This
paper focuses on an integrative “bricks-and-mortar”
approach involving bioactive glass nanoparticles (bricks) covalently
functionalized with a customized polymer (mortar) combined with the
freeze-casting process. With the aim of obtaining a macroporous composite
for bone substitution, composed of a spatially homogeneous assembly
of nanoscale objects, we establish a method for the systematic elaboration
of nanocomposite scaffolds. It was implemented through several steps
from the synthesis of functionalized poly(d,l-lactide) (PDLLA)
and SiO2–CaO binary bioactive glass nanoparticles
(diameter around 164 nm) to the unidirectional freeze-casting process.
The different stages include the first description of controlled PDLLA
(M
n 8400 g·mol–1) grafting onto bioactive glass nanoparticle surfaces, their fine
characterization and grafting quantification, and their mixing with
free PDLLA chains (83 400 g·mol–1) during
suspension formulation. This paper emphasizes the effect of the working
temperature during the freeze-casting process on the multiscale spatial
organization of resulting scaffolds such as the porosity morphology
(lamellar and tubular), size (from 30 to 380 μm), anisotropy,
and orientation. In addition to porosity, our results demonstrate
a rosary-like organization of PDLLA-grafted nanoparticles in pore
walls. The higher homogeneity in the spatial distribution of grafted
nanoparticles over the height of scaffolds and at a micron scale confirms
the validity of the “bricks-and-mortar” concept to prevent
or limit aggregation. In particular, this study highlights the correlation
between nanoparticle functionalization and mechanical properties,
especially the recovery rate after compression tests. These results
lay the foundation for the development of tunable materials for bone
substitution, via potential enhancement of bioactivity and cell colonization.