Corrosion is normally an undesirable phenomenon in engineering applications. In the field of biomedical applications, however, implants that ‘biocorrode’ are of considerable interest. Deploying them not only abrogates the need for implant-removal surgery, but also circumvents the long-term negative effects of permanent implants1. In this context magnesium is an attractive biodegradable material, but its corrosion is accompanied by hydrogen evolution2, which is problematic in many biomedical applications. Whereas the degradation and thus the hydrogen evolution of crystalline Mg alloys can be altered only within a very limited range, Mg-based glasses offer extended solubility for alloying elements plus a homogeneous single-phase structure, both of which may alter corrosion behaviour significantly3,4. Here we report on a distinct reduction in hydrogen evolution in Zn-rich MgZnCa glasses. Above a particular Zn-alloying threshold (≈28 at.%), a Zn- and oxygen-rich passivating layer forms on the alloy surface, which we explain by a model based on the calculated Pourbaix diagram of Zn in simulated body fluid. We document animal studies that confirm the great reduction in hydrogen evolution and reveal the same good tissue compatibility as seen for crystalline Mg implants. Thus, the glassy Mg60+xZn35−xCa5 (0≤x≤7) alloys show great potential for deployment in a new generation of biodegradable implants.
This is a preview of subscription content
Subscribe to Journal
Get full journal access for 1 year
only $8.25 per issue
All prices are NET prices.
VAT will be added later in the checkout.
Tax calculation will be finalised during checkout.
Get time limited or full article access on ReadCube.
All prices are NET prices.
Erne, P., Schier, M. & Resink, T. J. The road to bioabsorbable stents: Reaching clinical reality? Cardiovasc. Inter. Rad. 29, 11–16 (2006).
Witte, F. et al. In vitro and in vivo corrosion measurements of magnesium alloys. Biomaterials 27, 1013–1018 (2006).
Song, G. L. & Atrens, A. Understanding magnesium corrosion—a framework for improved alloy performance. Adv. Eng. Mater. 5, 837–858 (2003).
Scully, J. R., Gebert, A. & Payer, J. H. Corrosion and related mechanical properties of bulk metallic glasses. J. Mater. Res. 22, 302–313 (2007).
Staiger, M. P., Pietak, A. M., Huadmai, J. & Dias, G. Magnesium and its alloys as orthopaedic biomaterials: A review. Biomaterials 27, 1728–1734 (2006).
Heublein, B. et al. Biocorrosion of magnesium alloys: A new principle in cardiovascular implant technology? Heart 89, 651–656 (2003).
Erbel, R. et al. Temporary scaffolding of coronary arteries with bioabsorbable magnesium stents: A prospective, non-randomised multicentre trial. Lancet 369, 1869–1875 (2007).
Hermawan, H., Alamdari, H., Mantovani, D. & Dubé, D. Iron–manganese: New class of metallic degradable biomaterials prepared by powder metallurgy. Powder Metall. 51, 38–45 (2008).
Peuster, M. et al. Long-term biocompatibility of a corrodible peripheral iron stent in the porcine descending aorta. Biomaterials 27, 4955–4962 (2006).
McBride, E. D. Magnesium screw and nail transfixation in fractures. South. Med. J. 31, 508–515 (1938).
Verbrugge, J. La tolérance du tissu osseux vis-à-vis du magnésium métallique. Presse Méd. 55, 1112–1114 (1933).
Verbrugge, J. Le matériel métallique résorbable en chirurgie osseuse. Presse Méd. 23, 460–465 (1934).
Witte, F. et al. In vivo corrosion of four magnesium alloys and the associated bone response. Biomaterials 26, 3557–3563 (2005).
Peeters, P., Bosiers, M., Verbist, J., Deloose, K. & Heublein, B. Preliminary results after application of absorbable metal stents in patients with critical limb ischemia. J. Endovasc. Ther. 12, 1–5 (2005).
Di Mario, C. et al. Drug-eluting bioabsorbable magnesium stent. J. Interv. Cardiol. 17, 391–395 (2004).
Song, G. L., Atrens, A. & StJohn, D. in Magnesium Technol. (ed. Hryn, J. N.) 255–262 (TMS, 2001).
Song, G. L. & Atrens, A. Corrosion mechanisms of magnesium alloys. Adv. Eng. Mater. 1, 11–33 (1999).
Inoue, A. in Bulk Amorphous Alloys, Preparation and Fundamental Characteristics (eds Magini, M. & Wohlbier, F. H.) (Trans Tech Publications, 1998).
Johnson, W. L. Bulk glass-forming metallic alloys: Science and technology. MRS Bull. 24, 42–56 (1999).
Löffler, J. F. Bulk metallic glasses. Intermetallics 11, 529–540 (2003).
Greer, A. L. & Ma, E. Bulk metallic glasses: At the cutting edge of metals research. MRS Bull. 32, 611–615 (2007).
Li, Y. et al. Formation of bulk metallic glasses and their composites. MRS Bull. 32, 624–628 (2007).
Greer, A. L. Metallic glasses... on the threshold. Mater. Today 12, 14–22 (2009).
Gu, X., Shiflet, G. J., Guo, F. Q. & Poon, S. J. Mg–Ca–Zn bulk metallic glasses with high strength and significant ductility. J. Mater. Res. 20, 1935–1938 (2005).
Zhao, Y. Y., Ma, E. & Xu, J. Reliability of compressive fracture strength of Mg–Zn–Ca bulk metallic glasses: Flaw sensitivity and Weibull statistics. Scr. Mater. 58, 496–499 (2008).
Zberg, B., Arata, E. R., Uggowitzer, P. J. & Löffler, J. F. Tensile properties of glassy MgZnCa wires and reliability analysis using Weibull statistics. Acta Mater. 57, 3223–3231 (2009).
Hänzi, A. C. et al. Design strategy for microalloyed ultra-ductile magnesium alloys. Phil. Mag. Lett. 89, 377–390 (2009).
Löffler, J. F., Kündig, A. A. & Dalla Torre, F. H. in Materials Processing Handbook (eds Groza, J. R., Shackelford, J. F., Lavernia, E. J. & Powers, M. T.) (CRC Press, 2007).
Müller, L. & Müller, F. A. Preparation of SBF with different HCO3− content and its influence on the composition of biomimetic apatites. Acta Biomater. 2, 181–189 (2006).
Rettig, R. & Virtanen, S. Composition of corrosion layers on a magnesium rare-earth alloy in simulated body fluids. J. Biomed. Mater. Res. A 88A, 359–369 (2009).
Hänzi, A. C., Sologubenko, A. S. & Uggowitzer, P. J. Design strategy for new bioabsorbable Mg–Y–Zn alloys for medical applications. Int. J. Mater. Res. 100, 1127–1136 (2009).
The authors are grateful for the support of the Swiss Innovation Promotion Agency (CTI Project 7616.2 LSPP-LS).
About this article
Cite this article
Zberg, B., Uggowitzer, P. & Löffler, J. MgZnCa glasses without clinically observable hydrogen evolution for biodegradable implants. Nature Mater 8, 887–891 (2009). https://doi.org/10.1038/nmat2542
Nature Communications (2022)
Corrosion, Corrosion Fatigue, and Protection of Magnesium Alloys: Mechanisms, Measurements, and Mitigation
Journal of Materials Engineering and Performance (2022)
Progress in Biomaterials (2022)
Journal of Materials Science (2022)
Metallurgical and Materials Transactions A (2022)