Spinodal Zr-Nb alloys with ultrahigh elastic admissible strain and low magnetic susceptibility for orthopedic applications.

Metallic biomaterials, such as stainless steels, cobalt-chromium-molybdenum (Co-Cr-Mo) alloys, and titanium (Ti) alloys, have long been used as load-bearing implant materials due to their metallic mechanical strength, corrosion resistance, and biocompatibility. However, their magnetic susceptibility and elastic modulus of more than 100 GPa significantly restrict their therapeutic applicability. In this study, spinodal Zr60Nb40, Zr50Nb50, and Zr40Nb60 (at.%) alloys were selected from the miscibility gap based on the Zr-Nb binary phase diagram and prepared by casting, cold rolling, and aging. Their microstructure, mechanical properties, corrosion resistance, magnetic susceptibility, and biocompatibility were systematically evaluated. Spinodal decomposition to alternating nanoscale Zr-rich ß1 and Nb-rich ß2 phases occurred in the cold-rolled Zr-Nb alloys during aging treatment at 650 °C. In addition, a minor amount of α phase was precipitated in Zr60Nb40 due to the thermodynamic instability of the Zr-rich ß1 phase. Spinodal decomposition significantly improved the mechanical strength of the alloys due to nanosized dual-cubic reinforcement. The Zr-Nb alloys showed an electrochemical corrosion rate of 94-262 nm per year in Hanks' solution because of formation of dense passive films composed of ZrO2 and Nb2O5 during the polarization process. The magnetic susceptibilities of the Zr-Nb alloys were significantly lower than those of commercial Co-Cr-Mo and Ti alloys. The cell viability of the Zr-Nb alloys was more than 98 % toward MC3T3-E1 cells. Overall, the spinodal Zr-Nb alloys have enormous potential as bone-implant materials due to their outstanding overall mechanical properties, extraordinary corrosion resistance, low magnetic susceptibility, and sufficient bicompatibility. STATEMENT OF SIGNIFICANCE: This work reports on spinodal Zr-Nb alloys with heterostructure. Spinodal decomposition significantly improved their mechanical strength due to the nanosized dual-cubic reinforcement. The Zr-Nb alloys showed large corrosion resistance in Hanks' solution because of formation of dense passivation films composed of ZrO2 and Nb2O5 during the polarization process. The magnetic susceptibilities of the Zr-Nb alloys were significantly lower than those of commercial Co-Cr-Mo and Ti alloys. The cell viability of the Zr-Nb alloys was more than 98 % toward MC3T3-E1 cells. The results demonstrate that spinodal Zr-Nb alloys have enormous potential as bone-implant materials due to their outstanding overall mechanical properties, high corrosion resistance, low magnetic susceptibility, and sufficient biocompatibility.

A biodegradable Zn-5Gd alloy with biomechanical compatibility, cytocompatibility, antibacterial ability, and in vitro and in vivo osteogenesis for orthopedic applications.

Zinc (Zn) and some of its alloys are recognized as promising biodegradable implant materials due to their acceptable biocompatibility, facile processability, and moderate degradation rate. Nevertheless, the limited mechanical properties and stability of as-cast Zn alloys hinder their clinical application. In this work, hot-rolled (HR) and hot-extruded (HE) Zn-5 wt.% gadolinium (Zn-5Gd) samples were prepared by casting and respectively combining with hot rolling and hot extrusion for bone-implant applications. Their microstructure evolution, mechanical properties, corrosion behavior, cytotoxicity, antibacterial ability, and in vitro and in vivo osteogenesis were systematically evaluated. The HR and HE Zn-5Gd exhibited significantly improved mechanical properties compared with those of their pure Zn counterparts and the HR Zn-5Gd showed a unique combination of tensile properties with an ultimate tensile strength of ∼311.6 MPa, yield strength of ∼236.5 MPa, and elongation of ∼40.6%, all of which are greater than the mechanical properties required for bone-implant materials. The HR and HE Zn-5Gd showed higher corrosion resistance than their pure Zn counterpart in Hanks' solution and the HE Zn-5Gd had the lowest corrosion rate of 155 µm/y measured by electrochemical corrosion and degradation rate of 26.9 µm/y measured by immersion testing. The HR and HE Zn-5Gd showed high cytocompatibility toward MC3T3-E1 and MG-63 cells, high antibacterial effects against S. aureus, and better in vitro osteogenic activity than their pure Zn counterparts. Furthermore, the HE Zn-5Gd exhibited better in vivo biocompatibility, osteogenesis, and osteointegration ability than pure Zn and pure Ti. STATEMENT OF SIGNIFICANCE: This work reports the mechanical properties, corrosion behaviors, cytocompatibility, antibacterial ability, in vitro and in vivo osteogenesis of biodegradable Zn-Gd alloy for bone-implant applications. Our findings demonstrate that the hot-rolled (HR) Zn-5Gd showed a unique combination of tensile properties with an ultimate tensile strength of ∼311.6 MPa, yield strength of ∼236.5 MPa, and elongation of ∼40.6%. The HR and HE Zn-5Gd showed higher corrosion resistance than their pure Zn counterpart in Hanks' solution. The HR and HE Zn-5Gd showed high cytocompatibility toward MC3T3-E1 and MG-63 cells, good antibacterial effects against S. aureus, and better in vitro osteogenic activity. Furthermore, the HE Zn-5Gd exhibited better in vivo biocompatibility, osteogenesis, and osteointegration ability than pure Zn and pure Ti.

