Peter J. Uggowitzer

Magnesium alloys for temporary implants in osteosynthesis: In vivo studies of their degradation and interaction with bone

This study investigates the bone and tissue response to degrading magnesium pin implants in the growing rat skeleton by continuous in vivo microfocus computed tomography (μCT) monitoring over the entire pin degradation period, with special focus on bone remodeling after implant dissolution. The influence of gas release on tissue performance upon degradation of the magnesium implant is also addressed. Two different magnesium alloys - one fast degrading (ZX50) and one slowly degrading (WZ21) - were used for evaluating the bone response in 32 male Sprague-Dawley rats. After femoral pin implantation μCTs were performed every 4 weeks over the 24 weeks of the study period. ZX50 pins exhibited early degradation and released large hydrogen gas volumes. While considerable callus formation occurred, the bone function was not permanently harmed and the bone recovered unexpectedly quickly after complete pin degradation. WZ21 pins kept their integrity for more than 4 weeks and showed good osteoconductive properties by enhancing bone accumulation at the pin surface. Despite excessive gas formation, the magnesium pins did not harm bone regeneration. At smaller degradation rates, gas evolution remained unproblematic and the magnesium implants showed good biocompatibility. Online μCT monitoring is shown to be suitable for evaluating materials degradation and bone response in vivo, providing continuous information on the implant and tissue performance in the same living animal.

Design strategy for biodegradable Fe-based alloys for medical applications☆

The aim of this article is to describe a design strategy for the development of new biodegradable Fe-based alloys offering a performance considered appropriate for temporary implant applications, in terms of both an enhanced degradation rate compared to pure iron, and suitable strength and ductility. The design strategy is based on electrochemical, microstructural and toxicological considerations. The influence of alloying elements on the electrochemical modification of the Fe matrix and the controlled formation of noble intermetallic phases is deployed. Such intermetallic phases are responsible for both an increased degradation rate and enhanced strength. Manganese and palladium have been shown to be suitable alloying additions for this design strategy: Mn lowers the standard electrode potential, while Pd forms noble (Fe,Mn)Pd intermetallics that act as cathodic sites. We discuss the efficiency and the potential of the design approach, and evaluate the resulting characteristics of the new alloys using metal-physical experiments including electrochemical measurements, phase identification analysis and electron microscopy studies. The newly developed Fe-Mn-Pd alloys reveal a degradation resistance that is one order of magnitude lower than observed for pure iron. Additionally, the mechanical performance is shown to be adjustable not only by the choice of alloying elements but also by heat treatment procedures; high strength values >1400MPa at ductility levels >10% can be achieved. Thus, the new alloys offer an attractive combination of electrochemical and mechanical characteristics considered suitable for biodegradable medical applications.

On the biodegradation performance of an Mg–Y–RE alloy with various surface conditions in simulated body fluid

This study documents the influence of different surface conditions produced by various heat treatments on the in vitro degradation performance of an Mg-Y-RE alloy (WE43) investigated by immersion in simulated body fluid. WE43 samples were, respectively (i) annealed at 525 degrees C (plus artificial aging at 250 degrees C in one case) and afterwards polished; and (ii) polished, annealed at 500 degrees C in air and subsequently investigated in the oxidized state. Thermogravimetric analysis (TGA) indicates a mass gain during oxidation in air, following a square-root law over time. X-ray diffraction spectra imply a growing Y(2)O(3) layer upon oxidation, and Auger electron spectroscopy depth profiles show an increased oxide layer thickness which develops according to the behavior observed by TGA. Macroscopically, the degradation performance of the differently heat-treated samples can be divided into two groups. Annealed and polished samples show a fast and homogeneous degradation which slows with time. Their degradation behavior is approximated by a parabolic law. Oxidized samples exhibit a slow initial degradation rate which increases when the protection of the oxide layer is reduced. Overall, they reveal a sigmoidal degradation behavior. Here the differing degradation performances of the annealed-polished and the oxidized samples are related to the different surface conditions and explained on the basis of a depletion hypothesis.

On the silicon spheroidization in Al–Si alloys

Abstract It is commonly known that eutectic silicon spheroidizes during a T6 solution heat treatment in Al–Si cast alloys. This spheroidization of the brittle silicon is the main reason for the good fracture elongation values in peak hardened T6 condition. As the silicon spheroidization is known as a side effect of common T6 treatment, there is little known about the influence of sole silicon spheroidization on the mechanical properties. The following paper presents fundamental aspects of the spheroidization process of eutectic silicon in Al–Si cast alloys. It is theoretically as well as experimentally found that the disintegration and spheroidization of well modified eutectic silicon is finished within minutes of exposure to temperatures above 500 °C. The application of this new silicon spheroidization treatment (SST) to thixoformed components results in outstanding fracture elongation values (up to 18%) at good yield strength level (∼230 MPa). FEM simulations of the short high temperature heat treatment confirm a short process time for successful SST even for components with notably variable wall thicknesses.

