Debao Liu

Microstructure and Properties of Biodegradable β-TCP Reinforced Mg-Zn-Zr Composites

Magnesium alloys have good biocompatibility, but their mechanical properties and corrosion resistance may not be satisfied for using as degradable materials within bone due to its high corrosion rate in the physiological environment. Nano β-TCP particles were added into Mg-Zn-Zr alloy to improve its microstructure and the properties. As-extruded Mg-3Zn-0.8Zr alloy and Mg-3Zn-0.8Zr/xβ-TCP (x=0.5%, 1.0% and 1.5%) composites were respectively fabricated. The grains of Mg-Zn-Zr/β-TCP composites were significantly refined. The results of the tensile tests indicate that the ultimate tensile strength and the elongation of composites were improved with the addition of β-TCP. The electrochemical test result in simulation body fluid shows that the corrosion resistance of the composites was strongly enhanced comparing with that of the alloy. The corrosion potential of Mg-3Zn0.8-Zr/1.0β-TCP composite is -1.547 V and its corrosion current density is 1.20×10^(-6) A/cm^2 .

In vivo comparative property study of the bioactivity of coated Mg–3Zn–0.8Zr alloy

In this in vivo study, degradable Mg-3Zn-0.8Zr cylinders were coated with a calcium phosphorus compound (Ca-P) layer or a magnesium fluoride (MgF2) layer; uncoated Mg-3Zn-0.8Zr alloy was used as a control. These were then implanted intramedullary into the femora of nine Japanese big-ear white rabbits for implantation periods of 1, 2 and 3 months. During the postoperative observation period with radiographic examination, the results showed that the MgF2-coated implants were tolerated well compared to the Ca-P-coated implants and uncoated implants. Moreover, large amounts of cells, rich fibrillar collagen and calcium and phosphorus products were found on the surface of the MgF2-coated implants using scanning electron microscopy. Micro-computed tomography further showed a slight decrease in volume (23.85%) and a greater increase in new bone mass (new bone volume fraction=11.56%, tissue mineral density=248.81 mg/cm(3)) for the MgF2-coated implants in comparison to uncoated and Ca-P compound-coated implants after 3 months of implantation.

Effects of gas produced by degradation of Mg–Zn–Zr Alloy on cancellous bone tissue

Mg-Zn-Zr alloy cylinders were implanted into the femoral condyles of Japanese big-ear white rabbits. X-ray showed that by 12 weeks following implantation the implant became obscure, around which the low-density area appeared and enlarged. By 24 weeks, the implant was more obscure and the density of the surrounding cancellous bone increased. Scanning electron microscopy examination showed bone tissue on the surface of the alloy attached by living fibers at 12 weeks. Micro-CT confirmed that new bone tissue on the surface of the residual alloy implant increased from 12 weeks to 24 weeks. By 12 weeks, many cavities in the cancellous bone tissue around the implant were noted with a CT value, similar to gas value, and increasing by 24 weeks (P<0.01). Histological examination of hard tissue slices showed that bone tissue was visibly attached to the alloy in the femoral condyle at 12 weeks. The trabecular bone tissues became more intact and dense, and the cavities were filled with soft tissue at 24 weeks. In general, gas produced by the degradation of the Mg-Zn-Zr alloy can cause cavitation within cancellous bone, which does not affect osteogenesis of Mg alloy.

