Reaction kinetics of dual setting α-tricalcium phosphate cements.

Addition of ductile polymers to calcium-deficient hydroxyapatite (CDHA)-forming bone cements based on α-tricalcium phosphate (α-TCP) is a promising approach to improve the mechanical performance of α-TCP cements and extend their application to load-bearing defects, which is else impeded by the brittleness of the hardened cement. One suitable polymer is poly-(2-hydroxyethylmethacrylate) (p-HEMA), which forms during cement setting by radical polymerisation of the monomer. In this study the hydration kinetics and the mechanical performance of α-TCP cements modified with addition of different HEMA concentrations (0-50 wt% in the cement liquid) was investigated by quantitative in situ XRD and four-point bending tests. Morphology of CDHA crystals was monitored by scanning electron microscopy. The hydration of α-TCP to CDHA was increasingly impeded and the visible crystal size of CDHA increasingly reduced with increasing HEMA concentration. Modification of the cements by adding 50 wt% HEMA to the cement liquid changed the brittle performance of the hardened cement to a pseudoplastic behaviour, reduced the flexural modulus and increased the work of fracture, while lower HEMA concentrations had no significant effect on these parameters. In such a composite, the extent of CDHA formation was considerably reduced (34.0 ± 1.8 wt% CDHA with 50 % HEMA compared to 54.1 ± 2.4 wt% CDHA in the reference formed after 48 h), while the general reaction kinetics were not changed. In conclusion, while the extent of CDHA formation was decreased, the mechanical properties were noticeably improved by addition of HEMA. Hence, α-TCP/HEMA composites might be suitable for application in some load-bearing defects and have adequate properties for mechanical treatment after implantation, like insertion of screws.

Fabrication and cytocompatibility of spherical magnesium ammonium phosphate granules.

Magnesium phosphate compounds, as for example struvite (MgNH4PO4·6H2O), have comparable characteristics to calcium phosphate bone substitutes, but degrade faster under physiological conditions. In the present work, we used a struvite forming calcium doped magnesium phosphate cement with the formulation Ca0.75Mg2.25(PO4)2 and an ammonium phosphate containing aqueous solution to produce round-shaped granules. For the fabrication of spherical granules, the cement paste was dispersed in a lipophilic liquid and stabilized by surfactants. The granules were characterized with respect to morphology, size distribution, phase composition, compressive strength, biocompatibility and solubility. In general, it was seen that small granules can hardly be produced by means of emulsification, when the raw material is a hydraulic paste, because long setting times promote coalescence of initially small unhardened cement droplets. Here, this problem was solved by using an aqueous solution containing both the secondary (NH4)2HPO4 and primary ammonium phosphates NH4H2PO4 to accelerate the setting reaction. This resulted in granules with 97 wt.% having a size in the range between 200 and 1,000 µm. The novel solution composition doubled the compressive strength of the cement to 37 ± 5 MPa without affecting either the conversion to struvite or the cytocompatibility using human fetal osteoblasts.