Thomas Ebel

Hybrid implants composed of magnesium and titanium are a promising direction in orthopaedics, as these implants combine the stability of titanium with the biological activity of magnesium. These partly soluble implants require careful investigation, as the degradation of magnesium releases hydrogen, which can enter the Ti matrix and thus alter the mechanical properties. To investigate this scenario and quantify the hydrogen uptake along with its structural impacts, we employed inert gas fusion, scanning electron microscopy, X-ray diffraction, and a combination of synchrotron absorption and X-ray diffraction tomography. These techniques enabled us to investigate the concentration and distribution of hydrogen and the formation of hydrides in the samples. Titanium hydride formation was observed in a region approximately 120 µm away from the titanium surface and correlates with the amount of absorbed hydrogen. We speculate that the degradation of magnesium at the magnesium/titanium implant interface leads to the penetration of hydrogen due to a combination of electrochemical and gaseous charging.

The β titanium alloys are key materials in lightweight and biomedical applications, due to the combination of excellent biocompatibility and mechanical properties. However, the Binder-based Powder Technologies such as Metal-Injection-Molding (MIM), Binder-Jetting and Fused-Filament-Fabrication, normally introduce three major processing-related defects in the as-sintered Ti-parts: (i) residual porosity, (ii) high impurity level and (iii) coarse-grained structure. The previous studies revealed that these processing defects invariably tend to be even more severe in β titanium alloys than in α/β Ti-6Al-4V alloy, all fabricated by powder metallurgical route. In this work, these processing defects and their likely origins in MIM β titanium alloys are analysed. Furthermore, the influence of these defects on damage tolerance and fracture mechanisms of MIM β titanium alloys under either static or dynamic loading is investigated. Based on the studies, strategic technical improvements in the processing to improve the reliability of MIM β titanium alloys products are proposed.

Binary MgCa alloys are one of the promising and well investigated biodegradable metals and therefore a good standard for the study of novel processing routes. In this investigation, novel powder metallurgical (PM) blending and sintering methods were applied for the generation of biodegradable MgCa test specimens, using metal injection moulding (MIM). In addition to the classical PM-blending route using Ca-containing master-alloys, Ca-containing ceramics and hydrides, as there are CaO and CaH_2, were used separately and in a stoichiometric mixture. In situ X-ray synchrotron radiation experiments were performed for a deeper understanding of alloy forming mechanisms during sintering. Mechanical and degradation performance was investigated by tensile testing and the monitoring of biodegradation under physiological conditions. Besides its sound strength of up to 144 MPa and degradation rate of 0.25 mm/a, the new redox alloying technique avoids the usage of any greenhouse active SF₆ gas (global warming potential 22,800) during alloying, keeping the earth’s atmosphere safer. Therefore, it can be concluded that Ca-containing ceramics and hybrids are attractive alternatives to obtain, comparable to Mg-based materials, thus enabling safer processing.

Multifunctional materials based on a combination of permanent and degradable metals open new perspectives for medical implants combining osseoconductivity and drug-delivery functions which can significantly decrease the number of implants’ revision. In this work, hybrid magnesium-titanium materials were produced via sintering, and the properties of the permanent titanium component before and after the degradation of the temporary magnesium part were evaluated. The changes of chemical composition and mechanical parameters were determined. Loading of hydrogen into the titanium part at room temperature was observed, which deteriorated the mechanical characteristics but could also simultaneously improve the biocompatibility of the permanent titanium implant. The control of degradation of the magnesium part and the modification of the titanium part are required for the development of partly degradable hybrid implants.

Fused filament fabrication (FFF) is a new procedure for the production of plastic parts, particularly if the parts have a complex geometry and are only needed in a limited quantity, e.g., in specific medical applications. In addition to the production of parts which are purely composed of polymers, fused filament fabrication can be successfully applied for the preparation of green bodies for sintering of metallic implant materials in medical applications. In this case, highly filled polymer–metal feedstocks, which contain a variety of polymeric components, are used. In this study, we focus on various polymer-metal feedstocks, investigate the rheological properties of these materials, and relate them to our results of FFF experiments. Small amplitudes of shear oscillations reveal that the linear range of the polymer–metal feedstocks under investigation is very small, which is caused by elastic and viscous interactions between the metallic particles. These interactions strongly influence or even dominate the flow properties of the feedstock depending on the applied shear stress. The magnitude of the complex viscosity strongly increases with decreasing angular frequency, which indicates the existence of an apparent yield stress. The viscosity increase caused by the high powder loading needed for sintering limits the maximum printing velocity and the minimum layer height. The apparent yield stress hinders the formation of smooth surfaces in the FFF process and slows down the welding of deposited layers. The influence of composition on the processing parameters (suitable temperature range) and part properties (e.g., surface roughness) is discussed on the basis of rheological data.

