Fabrication and characterization of biodegradable zinc matrix composites reinforced by uniformly dispersed beta-tricalcium phosphate via graphene oxide-assisted hetero-agglomeration

Highlights: • β-TCP/Zn composites fabricated by a novel GO-assisted hetero-agglomeration method • Excellent dispersion property and 3D network of β-TCP was achieved. • ZnO as "pod" and β-TCP as "pea" formed a unique "snap pea"-like grain boundary. • Special corrosion mechanism suppress localized corrosion and reduced corrosion rate. • β-TCP addition results in good cytocompatibility and enhanced osteogenic activity. The development of biodegradable Zn matrix composites has been considered a promising approach to achieving enhanced mechanical properties, controllable degradation rate, good biocompatibility, and good osseointegration as orthopedic implants. However, scant literature regarding Zn matrix composites has been reported because of the great difficulty in dispersing the nano-sized bioactive reinforcements uniformly within the Zn matrix. In the present study, a novel and effective method were employed to obtain Zn matrix composites reinforced by uniformly dispersed beta-tricalcium phosphate (β-TCP) via graphene oxide (GO)-assisted hetero-agglomeration and subsequent spark plasma sintering process. A very low-content (0.04 vol%) few-layered GO was used as a coupling reagent to connect the Zn matrix and nano-sized TCP particles. In an appropriate polarity solvent, the negatively charged GO sheets could combine with both the positively charged Zn powder and TCP particles by electrostatic attraction and charge neutralization. Due to the nature of hetero-agglomeration, the flexible GO sheet could adhere to the large Zn powder and attracted a certain amount of TCP particles to form a Zn/GO/TCP sandwich structure by charge neutralization thereby forming a uniform dispersion of TCP particles within Zn matrix. After the spark plasma sintering (SPS) process, the TCP particles incorporated with very thin ZnO layers (thickness of a few dozen nanometers) formed a homogeneous and unique 3D network-like distribution in as-sintered TCP/Zn composites. A unique "snap pea"-like structure was confirmed at the grain boundary of α-Zn grains, which consisted of the TCP particles as "pea" and thin ZnO layer as "pod". Due to the uniform dispersion of bioactive TCP particles and unique structure of the TCP incorporating grain boundary, as-sintered 3TCP/Zn matrix composites possessed yield strength (YS) of 140.8 ± 7.7 MPa, failure strain of 36.0 ± 2.8%, the moderate degradation rate of 19.1 ± 3.3 μm·y⁻¹ and good cytocompatibility to MC3T3-E1 cells. Moreover, osteogenic differentiation activity evaluation revealed that the addition of TCP could significantly improve the expressions of the osteogenic differentiation-related gene (ALP) in MC3T3-E1 cells, thereby resulting in improved osteogenic capability. Therefore, biodegradable 3TCP/Zn matrix composites fabricated by GO-assisted hetero-agglomeration and subsequent SPS process could be a promising material as orthopedic implants.