Control of biodegradation of a Mg alloy in simulated body fluid

Mg alloy AZ31 is an attractive candidate for coronary artery stents, as it possesses excellent biocompatibility in human body and good mechanical properties. However, AZ31 magnesium alloys generally have poor corrosion resistance in the body environment. This paper reports on the early stages of an investigation into the corrosion mechanism and the morphology of corrosion of AZ31 in simulated body fluid (SBF). The investigation will also consider ways of improving corrosion resistance of this alloy in SBF through the use of ionic liquids. The results to date have shown that AZ31 suffers severe localized pitting corrosion in SBF. The pits mainly develop adjacent to the Al-Mn intermetallic second phase in the α matrix. Energy Dispersive X-Ray Spectroscopy results revealed the presence of Mg, O, Ca, and P in the layer of corrosion product. Treatment of the AZ31 alloy prior to corrosion testing in SBF with the ionic liquid trimethyl (butyl) phosphonium diphenyl phosphate (P1444DPP) produced some increase in the corrosion resistance of the alloy.

Biodegradable Mg-Zr-Ca alloys for bone implant materials

Mg–Zr–Ca alloys were developed for new biodegradable bone implant materials. The microstructure and mechanical property of the Mg–xZr–yCa [x=0·5, 1·0% and y=1·0, 2·0% (wt-% hereafter)] alloys were characterised by optical microscopy, compressive and hardness tests. The in vitro cytotoxicity of the alloys was assessed using osteoblast-like SaOS₂ cells. The corrosion behaviour of these alloys was evaluated by soaking the alloys in simulated body fluid (SBF) and modified minimum essential medium (MMEM). Results indicated that the mechanical properties of the Mg–Zr–Ca are in the range of the mechanical properties of natural bone. The corrosion rate and biocompatibility decreases with the increase in the Ca content in the Mg–Zr–Ca alloys. The solutions of SBF and MMEM with the immersion of the Mg–Zr–Ca alloys show strong alkalisation. The Zr addition to the Mg–Zr–Ca alloys leads to an increase in the corrosion resistance, compressive strength and the ductility of the alloys, and a decrease in the elastic modulus of the Mg–Zr–Ca alloys.

Mg-Zr-Sr alloys as biodegradable implant materials

Novel Mg–Zr–Sr alloys have recently been developed for use as biodegradable implant materials. The Mg–Zr–Sr alloys were prepared by diluting Mg–Zr and Mg–Sr master alloys with pure Mg. The impact of Zr and Sr on the mechanical and biological properties has been thoroughly examined. The microstructures and mechanical properties of the alloys were characterized using optical microscopy, X-ray diffraction and compressive tests. The corrosion resistance was evaluated by electrochemical analysis and hydrogen evolution measurement. The in vitro biocompatibility was assessed using osteoblast-like SaOS2 cells and MTS and haemolysis tests. In vivo bone formation and biodegradability were studied in a rabbit model. The results indicated that both Zr and Sr are excellent candidates for Mg alloying elements in manufacturing biodegradable Mg alloy implants. Zr addition refined the grain size, improved the ductility, smoothed the grain boundaries and enhanced the corrosion resistance of Mg alloys. Sr addition led to an increase in compressive strength, better in vitro biocompatibility, and significantly higher bone formation in vivo. This study demonstrated that Mg–xZr–ySr alloys with x and y ⩽5 wt.% would make excellent biodegradable implant materials for load-bearing applications.