Mechanical properties, corrosion behavior, and cytotoxicity of biodegradable Zn/Mg multilayered composites prepared by accumulative roll bonding process.

Zinc (Zn), magnesium (Mg), and their respective alloys have attracted great attention as biodegradable bone-implant materials due to their excellent biocompatibility and biodegradability. However, the poor mechanical strength of Zn alloys and the rapid degradation rate of Mg alloys limit their clinical application. The manufacture of Zn and Mg bimetals may be a promising way to improve their mechanical and degradation properties. Here we report on Zn/Mg multilayered composites prepared via an accumulative roll bonding (ARB) process. With an increase in the number of ARB cycles, the thicknesses of the Zn layer and the Mg layer were reduced, while a large number of heterogeneous interfaces were introduced into the Zn/Mg multilayered composites. The composite samples after 14 ARB cycles showed the highest yield strength of 411±3 MPa and highest ultimate tensile strength of 501±3 MPa among all the ARB processed samples, significantly higher than those of the Zn/Zn and Mg/Mg multilayered samples. The Zn and Mg layers remained continuous in the Zn/Mg composite samples after annealing at 150 °C for 10 min, resulting in a decrease in yield strength from 411±3 MPa to 349±3 MPa but an increase in elongation from 8±1% to 28±1%. The degradation rate of the Zn/Mg multilayered composite samples in Hanks' solution was ranged from 127±18 µm/y to 6±1 µm/y. The Zn/Mg multilayered composites showed over 100% cell viability with their 25% and 12.5% extracts in relation to MG-63 cells after culturing for 3 d, indicating excellent cytocompatibility. STATEMENT OF SIGNIFICANCE: This work reports a biodegradable Zn/Mg multilayered composite prepared by accumulative roll bonding (ARB) process. The yield and ultimate tensile strength of the Zn/Mg multilayered composites were improved due to grain refinement and the introduction of a large number of heterogeneous interfaces. The composite samples after 14 ARB cycles showed the highest yield strength of 411±3 MPa and highest ultimate tensile strength of 501±3 MPa among all the ARB processed samples. The degradation rate of the Zn/Mg multilayered composite meets the required degradation rate for biodegradable bone-implant materials. The results demonstrated that it is a very promising approach to improve the strength and biocompatibility of biodegradable Zn-based alloys.

Phase Field Study on the Spinodal Decomposition of ß Phase in Zr-Nb-Ti Alloys.

In this study, a phase field method based on the Cahn-Hilliard equation was used to simulate the spinodal decomposition in Zr-Nb-Ti alloys, and the effects of Ti concentration and aging temperature (800-925 K) on the spinodal structure of the alloys for 1000 min were investigated. It was found that the spinodal decomposition occurred in the Zr-40Nb-20Ti, Zr-40Nb-25Ti and Zr-33Nb-29Ti alloys aged at 900 K with the formation of the Ti-rich phases and Ti-poor phases. The spinodal phases in the Zr-40Nb-20Ti, Zr-40Nb-25Ti and Zr-33Nb-29Ti alloys aged at 900 K were in an interconnected non-oriented maze-like shape, a discrete droplet-like shape and a clustering sheet-like shape in the early aging period, respectively. With the increase in Ti concentration of the Zr-Nb-Ti alloys, the wavelength of the concentration modulation increased but amplitude decreased. The aging temperature had an important influence on the spinodal decomposition of the Zr-Nb-Ti alloy system. For the Zr-40Nb-25Ti alloy, with the increase in the aging temperature, the shape of the rich Zr phase changed from an interconnected non-oriented maze-like shape to a discrete droplet-like shape, and the wavelength of the concentration modulate increased quickly to a stable value, but the amplitude decreased in the alloy. As the aging temperature increased to 925 K, the spinodal decomposition did not occur in the Zr-40Nb-25Ti alloy.

