Carsten Blawert

Magnesium alloys as implant materials--principles of property design for Mg-RE alloys.

Magnesium alloys have attracted increasing interest in the past years due to their potential as implant materials. This interest is based on the fact that magnesium and its alloys are degradable during their time of service in the human body. Moreover magnesium alloys offer a property profile that is very close or even similar to that of human bone. The chemical composition triggers the resulting microstructure and features of degradation. In addition, the entire manufacturing route has an influence on the morphology of the microstructure after processing. Therefore the composition and the manufacturing route have to be chosen carefully with regard to the requirements of an application. This paper discusses the influence of composition and heat treatments on the microstructure, mechanical properties and corrosion behaviour of cast Mg-Gd alloys. Recommendations are given for the design of future degradable magnesium based implant materials.

Microstructure and corrosion behavior of Mg-Sn-Ca alloys after extrusion

Abstract Mg-Sn-Ca alloys promise a reasonable corrosion resistance in combination with good creep resistance, likely due to the presence of Ca 2− x Mg x Sn and other phases. The selected alloys with 3% Sn and Ca in the range of 1%–2% have been extruded in order to achieve more homogeneous microstructure compared with the as-cast alloys. Optical microscopy(OM) and X-ray diffraction(XRD) techniques were used to study the microstructure and phases of these alloys. The corrosion behavior of these alloys was investigated by means of salt spray test and potentio-dynamic measurements. The results obtained on the alloys Mg-3Sn (T3), Mg-3Sn-1Ca (TX31), and Mg-3Sn-2Ca (TX32) indicate the presence of the same phases in as-cast and after extrusion, namely Mg 2 Sn, Ca 2− x Mg x Sn, and Ca 2− x Mg x Sn/Mg 2 Ca, respectively. However, due to the occurrence of extensive recrystallization in the extrusion process, the grain size has significantly reduced after extrusion. The reduction leads to the improvement of the corrosion resistance after extrusion which is then comparable with the commercial alloy AZ91D.

Wear behavior of plasma electrolytic oxidation (PEO) and hybrid coatings of PEO and laser on MRI 230D magnesium alloy

Wear resistant coatings were produced on a permanent mould cast MRI 230D Mg alloy by (a) PEO in silicate based electrolyte, (b) PEO in phosphate based electrolyte, (c) hybrid coatings of silicate PEO followed by laser surface alloying (LSA) with Al and Al2O3, and (d) hybrid coatings of phosphate PEO followed by LSA with Al and Al2O3. Microstructural characterization of the coatings was carried out by scanning electron microscopy (SEM) and X(ray diffraction. The tribological behavior of the coatings was investigated under dry sliding condition using linearly reciprocating ball-on-flat wear test. Both the PEO coatings exhibited a friction coefficient of about 0.8 and hybrid coatings exhibited a value of about 0.5 against the AISI 52100 steel ball as the friction partner, which were slightly reduced with the increase in applied load. The PEO coatings sustained the test without failure at 2 N load but failed at 5 N load due to micro-fracture caused by high contact stresses. The hybrid coatings did not get completely worn off at 2 N load but were completely removed exposing the substrate at 5 N load. The PEO coatings exhibited better wear resistance than the hybrid coatings and silicate PEO coatings exhibited better wear resistance than the phosphate PEO coatings. Both the PEO coatings melted/decomposed on laser irradiation and all the hybrid coatings exhibited similar microstructure and wear behavior irrespective of the nature of the primary PEO coating or laser energies. SEM examination of worn surfaces indicated abrasive wear combined with adhesive wear for all the specimens. The surface of the ball exhibited a discontinuous transfer layer after the wear test.

Investigations in the Magnesium-Tin System

Currently most magnesium alloys are based on the Mg-Al system and this system is reasonably well developed. Nevertheless, the alloy system has some disadvantages – while having excellent castability and adequate room temperature mechanical properties Mg-Al alloys show poor creep resistance. This has led to investigations in other magnesium based systems; magnesium forms alloys with a large number of elements and, indeed a number of magnesium systems show good creep resistance. In this work, the Mg-Sn system has been chosen for study. The Mg-Sn system shows some positive characteristics in terms of potential creep resistance; a high temperature stable phase is formed with magnesium Mg2Sn (melting point: 770°C) and this phase forms as a line compound (71wt% Sn), which is typically distributed around the grain boundaries. The effect of the addition of a range of ternary elements on the microstructure and creep properties has been studied.

Influence of circumferential notch and fatigue crack on the mechanical integrity of biodegradable magnesium‐based alloy in simulated body fluid

Applications of magnesium alloys as biodegradable orthopaedic implants are critically dependent on the mechanical integrity of the implant during service. In this study, the mechanical integrity of an AZ91 magnesium alloy was studied using a constant extension rate tensile (CERT) method. The samples in two different geometries that is, circumferentially notched (CN), and circumferentially notched and fatigue cracked (CNFC), were tested in air and in simulated body fluid (SBF). The test results show that the mechanical integrity of the AZ91 magnesium alloy decreased substantially (∼50%) in both the CN and CNFC samples exposed to SBF. Fracture surface analysis revealed secondary cracks suggesting stress corrosion cracking susceptibility of the alloy in SBF.