Microstructures, mechanical properties and in vitro corrosion behaviour of biodegradable Mg-Zr-Ca alloys

The microstructures, mechanical properties, corrosion behaviour and biocompatibility of the Mg-Zr-Ca alloys have been investigated for potential use in orthopaedic applications. The microstructures of the alloys were examined using X-ray diffraction analysis, optical microscopy and scanning electron microscopy. The mechanical properties of Mg-Zr-Ca alloys were determined from compressive tests. The corrosion behaviour has been investigated using an immersion test and electrochemical measurement. The biocompatibility was evaluated by cell growth factor using osteoblast-like SaOS2 cell. The experimental results indicate that the hot-rolled Mg-Zr-Ca alloys exhibit much finer microstructures than the as-cast Mg-Zr-Ca alloys which show coarse microstructures. The compressive strength of the hot-rolled alloys is much higher than that of the as-cast alloys and the human bone, which would offer appropriate mechanical properties for orthopaedic applications. The corrosion resistance of the alloys can be enhanced significantly by hot-rolling process. Hot-rolled Mg-0.5Zr-1Ca alloy (wt %) exhibits the lowest corrosion rate among all alloys studied in this paper. The hot-rolled Mg-0.5Zr-1Ca and Mg-1Zr-1Ca alloys exhibit better biocompatibility than other studied alloys and possess advanced mechanical properties, corrosion resistance and biocompatibility, suggesting that they have a great potential to be good candidates for orthopaedic applications. © 2012 Springer Science+Business Media New York.

Ionic liquid pretreatment as a means to control the corrosion behavior of magnesium alloys in simulated body fluid

Recently, the use of magnesium alloys as metallic implant materials for biodegradable coronary artery stents has been steadily growing in interest. However, AZ31 magnesium alloys present poor corrosion resistance in the body environment. This work reports on the use of a treatment with low-toxicity IL Trimethyl (butyl) phosphonium diphenyl phosphate P₁₄₄₄DPP, which provides corrosion protection for magnesium alloy AZ31 in simulated body fluid (SBF). Before IL treatment, surface was cleaned by HNO₃ and H₃PO₄ acid pickling solution. The effect of ionic liquid treatment on the corrosion performance of magnesium alloys AZ31in simulated body fluid has been investigated by electrochemical tests and the observation of surface morphology. The results show that this IL treatment succeeded in increasing the corrosion resistance of AZ31 when exposed to SBF.

In vitro studying corrosion behaviour of biocorrodible Mg alloys

The idea of bioabsorbable/biocorrodible stents has gained increasing attention in the last decade. Permanent coronary stents, traditionally made from 316L grade stainless steel, are routinely used for the treatment of blocked arteries. However, these stents can cause complications such as restenosis, thrombosis and the need for the patient to undergo prolonged antiplatelet therapy. Biodegradable metal stents provide an opportunity for the stent to remain in place for a period to ensure restoration of function and then degrade through a carefully controlled bio-corrosion process. Among the number of potentially suitable materials, Magnesium alloys have shown great promise as a stent material due to their non-toxicity [1] and the corrosion rates attainable in biological environments. However, a carefully controlled corrosion process is essential in order to avoid hyper hydrogen generation and the fatal consequences that follow. In addition uniform corrosion is a basic requirement to maintain the mechanical integrity and load bearing characteristics. Work being undertaken in our laboratories focuses on controlling the corrosion behaviour of magnesium in a simulated biological environment in the presence of protein. In the investigation reported here the Mg alloy has been examined using Scanning Electrochemical Microscope (SECM) to visualize the corrosion process and identify the corrosion pattern. Complementary bulk electrochemical techniques (EIS and potentiodynamic polarization) have been used to acquire kinetic and mechanistic information. Early results obtained by SECM have revealed the tendency towards pitting corrosion in the early stages which subsequently develops in to filiform corrosion.