Effect of Rolling Treatment on Microstructure, Mechanical Properties, and Corrosion Properties of WE43 Alloy.

Magnesium alloys show broad application prospects as biodegradable implanting materials due to their good biocompatibility, mechanical compatibility, and degradability. However, the influence mechanism of microstructure evolution during forming on the mechanical properties and corrosion resistance of the magnesium alloy process is not clear. Here, the effects of rolling deformation, such as cold rolling, warm rolling, and hot rolling, on the microstructure, mechanical properties, and corrosion resistance of the WE43 magnesium alloy were systematically studied. After rolling treatment, the grains of the alloy were significantly refined. Moreover, the crystal plane texture strength and basal plane density decreased first and then increased with the increase in rolling temperature. Compared with the as-cast alloy, the strength of the alloy after rolling was significantly improved. Among them, the warm-rolled alloy exhibited the best mechanical properties, with a tensile strength of 346.7 MPa and an elongation of 8.9%. The electrochemical experiments and immersion test showed that the hot working process can greatly improve the corrosion resistance of the WE43 alloy. The hot-rolled alloy had the best corrosion resistance, and its corrosion resistance rate was 0.1556 ± 0.18 mm/year.

In vitro and in vivo assessment of the effect of biodegradable magnesium alloys on osteogenesis.

Magnesium (Mg) and some of its alloys are considered promising biodegradable metallic biomaterials for bone implant applications. The osteogenesis effect of Mg alloys is widely reported; however, the underlying mechanisms are still not clear. In this study, pure Mg, Mg-3Zn, and Mg-2Zn-1Mn were prepared, and their degradation behavior, biocompatibility, and osteogenesis effect were systematically assessed both in vitro and in vivo. Primary rat bone marrow-derived mesenchymal stem cells (BMSCs) were used to evaluate the biocompatibility of the prepared Mg alloys, and a rat femur fracture model was used to assess the stimulating effect of these alloys on bone-tissue formation. Mg-2Zn-1Mn showed higher corrosion resistance and more stable degradation behavior than pure Mg and Mg-3Zn. Extracts of the three materials showed significant stimulating effects on osteogenic differentiation of BMSCs along with non-cytotoxicity. Implantation of Mg-2Zn-1Mn wires into the femur of rats demonstrated superior histocompatibility, stable degradation, and notable promotion of osteogenesis without systemic toxicity. Moreover, the results of both in vitro and in vivo assessments demonstrated that bone morphogenetic proteins and fibroblast growth factor receptors are involved in the stimulating effect of Mg alloys. STATEMENT OF SIGNIFICANCE: This work reports the degradation behavior, biocompatibility, and osteogenic effect of pure Mg and Mg-3Zn and Mg-2Zn-1Mn alloys in both in vitro and in vivo conditions. Mg-2Zn-1Mn showed higher corrosion resistance and more stable degradation behavior than pure Mg and Mg-3Zn. The extracts of the three materials showed a significant stimulating effect on osteogenic differentiation of rat bone marrow-derived mesenchymal stem cells (BMSCs) along with non-cytotoxicity. Mg-2Zn-1Mn wires implanted into the femur of rats showed good histocompatibility, stable degradation, and notable promotion of osteogenesis without systemic toxicity. The results of the present study suggest that bone morphogenetic proteins (BMPs) and fibroblast growth factor receptors (FGFRs) are involved in the stimulating effect of Mg alloys on osteogenesis.

Impact of scandium on mechanical properties, corrosion behavior, friction and wear performance, and cytotoxicity of a ß-type Ti-24Nb-38Zr-2Mo alloy for orthopedic applications.

