40 nm. An ultrasonic vibration test was used to evaluate the adhesion of the coatings, showing that the CS exhibited significantly improved adhesion capacity to the substrate. After being soaked in SBF for 7 days, apatite was deposited on the entire surfaces of the HA/CS coatings, indicating that the coating possesses excellent bioactivity.