High-Strength Low-Alloy (HSLA) Mg–Zn–Ca Alloys with Excellent Biodegradation Performance

Abstract

This article deals with the development of fine-grained high-strength low-alloy (HSLA) magnesium alloys intended for use as biodegradable implant material. The alloys contain solely low amounts of Zn and Ca as alloying elements. We illustrate the development path starting from the high-Zn-containing ZX50 (MgZn5Ca0.25) alloy with conventional purity, to an ultrahigh-purity ZX50 modification, and further to the ultrahigh-purity Zn-lean alloy ZX10 (MgZn1Ca0.3). It is shown that alloys with high Zn-content are prone to biocorrosion in various environments, most probably because of the presence of the intermetallic phase Mg6Zn3Ca2. A reduction of the Zn content results in (Mg,Zn)2Ca phase formation. This phase is less noble than the Mg-matrix and therefore, in contrast to Mg6Zn3Ca2, does not act as cathodic site. A fine-grained microstructure is achieved by the controlled formation of fine and homogeneously distributed (Mg,Zn)2Ca precipitates, which influence dynamic recrystallization and grain growth during hot forming. Such design scheme is comparable to that of HSLA steels, where low amounts of alloying elements are intended to produce a very fine dispersion of particles to increase the material’s strength by refining the grain size. Consequently our new, ultrapure ZX10 alloy exhibits high strength (yield strength R p = 240 MPa, ultimate tensile strength R m = 255 MPa) and simultaneously high ductility (elongation to fracture A = 27%), as well as low mechanical anisotropy. Because of the anodic nature of the (Mg,Zn)2Ca particles used in the HSLA concept, the in vivo degradation in a rat femur implantation study is very slow and homogeneous without clinically observable hydrogen evolution, making the ZX10 alloy a promising material for biodegradable implants.