ß-type titanium (Ti) alloys have been extensively investigated as orthopedic implant materials due to their unique combination of low elastic modulus, high specific strength, corrosion resistance, and biocompatibility. In this study the mechanical properties, corrosion behavior, friction and wear performance, and cytotoxicity of ß-type Ti-24Nb-38Zr-2Mo (TNZM) and Ti-24Nb-38Zr-2Mo-0.1Sc (TNZMS) have been comparatively investigated for orthopedic applications. Cold-rolling (CR) and cold-rolling plus solution-treatment (CR+ST) were performed on the as-cast (AC) alloys and their microstructures and material properties were characterized. The impact of Sc addition on the mechanical and corrosion properties, friction and wear behavior, and in vitro cytocompatibility of the TNZMS alloy was assessed. The CR+ST TNZMS alloy exhibited the best combination of properties among all the alloy samples, with a yield strength of 780 MPa, ultimate strength of 809 MPa, elongation of 19%, Young's modulus of 65.4 GPa, and hardness of 265 HV. Electrochemical testing in Hanks' Solution indicated that the CR+ST TNZMS sample also showed the highest corrosion resistance with a corrosion potential of -0.234 V, corrosion current density of 0.07 µA/cm2, and corrosion rate of 1.2 µm/y. Friction and wear testing revealed that the TNZMS alloy showed higher wear resistance compared to the TNZM alloy and the wear resistance of the different samples was ranked CR > CR+ST > AC. Finally, both the CR+ST TNZM and TNZMS showed no-cytotoxicity towards MG-63 cells and the TNZMS exhibited slightly higher cytocompatibility than the TNZM alloy. STATEMENT OF SIGNIFICANCE: This work reports the ß-type Ti-24Nb-38Zr-2Mo (TNZM) and Ti-24Nb-38Zr-2Mo-0.1Sc (TNZMS) alloys fabricated by as-cast (AC), cold-rolling (CR), and cold-rolling plus solution-treatment (CR+ST) for potential orthopedic applications. The experimental results showed that the TNZMS alloy exhibited significantly enhanced mechanical, wear, and corrosion properties than those of TNZM alloy; and the CR+ST TNZMS possess a unique combination of the best mechanical and corrosion properties including a yield strength of 780 MPa, ultimate strength of 809 MPa, elongation of 19%, Young's modulus of 65.4 GPa, and corrosion rate of 1.2 µm/y in Hanks' Solution. Both the CR+ST TNZM and TNZMS alloys exhibited non-cytotoxicity towards MG-63 cells and TNZMS showed a higher cytocompatibility than that of TNZM.

Biodegradable Zn-3Mg-0.7Mg2Si composite fabricated by high-pressure solidification for bone implant applications.

Zinc (Zn)-based alloys have been considered potential biodegradable materials for medical applications due to their good biodegradability and biocompatibility. However, the insufficient mechanical properties of pure Zn do not meet the requirements of biodegradable implants. In this study, we have developed a biodegradable Zn-3Mg-0.7Mg2Si composite fabricated by high-pressure solidification. Microstructural characterization revealed that the high-pressure solidified (HPS) composite exhibited uniformly distributed fine MgZn2 granules in an α-Zn matrix. Comprehensive tests indicated that the HPS composite exhibited exceptionally high compression properties including a compressive yield strength of 406.2 MPa, an ultimate compressive strength of 1181.2 MPa, and plastic deformation up to 60% strain without cracking or fracturing. Potentiodynamic polarization tests revealed that the HPS composite showed a corrosion potential of -0.930 V, a corrosion current density of 3.5 µA/cm2, and a corrosion rate of 46.2 µm/y. Immersion tests revealed that the degradation rate of the HPS composite after immersion in Hanks' solution for 1 month and 3 months was 42.8 µm/y and 37.8 µm/y, respectively. Furthermore, an extract of the HPS composite exhibited good cytocompatibility compared with as-cast (AC) pure Zn and an AC composite at a concentration of ≤25%. These results suggest that the HPS Zn-3Mg-0.7Mg2Si composite can be anticipated as a promising biodegradable material for orthopedic applications.

Preparation of TiO2 Nanotube Array on the Pure Titanium Surface by Anodization Method and Its Hydrophilicity.

In this work, a highly ordered TiO2 nanotube array on pure titanium (Ti) was prepared by anodization. The effects of the applied voltage and anodization time on the microstructure of the TiO2 nanotube arrays were investigated, and their hydrophilicity was evaluated by the water contact angle measurement. It was found that a highly ordered array of TiO2 nanotubes can be formed on the surface of pure Ti by anodized under the applied voltage of 20 V and the anodization time in the range of 6-12 h, and the nanotube diameter and length can be regulated by anodization time. The as-prepared TiO2 nanotubes were in an amorphous structure. After annealing at 550°C for 3 h, the amorphous TiO2 can be transformed to the anatase TiO2 through crystallization. The anatase TiO2 array exhibited a greatly improved hydrophilicity, depending on the order degree of the array and the diameter of the nanotubes. The sample anodized at 20 V for 12 h and then annealed at 550°C for 3 h exhibited a superhydrophilicity due to its highly ordered anatase TiO2 nanotube array with a tube diameter of 103.5 nm.

