Enhancing the Mechanical Properties of Biodegradable Mg Alloys Processed by Warm HPT and Thermal Treatments.

In this study, several biodegradable Mg alloys (Mg5Zn, Mg5Zn0.3Ca, Mg5Zn0.15Ca, and Mg5Zn0.15Ca0.15Zr, numbers in wt%) were investigated after thermomechanical processing via high-pressure torsion (HPT) at elevated temperature as well as after additional heat treatments. Indirect and direct analyses of microstructure revealed that the significant strength increases arise not only from dislocations and precipitates but also from vacancy agglomerates. By contrast with former low-temperature processing routes applied by the authors, a significant ductility was obtained because of temperature-induced dynamic recovery. The low initial values of Young's modulus were not significantly affected by warm HPT-processing. nor by heat treatments afterwards. Also, corrosion resistance did not change or even increase during those treatments. Altogether, the study reveals a viable processing route for the optimization of Mg alloys to provide enhanced mechanical properties while leaving the corrosion properties unaffected, suggesting it for the use as biodegradable implant material.

Surface Analysis of Biodegradable Mg-Alloys after Immersion in Simulated Body Fluid.

Two binary biodegradable Mg-alloys and one ternary biodegradable Mg-alloy (Mg-0.3Ca, Mg-5Zn and Mg-5Zn-0.3Ca, all in wt%) were investigated. Surface-sensitive X-ray photoelectron spectroscopy analyses (XPS) of the alloy surfaces before and after immersion in simulated body fluid (SBF) were performed. The XPS analysis of the samples before the immersion in SBF revealed that the top layer of the alloy might have a non-homogeneous composition relative to the bulk. Degradation during the SBF immersion testing was monitored by measuring the evolution of H2. It was possible to evaluate the thickness of the sample degradation layers after the SBF immersion based on scanning electron microscopy (SEM) of the tilted sample. The thickness was in the order of 10-100 µm. The typical bio-corrosion products of all of the investigated alloys consisted of Mg, Ca, P and O, which suggests the formation of apatite (calcium phosphate hydroxide), magnesium hydrogen phosphate hydrate and magnesium hydroxide. The bioapplicability of the analyzed alloys with regard to surface composition and degradation kinetics is discussed.

Microstructure, mechanical properties, and degradation of Mg-Ag alloy after equal-channel angular pressing.

Enhancing the strength of Mg-based biodegradable alloys without decreasing their corrosion resistance is a major engineering challenge. In addition, the growing demand for effective reduction of infections and inflammation after implant placement motivates the design of alloys with appropriate compositions or coatings. One promising alloying element is silver, whose antibacterial effect has long been known. Therefore, a Mg-4% Ag alloy was selected for this study. The alloy was investigated under three conditions: as-cast, after T4 treatment, and after T4 treatment with subsequent equal-channel angular pressing (ECAP) using a newly developed double-ECAP die, which offers an equivalent strain per pass of 1.6. The first pass through the double-ECAP die was conducted at 370 °C and the second at 330 °C using route BC. The microstructure of the as-cast Mg-4% Ag consisted of large grains (several hundred microns) and a dendritic structure with micron-sized Mg54Ag17 precipitates. T4 heat treatment caused dissolution of the dendrites and formation of a solid solution without changing the grain size. Consequently, the ultimate compressive strength (UCS) was increased by approximately 30%, and the compressive strain at fracture reached approximately 23%. The compressive yield strength (CYS) remained nearly constant at approximately 30 MPa. Subsequent ECAP led to strong grain refinement (from 350 µm to 38 µm after one pass and 15 µm after two passes) and further increases in the CYS and UCS, to 45 and 300 MPa after the first pass and 62 and 325 MPa after the second pass, respectively. The as-cast alloy exhibited a very high degradation rate in a simulated body fluid at approximately 36 °C. The degradation rate of the alloy after T4 treatment was much lower. Subsequent ECAP had no significant effect on the degradation properties. Thus, it can be concluded that grain refinement has little effect on the degradation rate.