Nanofibrillar micelles and entrapped vesicles from biodegradable block copolymer/polyelectrolyte complexes in aqueous media

Here we report a viable route to fibrillar micelles and entrapped vesicles in aqueous solutions. Nanofibrillar micelles and entrapped vesicles were prepared from complexes of a biodegradable block copolymer poly(ethylene oxide)-block-poly(lactide) (PEO-b-PLA) and a polyelectrolyte poly(acrylic acid) (PAA) in aqueous media and directly visualized using cryogenic transmission electron microscopy (cryo-TEM). The self-assembly and the morphological changes in the complexes were induced by the addition of PAA/water solution into the PEO-b-PLA in tetrahydrofuran followed by dialysis against water. A variety of morphologies including spherical wormlike and fibrillar micelles, and both unilamellar and entrapped vesicles, were observed, depending on the composition, complementary binding sites of PAA and PEO, and the change in the interfacial energy. Increasing the water content in each [AA]/[EO] ratio led to a morphological transition from spheres to vesicles, displaying both the composition- and dilution-dependent micellar-to-vesicular morphological transitions.

Zirconium, calcium, and strontium contents in magnesium based biodegradable alloys modulate the efficiency of implant-induced osseointegration

Development of new biodegradable implants and devices is necessary to meet the increasing needs of regenerative orthopedic procedures. An important consideration while formulating new implant materials is that they should physicochemically and biologically mimic bone-like properties. In earlier studies, we have developed and characterized magnesium based biodegradable alloys, in particular magnesium-zirconium (Mg-Zr) alloys. Here we have reported the biological properties of four Mg-Zr alloys containing different quantities of strontium or calcium. The alloys were implanted in small cavities made in femur bones of New Zealand White rabbits, and the quantitative and qualitative assessments of newly induced bone tissue were carried out. A total of 30 experimental animals, three for each implant type, were studied, and bone induction was assessed by histological, immunohistochemical and radiological methods; cavities in the femurs with no implants and observed for the same period of time were kept as controls. Our results showed that Mg-Zr alloys containing appropriate quantities of strontium were more efficient in inducing good quality mineralized bone than other alloys. Our results have been discussed in the context of physicochemical and biological properties of the alloys, and they could be very useful in determining the nature of future generations of biodegradable orthopedic implants.

A Conducting-Polymer Platform with Biodegradable Fibers for Stimulation and Guidance of Axonal Growth

A biosynthetic platform composed of a conducting polypyrrole sheet embedded with unidirectional biodegradable polymer fibers is described (see image; scale bar = 50 µm). Such hybrid systems can promote rapid directional nerve growth for neuro-regenerative scaffolds and act as interfaces between the electronic circuitry of medical bionic devices and the nervous system.

Wet-Spun Biodegradable Fibers on Conducting Platforms: Novel Architectures for Muscle Regeneration

Novel biosynthetic platforms supporting ex vivo growth of partially differentiated muscle cells in an aligned linear orientation that is consistent with the structural requirements of muscle tissue are described. These platforms consist of biodegradable polymer fibers spatially aligned on a conducting polymer substrate. Long multinucleated myotubes are formed from differentiation of adherent myoblasts, which align longitudinally to the fiber axis to form linear cell-seeded biosynthetic fiber constructs. The biodegradable polymer fibers bearing undifferentiated myoblasts can be detached from the substrate following culture. The ability to remove the muscle cell-seeded polymer fibers when required provides the means to use the biodegradable fibers as linear muscle-seeded scaffold components suitable for in vivo implantation into muscle. These fibers are shown to promote differentiation of muscle cells in a highly organized linear unbranched format in vitro and thereby potentially facilitate more stable integration into recipient tissue, providing structural support and mechanical protection for the donor cells. In addition, the conducting substrate on which the fibers are placed provides the potential to develop electrical stimulation paradigms for optimizing the ex vivo growth and synchronization of muscle cells on the biodegradable fibers prior to implantation into diseased or damaged muscle tissue.

Cellulose-based biodegradable blends and composites regenerated from ionic liquids

This thesis presents the fabrication of biodegradable polymer blends and composites with the assistance of ionic liquids. The work included preparation and characterization of cellulose/PCL blend films, cellulose/ PCL-PDMS-PCL blend films, cellulose/ PVAL blend films and cellulose/clay composite films. An efficient and feasible approach of reducing plastic pollution was developed.