Development of biodegradable Zn-1Mg-0.1RE (RE = Er, Dy, and Ho) alloys for biomedical applications.

Zinc (Zn) and its alloys are receiving great attention as promising biodegradable materials due to their suitable corrosion resistance, good biocompatibility, and highly desirable biofunctionality. Nevertheless, the low mechanical strength of pure Zn impedes its practical clinical application and there have been calls for further research into the Zn alloys and thermomechanical processes to enhance their mechanical properties and biocompatibility. Here, we report on the alloying efficacy of rare earth elements (REEs) including erbium (Er), dysprosium (Dy), and holmium (Ho) on the microstructure, mechanical properties, corrosion and wear behavior, and in vitro biological properties of Zn-1Mg-0.1RE alloys. Microstructural characterization revealed that the addition of 0.1 wt.% REEs had a significant refining effect on the grain size of the α-Zn matrix and the second phases of the alloys. Alloying of the REEs and hot-rolling effectively improved the mechanical properties due to both precipitation strengthening of the second phases of ErZn5, DyZn5, and Ho2Zn17 and grain-refinement strengthening. The highest ultimate tensile strength of 259.4 MPa and yield strength of 234.8 MPa with elongation of 16.8% were achieved in the hot-rolled Zn-1Mg-0.1Ho. Alloying of REEs also improved the wear and corrosion resistance, and slowed down the degradation rate in Hanks' solution. Zn-1Mg-0.1Er showed the highest cytocompatibility of MC3T3-E1 cells cultured directly on the alloy surface and of MG-63 cells cultured in the alloy extract. Zn-1Mg-0.1Dy showed the best anticoagulant property among all the alloys. Overall, these Zn-1Mg-0.1RE (Er, Dy, and Ho) alloys can be considered promising biodegradable metallic materials for orthopedic applications.

Biodegradable ternary Zn-3Ge-0.5X (X=Cu, Mg, and Fe) alloys for orthopedic applications.

Biodegradable zinc (Zn) and its alloys have great potential to be used for orthopedic applications due to their suitable degradation rate and good biocompatibility. However, pure Zn has insufficient mechanical properties, such as low strength and hardness, and poor plasticity, which limits its clinical applications. Here, we report on a new series of ternary Zn-3Ge-0.5X (X=Cu, Mg, and Fe) alloys aiming to achieve good corrosion resistance and biocompatibility, and enhanced mechanical properties via micro-alloying with copper (Cu), magnesium (Mg), and iron (Fe). Hot-rolling has also been applied to the new ternary alloys to further enhance their mechanical properties. Mechanical testing results indicate that both the strength and hardness of hot-rolled Zn-3Ge are significantly improved with micro-alloying of Cu, Mg, and Fe; of which the hot-rolled Zn-3Ge-0.5Mg exhibits the highest ultimate tensile strength of 253.4 MPa and yield strength of 208.5 MPa among all the alloys, 25.9% and 44.7% higher than those of the hot-rolled Zn-3Ge. The degradation rate of the as-cast alloys is lower than that of the hot-rolled alloys in Hanks' solution for 1 month and the hot-rolled Zn-3Ge-0.5Mg alloy exhibits the highest degradation rate of 0.075 mm/y. CCK-8 assay using MG-63 cells indicates that the diluted extracts of Zn-3Ge-0.5X (X=Cu, Mg, and Fe) alloys with concentrations of 12.5% and 25% exhibit no or slight cytotoxicity, and the diluted extracts of Zn-3Ge-0.5Cu alloys show high cell viability of over 100%, showing the best cytocompatibility.

Microstructure, mechanical properties, degradation behavior, and biocompatibility of porous Fe-Mn alloys fabricated by sponge impregnation and sintering techniques.