Exceptional Strengthening of Biodegradable Mg-Zn-Ca Alloys through High Pressure Torsion and Subsequent Heat Treatment.

In this study, two biodegradable Mg-Zn-Ca alloys with alloy content of less than 1 wt % were strengthened via high pressure torsion (HPT). A subsequent heat treatment at temperatures of around 0.45 Tm led to an additional, sometimes even larger increase in both hardness and tensile strength. A hardness of more than 110 HV and tensile strength of more than 300 MPa were achieved in Mg-0.2Zn-0.5Ca by this procedure. Microstructural analyses were conducted by scanning and transmission electron microscopy (SEM and TEM, respectively) and atom probe tomography (APT) to reveal the origin of this strength increase. They indicated a grain size in the sub-micron range, Ca-rich precipitates, and segregation of the alloying elements at the grain boundaries after HPT-processing. While the grain size and segregation remained mostly unchanged during the heat treatment, the size and density of the precipitates increased slightly. However, estimates with an Orowan-type equation showed that precipitation hardening cannot account for the strength increase observed. Instead, the high concentration of vacancies after HPT-processing is thought to lead to the formation of vacancy agglomerates and dislocation loops in the basal plane, where they represent particularly strong obstacles to dislocation movement, thus, accounting for the considerable strength increase observed. This idea is substantiated by theoretical considerations and quenching experiments, which also show an increase in hardness when the same heat treatment is applied.

Mechanical properties, structural and texture evolution of biocompatible Ti-45Nb alloy processed by severe plastic deformation.

Biocompatible ß Ti-45Nb (wt%) alloys were subjected to different methods of severe plastic deformation (SPD) in order to increase the mechanical strength without increasing the low Young׳s modulus thus avoiding the stress shielding effect. The mechanical properties, microstructural changes and texture evolution were investigated, by means of tensile, microhardness and nanoindentation tests, as well as TEM and XRD. Significant increases of hardness and ultimate tensile strength up to a factor 1.6 and 2, respectively, could be achieved depending on the SPD method applied (hydrostatic extrusion - HE, high pressure torsion - HPT, and rolling and folding - R&F), while maintaining the considerable ductility. Due to the high content of ß-stabilizing Nb, the initial lattice structure turned out to be stable upon all of the SPD methods applied. This explains why with all SPD methods the apparent Young׳s modulus measured by nanoindentation did not exceed that of the non-processed material. For its variations below that level, they could be quantitatively related to changes in the SPD-induced texture, by means of calculations of the Young׳s modulus on basis of the texture data which were carefully measured for all different SPD techniques and strains. This is especially true for the significant decrease of Young׳s modulus for increasing R&F processing which is thus identified as a texture effect. Considering the mechanical biocompatibility (percentage of hardness over Young׳s modulus), a value of 3-4% is achieved with all the SPD routes applied which recommends them for enhancing ß Ti-alloys for biomedical applications.

Changes in microstructure and physical properties of skutterudites after severe plastic deformation.

The best p-type skutterudites with ZT > 1.1 so far are didymium (DD) filled, Fe/Co substituted, Sb-based skutterudites. DD0.68Fe3CoSb12 was prepared using an annealing-reacting-melting-quenching technique followed by ball milling and hot pressing. After severe plastic deformation via high-pressure torsion (HPT), no phase changes but particular structural variations were achieved, leading to modified transport properties with higher ZT values. Although after measurement-induced heating some of the HPT induced defects were annealed out, a still attractive ZT-value was preserved. In this paper we focus on explanations for these changes via TEM investigations, Raman spectroscopy and texture measurements. The grain sizes and dislocation densities, evaluated from TEM images, showed that (i) the majority of cracks generated during high-pressure torsion are healed during annealing, leaving only small pores, that (ii) the grains have grown, and that (iii) the dislocation density is decreased. While Raman spectra indicate that after HPT processing and annealing the vibration modes related to the shorter Sb-Sb bonds in the Sb4 rings are more affected than those related to the longer Sb-Sb bonds, almost no visible changes were observed in the pole intensity and/or orientation.