Mg-xGd alloys show potential to be used for degradable implants. As rare earth containing alloys, they are also of special interest for wrought products. All applications from medical to engineering uses require a low and controlled degradation or corrosion rate without pitting. Impurities from fabrication or machining, like Fe inclusions, encourage pitting, which inhibits uniform material degradation. This work investigates a suitable etching method to remove surface contamination and to understand the influence of etching on surface morphology. Acetic acid (HAc) etching as chemical surface treatment has been used to remove contamination from the surface. Extruded Mg-xGd (x = 2, 5 and 10) discs were etched with 250 g/L HAc solution in a volume of 5 mL or 10 mL for different times. The microstructure in the near surface region was characterized. Surface characterization was done by SEM, EDS, interferometry, and ToF-SIMS (time-of-flight secondary ion mass spectrometry) analysis. Different etching kinetics were observed due to microstructure and the volume of etching solution. Gd rich particles and higher etching temperatures due to smaller etchant volumes promote the formation of pits. Removal of 2–9 µm of material from the surface was sufficient to remove surface Fe contamination and to result in a plain surface morphology.

This report reviews the effects of chemical, physical, and mechanical surface treatments on the degradation behavior of Mg alloys via their influence on the roughness and surface morphology. Many studies have been focused on technically-used AZ alloys and a few investigations regarding the surface treatment of biodegradable and Al-free Mg alloys, especially under physiological conditions. These treatments tailor the surface roughness, homogenize the morphology, and decrease the degradation rate of the alloys. Conversely, there have also been reports which showed that rough surfaces lead to less pitting and good cell adherence. Besides roughness, there are many other parameters which are much more important than roughness when regarding the degradation behavior of an alloy. These studies, which indicate the relationship between surface treatments, roughness and degradation, require further elaboration, particularly for biomedical Mg alloy applications.

During metal injection moulding (MIM) processing, titanium tends to react with carbon from the polymeric binder. Thus, carbides, which can effect embrittlement, might be formed if the carbon solubility of the alloy is exceeded. Especially in β-titanium alloys, this is a critical issue, because β-phase stabilising elements like V, Mo and Nb decrease the carbon solubility of the Ti-matrix. This study summarises studies with different approaches to limit carbide precipitation in a Ti–22wt-%Nb alloy processed by MIM. Adding Zr led to a significant reduction in the amount and size of carbides due to an increase in the lattice constant. Furthermore, boron was added supporting a finer distribution of the carbides. Scanning electron microscopy and transmission electron microscopy investigations reveal the role of the elemental additions and analyse the structure of the different carbides formed. Combinations with heat treatments led to significant reduction in the amount of carbides.

The current physiological in vitro tests of Mg degradation follow the procedure stated according to the ASTM standard. This standard, although useful in predicting the initial degradation behavior of an alloy, has its limitations in interpreting the same for longer periods of immersion in cell culture media. This is an important consequence as the alloy’s degradation is time dependent. Even if two different alloys show similar corrosion rates in a short term experiment, their degradation characteristics might differ with increased immersion times. Furthermore, studies concerning Mg corrosion extrapolate the corrosion rate from a single time point measurement to the order of a year (mm/y), which might not be appropriate because of time dependent degradation behavior. In this work, the above issues are addressed and a new methodology of performing long-term immersion tests in determining the degradation rates of Mg alloys was put forth. For this purpose, cast and extruded Mg-2Ag and powder pressed and sintered Mg-0.3Ca alloy systems were chosen. DMEM Glutamax +10% FBS (Fetal Bovine Serum) +1% Penicillin streptomycin was used as cell culture medium. The advantages of such a method in predicting the degradation rates in vivo deduced from in vitro experiments are discussed.