In this study, porous iron (Fe)-manganese (Mn) alloys with high porosity were successfully prepared by sponge impregnation and sintering (SIS). The compositions of the porous Fe-Mn alloys were strongly dependent on the sintering temperature, and the Mn content was ~44, 30, and 12 wt.% for alloys sintered at 1100, 1150, and 1200 °C, respectively. The porous Fe-Mn alloys exhibited a well-interconnected porous structure with ~85% porosity and average pore size ranging from 375 to 500 um. The porous Fe-44Mn and Fe-30Mn alloys were mainly composed of a γ-austenite phase, while the porous Fe-12Mn was composed of an α-ferrite phase. The yield strength and elastic modulus of the porous Fe-Mn alloys ranged from 6 to 10 MPa and from 0.12 to 0.37 GPa, respectively, similar to those of cancellous bone. The degradation rate of the porous Fe-Mn alloys decreased over time during immersion in simulated body fluid (SBF), and was 1.0 mm/year for Fe-44Mn, 0.81 mm/year for Fe-30Mn, 0.41 mm/year for Fe-12Mn, and 0.33 mm/year for pure Fe after 14 d SBF immersion. Moreover, the porous Fe-Mn alloys exhibited good biocompatibility with clearly enhanced cell proliferation after direct culturing of osteoblastic MC3T3-E1 cells for 7 d. Thus, these porous Fe-Mn alloys can be anticipated to be promising biodegradable implant materials. STATEMENT OF SIGNIFICANCE: This work reports on porous Fe-Mn alloys with high porosity, suitable mechanical properties and degradation rate, and good biocompatibility. The porous alloys prepared by sponge impregnation and sintering exhibited a well-interconnected porous structure with ~85% porosity and average pore size ranging from 375 to 500 um. The yield strength and elastic modulus of the porous alloys ranged from 6 to 10 MPa and from 0.12 to 0.37 GPa, respectively, similar to those of cancellous bone. The degradation rates in simulated body fluid (SBF) were ~1.0 mm/year for Fe-44Mn, 0.81 mm/year for Fe-30Mn, and 0.41 mm/year for Fe-12Mn, respectively. Moreover, the porous Fe-Mn alloys exhibited good biocompatibility with enhanced cell proliferation after direct culturing of osteoblastic MC3T3-E1 cells.

Gamma-ray irradiation effects on tantalum thin film for improved mechanical compatibility and cytocompatibility.

In this work, tantalum thin films were prepared on titanium substrates by an ion beam sputtering method. Tantalum thin films were irradiated by gamma-ray with different total dose levels. The effect of irradiation on the phase composition, microstructure, surface morphology, and chemical resistance were analyzed. Besides, in vitro cytocompatibility of tantalum films treated with different radiation doses were evaluated via 3T3-E1 cells. Experimental results showed that higher radiation dose resulted in reductions in crystalline nature, denser morphology, lower elastic modulus, less oxygen vacancies and better corrosion resistance. Additionally, 3T3-E1 cells adhered and spread well on the surface of tantalum film with irradiation exposure to 10 kGy. The dense surface morphology, less density of chemical defects and amorphous phase produced by the gamma-ray irradiation played a major role in the improvement of mechanical compatibility, electrochemical stability property along with the cytocompatibility of the tantalum films.

A biodegradable Zn-1Cu-0.1Ti alloy with antibacterial properties for orthopedic applications.

Zinc (Zn) alloys are receiving increasing attention in the field of biodegradable implant materials due to their unique combination of suitable biodegradability and good biological functionalities. However, the currently existing industrial Zn alloys are not necessarily biocompatible, nor sufficiently mechanically strong and wear-resistant. In this study, a Zn-1Cu-0.1Ti alloy is developed with enhanced mechanical strength, corrosion wear property, biocompatibility, and antibacterial ability for biodegradable implant material applications. HR and HR + CR were performed on the as-cast alloy and its microstructure, mechanical properties, frictional and wear behaviors, corrosion resistance, in vitro cytocompatibility, and antibacterial ability were systematically assessed. The microstructures of the Zn-1Cu-0.1Ti alloy after different deformation conditions included a η-Zn phase, a ε-CuZn5 phase, and an intermetallic phase of TiZn16. The HR+CR sample of Zn-1Cu-0.1Ti exhibited a yield strength of 204.2 MPa, an ultimate tensile strength of 249.9 MPa, and an elongation of 75.2%; significantly higher than those of the HR alloy and the AC alloy. The degradation rate in Hanks' solution was 0.029 mm/y for the AC alloy, 0.032 mm/y for the HR+CR alloy, and 0.034 mm/y for the HR alloy. The HR Zn-1Cu-0.1Ti alloy showed the best wear resistance, followed by the AC alloy and the alloy after HR + CR. The extract of the AC Zn-1Cu-0.1Ti alloy showed over 80% cell viability with MC3T3-E1 pre-osteoblast and MG-63 osteosarcoma cells at a concentration of ≤ 25%. The as-cast Zn-1Cu-0.1Ti alloy showed good blood compatibility and antibacterial ability. STATEMENT OF SIGNIFICANCE: This work repots a Zn-1Cu-0.1Ti alloy with enhanced mechanical strength, corrosion wear property, biocompatibility, and antibacterial ability for biodegradable implant applications. Our findings showed that Zn-1Cu-0.1Ti after hot-rolling plus cold-rolling exhibited a yield strength of 204.2 MPa, an ultimate tensile strength of 249.9 MPa, an elongation of 75.2%, and a degradation rate of 0.032 mm/y in Hanks' Solution. The hot-rolled Zn-1Cu-0.1Ti showed the best wear resistance. The extract of the as-cast alloy at a concentration of ≤ 25% showed over 80% cell viability with MC3T3-E1 and MG-63 cells. The Zn-1Cu-0.1Ti alloy showed good hemocompatibility and antibacterial ability.