Fabrication and characterization of a biodegradable Mg–2Zn–0.5Ca/1β-TCP composite

A biodegradable magnesium matrix and beta-tricalcium phosphate (β-TCP) particles reinforced composite Mg-2Zn-0.5Ca/1beta-TCP (wt.%) was fabricated for biomedical applications by the novel route of combined high shear solidification (HSS) and equal channel angular extrusion (ECAE). The as-cast composite obtained by HSS showed a fine and equiaxed grain structure with globally uniformly distributed β-TCP particles in aggregates of 2-25 μm in size. The ECAE processing at 300 °C resulted in further microstructural refinement and the improvement of β-TCP particle distribution. During ECAE, the β-TCP aggregates were broken into smaller ones or individual particles, forming a dispersion in the matrix. Such fabricated composite exhibited enhanced hardness and in vitro corrosion resistance. The enhanced hardness was attributed to both the addition of β-TCP particles and grain refinement while the development of a Ca-P rich surface layer from β-TCP during corrosion was responsible for the improvement in corrosion resistance. The composite was characterized in terms of microstructural evolution during fabrication, mechanical properties and electrochemical performance during polarization and immersion tests in a simulated body fluid. Discussions are made on the benefits of both HSS and ECAE and the mechanisms responsible for the enhanced corrosion resistance.

The Influence of Zn Content on the Corrosion and Wear Performance of Mg-Zn-Ca Alloy in Simulated Body Fluid

Mg-Zn-Ca alloy has been attracting increasing attention as a potential biodegradable implant material. In this paper, Mg-3Zn-0.2Ca and Mg-4Zn-0.2Ca alloys were prepared by means of vacuum melting and subsequent hot extrusion process. The influences of Zn content on the microstructure, mechanical properties, and corrosion and wear behavior of Mg-Zn-Ca alloys in simulated body fluid (SBF) were studied. The results show that with increased Zn content, the grain size and corrosion resistance were decreased, while the mechanical strength and wear resistance were increased, under both dry sliding and SBF-lubricated conditions. For the same Mg-Zn-Ca alloy, the wear loss rate under SBF lubrication was higher than dry sliding condition, indicating a strong corrosion-assisted wear effect of SBF to the Mg-Zn-Ca alloy.

In vitro and in vivo corrosion, mechanical properties and biocompatibility evaluation of MgF2-coated Mg-Zn-Zr alloy as cancellous screws

Magnesium (Mg) and its alloys as biodegradable materials have received much attention in the orthopedics applications; however, the corrosion behavior of these metals in vivo remains challenging. In this work, a dense and nanoscale magnesium fluoride (MgF2) coating was deposited on the surface of Mg-Zn-Zr (MZZ) alloy cancellous screw. The MZZ cancellous screw with MgF2 coating maintained an integrated shape and high yield tensile stress after 30days immersion in SBF, comparing with the bare screw. Hydrogen releasing rate of the MZZ samples was suppressed at a lower level at the initial stage, which is in favour of the adhesion of the cells. And in vivo experiments indicated that MgF2-coated MZZ screws presented advantages in cytocompatibility, osteoconductivity and osteogenesis of cancellous bone in rabbits. Corrosion rate in vivo perfusion environment increased very slowly with time in long-term study, which was an opposite trend in vitro static immersion test. Moreover, maximum corrosion rate (CRmax), a critical calculation method of corrosion rate was introduced to predict fracture regions of the sample. The MZZ alloy with MgF2 coating possesses a great potential for clinical applications for internal fracture fixation repair.

The effect of nano-hydroxyapatite on the microstructure and properties of Mg–3Zn–0.5Zr alloy

In order to meet the clinical application requirements of biodegradable materials in orthopedic surgery field, novel Mg–3Zn–0.5Zr/xHA (x = 0, 0.5, 1 and 1.5 wt%) composites have been developed by melting under the mechanical stirring and the heat extrusion route. The thorough examination on the effect of nano-hydroxyapatite (nano-HA) particles on the microstructure, mechanical properties and corrosion resistance of Mg–3Zn–0.5Zr alloy was carried out. The results indicated that the gelatin-coated nano-HA particles could more uniformly distribute in the matrix and the grain size was refined to be approximately 10 µm. More non-basal dislocations presented in the composite with the increment of nano-HA particles. Compared with the Mg–3Zn–0.5Zr alloy, the ultimate tensile strength, yield strength and elongation of the Mg–3Zn–0.5Zr/1.5HA composite had been improved and reached 302 MPa, 275 MPa and 20.9%, respectively. Furthermore, Mg–3Zn–0.5Zr/1HA composite showed the optimal degradation rate of 6.45 mm/yr in the in vitro corrosion tests. From the clinical application requirements of biodegradable materials point of view, the composite containing 1 wt% nano-HA particles could be evidently believed to be a promising bone fixation material for the application.