In vivo degradation performance of micro-arc-oxidized magnesium implants: A micro-CT study in rats

Biodegradable Mg alloys are of great interest for osteosynthetic applications because they do not require surgical removal after they have served their purpose. In this study, fast-degrading ZX50 Mg-based implants were surface-treated by micro-arc oxidation (MAO), to alter the initial degradation, and implanted along with untreated ZX50 controls in the femoral legs of 20 male Sprague-Dawley rats. Their degradation was monitored by microfocus computed tomography (μCT) over a total observation period of 24weeks, and histological analysis was performed after 4, 12 and 24weeks. While the MAO-treated samples showed almost no corrosion in the first week, they revealed an accelerated degradation rate after the third week, even faster than that of the untreated ZX50 implants. This increase in degradation rate can be explained by an increase in the surface-area-to-volume ratio of MAO-treated implants, which degrade inhomogeneously via localized corrosion attacks. The histological analyses show that the initially improved corrosion resistance of the MAO implants has a positive effect on bone and tissue response: The reduced hydrogen evolution (due to reduced corrosion) makes possible increased osteoblast apposition from the very beginning, thus generating a stable bone-implant interface. As such, MAO treatment appears to be very interesting for osteosynthetic implant applications, as it delays implant degradation immediately after implantation, enhances fracture stabilization, minimizes the burden on the postoperatively irritated surrounding tissue and generates good bone-implant connections, followed by accelerated degradation in the later stage of bone healing.

On the effect of nitrogen on the dislocation structure of austenitic stainless steel

The strengthening and work hardening characteristics of high nitrogen austenitic steel have been investigated by TEM in order to explain the outstanding mechanical properties, which are very high yield strength and good toughness. It is shown that plastic deformation of those steels always occurs by a combination of planar glide and mechanical twinning. However, the critical stress/strain conditions for the onset of mechanical twinning depend strongly on the actual nitrogen content. Specifically, as the nitrogen content is increased, the onset of deformation twinning is shifted to lower strains and higher stresses, i.e. the more important becomes the contribution of deformation twinning to the total strain. The observed behaviour is explained by the influence of nitrogen on internal friction and stacking fault energy. It is concluded that the high yield strength of cold worked nitrogen-bearing steel is essentially due to tight stackings of twins and stacking faults. Apart from regular structure evolution, inhomogeneous structures are observed, which can be explained in terms of texture formation and the dynamic properties of stacking faults under stress.

Degradation performance of biodegradable Fe-Mn-C(-Pd) alloys

Biodegradable metals offer great potential in circumventing the long-term risks and side effects of medical implants. Austenitic Fe-Mn-C-Pd alloys feature a well-balanced combination of high strength and considerable ductility which make them attractive for use as degradable implant material. The focus of this study is the evaluation of the degradation performance of these alloys by means of immersion testing and electrochemical impedance spectroscopy in simulated body fluid. The Fe-Mn-C-Pd alloys are characterized by an increased degradation rate compared to pure Fe, as revealed by both techniques. Electrochemical measurements turned out to be a sensitive tool for investigating the degradation behavior. They not only show that the polarization resistance is a measure of corrosion tendency, but also provide information on the evolution of the degradation product layers. The mass loss data from immersion tests indicate a decreasing degradation rate for longer times due to the formation of degradation products on the sample surfaces. The results are discussed in detail in terms of the degradation mechanism of Fe-based alloys in physiological media.

Influence of trace impurities on the in vitro and in vivo degradation of biodegradable Mg-5Zn-0.3Ca alloys

The hydrogen evolution method and animal experiments were deployed to investigate the effect of trace impurity elements on the degradation behavior of high-strength Mg alloys of type ZX50 (Mg-5Zn-0.3Ca). It is shown that trace impurity elements increase the degradation rate, predominantly in the initial period of the tests, and also increase the materials susceptibility to localized corrosion attack. These effects are explained on the basis of the corrosion potential of the intermetallic phases present in the alloys. The Zn-rich phases present in ZX50 are nobler than the Mg matrix, and thus act as cathodic sites. The impurity elements Fe and Mn in the alloy of conventional purity are incorporated in these Zn-rich intermetallic phases and therefore increase their cathodic efficiency. A design rule for circumventing the formation of noble intermetallic particles and thus avoiding galvanically accelerated dissolution of the Mg matrix is proposed.

In-vitro characterization of stress corrosion cracking of aluminium-free magnesium alloys for temporary bio-implant applications

The complex interaction between physiological stresses and corrosive human body fluid may cause premature failure of metallic biomaterials due to the phenomenon of stress corrosion cracking. In this study, the susceptibility to stress corrosion cracking of biodegradable and aluminium-free magnesium alloys ZX50, WZ21 and WE43 was investigated by slow strain rate tensile testing in a simulated human body fluid. Slow strain rate tensile testing results indicated that each alloy was susceptible to stress corrosion cracking, and this was confirmed by fractographic features of transgranular and/or intergranular cracking. However, the variation in alloy susceptibility to stress corrosion cracking is explained on the basis of their electrochemical and microstructural characteristics.

Cellular reactions to biodegradable magnesium alloys on human growth plate chondrocytes and osteoblasts

PurposeIn recent decades operative fracture treatment using elastic stable intramedullary nails (ESINs) has mainly taken precedence over conservative alternatives in children. The development of biodegradable materials that could be used for ESINs would be a further step towards treatment improvement. Due to its mechanical and elastic properties, magnesium seems to be an ideal material for biodegradable implant application. The aim of this study was therefore to investigate the cellular reaction to biodegradable magnesium implants in vitro.MethodsPrimary human growth plate chondrocytes and MG63 osteoblasts were used for this study. Viability and metabolic activity in response to the eluate of a rapidly and a slower degrading magnesium alloy were investigated. Furthermore, changes in gene expression were assessed and live cell imaging was performed.ResultsA superior performance of the slower degrading WZ21 alloy’s eluate was detected regarding cell viability and metabolic activity, cell proliferation and morphology. However, the ZX50 alloy’s eluate induced a favourable up-regulation of osteogenic markers in MG63 osteoblasts.ConclusionsThis study showed that magnesium alloys for use in biodegradable implant application are well tolerated in both osteoblasts and growth plate chondrocytes respectively.