Degradation behavior, cytotoxicity, hemolysis, and antibacterial properties of electro-deposited Zn-Cu metal foams as potential biodegradable bone implants.

Zinc (Zn) alloys have attracted much attention for biomedical applications due to their biodegradability, biocompatibility, and biological functionalities. Zn alloy foams have high potential to be used as regenerative medical implants by virtue of their porous structure, which allows new bone tissue ingrowth, their low elastic modulus approximating that of natural bone, and their biodegradation, which eliminates the need for follow-up surgery to remove the implants after bone tissue healing. In this context, a biodegradable Zn-Cu foam was fabricated by electrochemical deposition on a foamed Cu template and given a subsequent diffusion heat treatment. The microstructure, mechanical properties, degradation behavior, toxicity, hemolysis percentages, and antibacterial effects of the Zn-Cu foams were assessed for biomedical applications. The Zn-Cu foams exhibited a yield strength of ~12.1 MPa, a plateau strength of 16.8 MPa, and a strain over 50% under compression tests. The corrosion rate of the Zn-Cu foams measured by electrochemical polarization testing was 0.18 mm/y. The Zn-Cu foams showed good blood compatibility with a hemolysis percentage of less than 5%. Cytotoxicity assessment indicated that a 100% concentration of the Zn-Cu foam extract showed clear cytotoxicity against MC3T3-E1 osteoblast cells, but a 12.5% concentration of the extract showed > 90% cell viability. Moreover, the Zn-Cu foams showed good antibacterial effects. STATEMENT OF SIGNIFICANCE: This work reportsa biodegradable Zn-Cu foam with high mechanical strength and ductility, suitable degradation rate, good antibacterial capacity, and good hemolysis property and biocompatibility. The Zn-Cu foam exhibited a yield strength of ~12.1 MPa, a plateau strength of 16.8 MPa, and a strain over 50% under compression tests. The corrosion rate of the Zn-Cu foam measured by electrochemical polarization testing was 0.18 mm/y in Hanks' Solutions. The Zn-Cu foam showed good blood compatibility with a hemolysis percentage of less than 5%. Cytotoxicity assessment indicated that a 12.5% concentration of the foam extract showed > 90% cell viability. Moreover, the Zn-Cu foam showed good antibacterial effects against S. aureus.

Biocompatibility of Nanoscale Hydroxyapatite Coating on TiO2 Nanotubes.

In this study, a highly-ordered TiO2 nanotube array was successfully fabricated on the surface of a pure titanium foil using the anodization method, and a hydroxyapatite (HA) layer was electrochemically deposited on the vertically aligned titania (TiO2) nanotube array. The TiO2 nanotubes exhibited an inner diameter ranging from 44.5 to 136.8 nm, a wall thickness of 9.8 to 20 nm and a length of 1.25 to 3.94 µm, depending on the applied potential, and the anodization time and temperature. The TiO2 nanotubes provided a high number of nucleation sites for the HA precipitation during electrochemical deposition, resulting in the formation of a nanoscale HA layer with a particle size of about 50 nm. The bond strength between the HA coating and the nanotubular layer with an inner diameter of 136.8 nm was over 28.7 MPa, and the interlocking between the nanoscale HA and the TiO2 nanotubes may have been responsible for the high bond strength. The biocompatibility assessment was conducted on Ti foil with a composite coat of nanoscale HA and the TiO2 nanotube array by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) array with mesenchymal stem cells (MSCs). The mesenchymal stem cells adhered to and spread onto the nanoscale HA layer with plenty of extending filopodia, indicating excellent biocompatibility of the HA coat, the composite coat of nanoscale HA and the TiO2 nanotube array. The findings suggest that the nanoscale HA coating on the TiO2 nanotube array might be a promising way to improve the bond strength and the compatibility of the HA layer.