Effects of grain size on the corrosion resistance of pure magnesium by cooling rate-controlled solidification

The aim of this study was to investigate the effect of grain size on the corrosion resistance of pure magnesium developed for biomedical applications. High-purity magnesium samples with different grain size were prepared by the cooling rate-controlled solidification. Electrochemical and immersion tests were employed to measure the corrosion resistance of pure magnesium with different grain size. The electrochemical polarization curves indicated that the corrosion susceptibility increased as the grain size decrease. However, the electrochemical impedance spectroscopy (EIS) and immersion tests indicated that the corrosion resistance of pure magnesium is improved as the grain size decreases. The improvement in the corrosion resistance is attributed to refine grain can produce more uniform and density film on the surface of sample.

Biological activity evaluation of magnesium fluoride coated Mg-Zn-Zr alloy in vivo

AIM To explore the biodegradable characteristics and biological properties, which could promote new bone formation, of MgF2 coated magnesium alloy (Mg-3wt%Zn-0.5wt%Zr) in rabbits. METHODS Magnesium alloy with MgF2 coating was made and the MgF2/Mg-Zn-Zr was implanted in the femoral condyle of rabbits. Twelve healthy adult Japanese white rabbits in weight of 2.8-3.2kg were averagely divided into A(Mg-Zn-Zr) group and B(MgF2/MgZn-Zr) group. Indexes such as microstructural evolution, SEM scan, X-ray, Micro-CT and mechanical properties were observed and detected at 1th day, 2th, 4th, 8th, 12th, 24th week after implantation. RESULTS Low-density regions occurred around the cancellous bone, and the regions gradually expanded during the 12weeks after implantation. The implant was gradually absorbed from 12 to 24weeks. The density of surrounding cancellous bone increased compared with the 12th week data. The degradation rate of B group was lower than that of A group (P<0.01), while the density of the surrounding cancellous bone increased more evenly. In B group, SEM images after 12weeks showed the rich bone tissues on the alloy surface that were attached by active fibers. Micro-CT also presented alloy residue potholes on the surfaces of alloy combinated with bone tissues. Additionally, the trabecular bone had relatively integrated structures with surrounding cavities. CONCLUSIONS MgF2 can effectively decrease the degradation rate of Mg-Zn-Zr in vivo. Mg-Zn-Zr coated with MgF2 can effectively inhibit the corrosion, and delay the release of magnesium ions. The biological properties of the coating itself presented good biocompatibility and bioactivity.

Corrosion degradation behavior of Mg-Ca alloy with high Ca content in SBF

Abstract The corrosion degradation behavior of a Mg–Ca alloy with high Ca content aiming for a potential bone repair material in the simulated body fluid (SBF) was investigated. The microstructure and phase constitution of the pristine Mg–30%Ca (mass fraction) alloy were characterized with scanning electron microscopy (SEM) and X-ray diffraction (XRD). The Mg–30%Ca alloy samples were immersed in the SBF for 90 d, and the morphology, composition and cytotoxicity of the final corrosion product were examined. It is found that Mg–30%Ca alloy is composed of α-Mg and Mg 2 Ca phases. During the corrosion process in the SBF, the Mg 2 Ca phase acts as an anode and the α-Mg phase acts as a cathode. The final corrosion product of the Mg–30%Ca alloy in SBF includes a small amount of black precipitates and white suspended particles. The white suspended particles are Mg(OH) 2 and the black particles are believed to have a core–shell structure. The cytotoxicity experiments indicate that these black precipitates do not induce toxicity to cells.