Comparison of Corrosion Properties of Squeeze Cast and Thixocast MgZnRE Alloys

Thixocasting is a new semi-solid processing route for magnesium alloys; it is claimed that finer microstructures can be produced and as a consequence, better corrosion resistance can be achieved. Therefore, it is of great interest to compare the corrosion properties of two Mg-Zn-RE alloys produced by standard squeeze casting and new semi-solid casting technique. The influence of the two different processing routes and the replacement of rare earth elements by Ca additions on the corrosion behavior were studied in NaCl aqueous solutions by (a) analyzing the corrosion morphology, (b) measuring electrochemical polarization curves, and (c) carrying immersion tests at constant pH-value. Using light microscopy, scanning electron microscopy and X-ray diffraction, the corrosion results were related to the microstructures on the specific alloys. The results indicate that Ca cannot replace rare earth elements under corrosion aspects, but they also showed that the thixocasting process resulted in better corrosion resistance.

Corrosion Properties of Supersaturated Magnesium Alloy Systems

The range of applications for magnesium alloys is still limited due to their relatively poor corrosion behavior. In recent years, various new magnesium alloys were developed, some of them with improved corrosion properties, thus opening new fields of application. However, the number of alloying elements for the use in conventional cast processes is limited due to their interaction with liquid magnesium, other alloying elements or large differences in the melting temperatures. The possibilities for grain refinement by post-processing are also restricted. PVD techniques can help to produce supersaturated precipitation free and microcrystalline magnesium layers. Using ion beam and magnetron sputtering, binary or ternary Mg-Al, Mg-Ti and Mg-Sn alloy systems as well as standard alloys (AM50, AZ91 and AE42) were deposited on silicon and on magnesium substrates. The effect of the microstructure on the corrosion properties was studied by comparing as cast material and PVD coatings using potentiodynamic polarization, linear polarization resistance, and electrochemical impedance techniques.

Mechanical Properties and Stress Corrosion Cracking Behaviour of AZ31 Magnesium Alloy Laser Weldments

An AZ31 HP magnesium alloy was laser beam welded in autogenous mode with AZ61 filler using Nd-YAG laser system. Microstructural examination revealed that the laser beam weld metals obtained with or without filler material had an average grain size of about 12 μm. The microhardness and the tensile strength of the weldments were similar to those of the parent alloy. However, the stress corrosion cracking (SCC) behaviour of both the weldments assessed by slow strain rate tensile (SSRT) tests in ASTM D1384 solution was found to be slightly inferior to that of the parent alloy. It was observed that the stress corrosion cracks originated in the weld metal and propagated through the weld metal-HAZ regions in the autogenous weldment. On the other hand, in the weldment obtained with AZ61 filler material, the crack initiation and propagation was in the HAZ region. The localized damage of the magnesium hydroxide/oxide film formed on the surface of the specimens due to the exposure to the corrosive environment during the SSRT tests was found to be responsible for the SCC.

A study of degradation resistance and cytocompatibility of super-hydrophobic coating on magnesium

Calcium stearate based super-hydrophobic coating was deposited on plasma electrolytic oxidation (PEO) pre-treated magnesium substrate. The pre-treated magnesium and super-hydrophobic coating covered sample were characterized by scanning electron microscopy, X-ray diffraction and electrochemical corrosion measurements. The cytocompatibility and degradation resistance of magnesium, pre-treated magnesium and super-hydrophobic coating were analysed in terms of cell adhesion and osteoblast differentiation. The results indicate that the calcium stearate top coating shows super-hydrophobicity and that the surface is composed of micro/nanostructure. The super-hydrophobic coating covered sample shows higher barrier properties compared with the PEO pre-treated magnesium and bare magnesium. Human osteoblast proliferation, but not differentiation is enhanced by the PEO coating. Contrary, the super-hydrophobic coating reduces proliferation, but enhances differentiation of osteoblast, observable by the formation of hydroxyapatite. The combination of corrosion protection and cell reaction indicates that this system could be interesting for biomedical applications.

Properties of Sintered Mg Alloys for Biomedical Applications

In addition to the use as light weight construction material, magnesium alloys are also very suitable for future orthopaedic and traumatology applications. Common permanent implant materials such as titanium or stainless steel still suffer from stress shielding problems, causing bone resorption and implant loosening. In contrast, magnesium alloys provide elastic moduli and strengths matching those of cortical bone. In order to support osseointegration and vascularisation, an open porous surface structure of an Mg-implant is advantageous. The powder metallurgical processing route of Mg-alloys enables the generation of such parts. Powder blends with different sintering behaviour were produced via mixing pure Mg-powder with different Ca containing master alloy powders (MAP). As a result, sintering of these Mg alloy powders and blends became feasible. Sintered parts were investigated in view of shrinkage, porosity, grain size using SEM, EDX and XRD. In addition, compression tests were performed revealing ultimate compression strength up to 328 MPa, plastic compressibility of 22 % and compressive yield strength up to 90 MPa. Hence, the PM-route enables the production of parts with mechanical properties matching those of cortical bone.