Influence of Heat Treatments on Microstructure and Mechanical Properties of Ti⁻26Nb Alloy Elaborated In Situ by Laser Additive Manufacturing with Ti and Nb Mixed Powder.

In the present work, a Ti⁻26Nb alloy was elaborated in situ by laser additive manufacturing (LAM) with Ti and Nb mixed powders. The alloys were annealed at temperatures ranging from 650 °C to 925 °C, and the effects of the annealing temperature on the microstructure and mechanical properties were investigated. It has been found that the microstructure of the as-deposited alloy obtained in the present conditions is characterized by columnar prior ß grains with a relatively strong <001> fiber texture in the build direction. The as-deposited alloy exhibits extremely high strength, and its ultimate tensile strength and yield strength are about 799 MPa and 768 MPa, respectively. The annealing temperature has significant effects on the microstructure and mechanical properties of the alloys. Annealing treatment can promote the dissolution of unmelted Nb particles and eliminate the micro-segregation of Nb at the elliptical-shaped grain boundaries, while increasing the grain size of the alloy. With an increase in annealing temperature, the strength of the alloy decreases but the ductility increases. The alloy annealed at 850 °C exhibits a balance of strength and ductility.

Microstructure, mechanical properties, biocompatibility, and in vitro corrosion and degradation behavior of a new Zn-5Ge alloy for biodegradable implant materials.

Zinc (Zn)-based alloys are considered a new class of biodegradable implant materials due to their superior chemical stability and processability compared to biodegradable magnesium (Mg) alloys. In this study, we report a new biodegradable Zn-5Ge alloy with highly desirable mechanical, corrosion, and biological properties. Microstructural characterization revealed the effective grain-refining effect of germanium (Ge) on the Zn alloy. Tensile test results indicated that the hot-rolled Zn-5Ge alloy showed an ultimate tensile strength of 237.0 MPa, a yield strength of 175.1 MPa, and an elongation of 21.6%; while as-cast pure Zn showed an ultimate tensile strength of 33.6 MPa, a yield strength of 29.3 MPa, and an elongation of 1.2%. The corrosion rates measured by potentiodynamic polarization tests in Hank's solution in ascending order are: as-cast Zn-5Ge (0.1272 mm/y) < as-cast pure Zn (0.1567 mm/y) < hot-rolled Zn-5Ge (0.2255 mm/y) < hot-rolled pure Zn (0.3057 mm/y). Immersion tests revealed that the degradation rate of as-cast Zn-5Ge is 0.042 mm/y, less than half of that of hot-rolled pure Zn and ∼62% of that of as-cast pure Zn. Moreover, the Zn-5Ge alloy showed excellent in vitro hemocompatibility and the addition of 5% Ge effectively enhanced the hemocompatibility of pure Zn. CCK-8 assay using murine preosteoblast MC3T3-E1 cells indicated that the diluted extracts at a concentration <12.5% of both the as-cast Zn-5Ge alloy and pure Zn showed grade 0 cytotoxicity; the diluted extracts at the concentrations of 50% and 25% of Zn-5Ge alloy showed a significantly higher cell viability than those of pure Zn. STATEMENT OF SIGNIFICANCE: Zinc (Zn)-based alloys are currently considered a new class of biodegradable implant materials due to their excellent processability. Here, we report a novel Zn-5Ge alloy with highly desirable mechanical, corrosion and biological properties. The tensile test results indicated that the hot-rolled Zn-5Ge alloy showed an ultimate tensile strength of 237.0 MPa, a yield strength of 175.1 MPa and an elongation of 21.6%; while as-cast pure Zn showed an ultimate tensile strength of 33.6 MPa, a yield strength of 29.3 MPa and an elongation of 1.2%. The corrosion rate measured by potentiodynamic polarization tests in Hank's solution in the ascending order is: as-cast Zn-5Ge (0.1272 mm/y) < as-cast pure Zn (0.1567 mm/y) < hot-rolled Zn-5Ge (0.2255 mm/y) < hot-rolled pure Zn (0.3057 mm/y). Immersion tests revealed that the degradation rate of the as-cast Zn-5Ge is 0.042 mm/y, less than half of that of the hot-rolled pure Zn, ∼62% of that of as-cast pure Zn. Moreover, the Zn-5Ge alloy showed excellent in vitro biocompatibility.