Novel biocomposites of poly(L-lactide) (PLLA) and poly(l-lactide-co-glycolide) (PLLGA) with 10 wt.% of surface-modified hydroxyapatite particles, designed for applications in bone tissue engineering, are presented in this paper. The surface of hydroxyapatite (HAP) was modified with polyethylene glycol by using l-lysine as a linker molecule. The modification strategy fulfilled two important goals: improvement of the adhesion between the HAP surface and PLLA and PLLGA matrices, and enhancement of the osteological bioactivity of the composites. The surface modifications of HAP were confirmed by attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), TGA, and elemental composition analysis. The influence of hydroxyapatite surface functionalization on the thermal and in vitro biological properties of PLLA- and PLLGA-based composites was investigated. Due to HAP modification with polyethylene glycol, the glass transition temperature of PLLA was reduced by about 24.5 °C, and melt and cold crystallization abilities were significantly improved. These achievements were scored based on respective shifting of onset of melt and cold crystallization temperatures and 1.6 times higher melt crystallization enthalpy compared with neat PLLA. The results showed that the surface-modified HAP particles were multifunctional and can act as nucleating agents, plasticizers, and bioactive moieties. Moreover, due to the presented surface modification of HAP, the crystallinity degree of PLLA and PLLGA and the polymorphic form of PLLA, the most important factors affecting mechanical properties and degradation behaviors, can be controlled.

We present a comparison of the influence of the conditioning temperature of microspheres made of medical grade poly(L-lactide) (PLLA) and polylactide with 4 wt % of D-lactide content (PLA) on the thermal and structural properties. The microspheres were fabricated using the solid-in-oil-in-water method for applications in additive manufacturing. The microspheres were annealed below the glass transition temperature (T_g), above T_g but below the onset of cold crystallization, and at two temperatures selected from the range of cold crystallization corresponding to the crystallization of the α’ and α form of poly(L-lactide), i.e., at 40, 70, 90, and 120 °C, in order to verify the influence of the conditioning temperature on the sinterability of the microspheres set as the sintering window (SW). Based on differential scanning calorimetry measurements, the SWs of the microspheres were evaluated with consideration of the existence of cold crystallization and reorganization of crystal polymorphs. The results indicated that the conditioning temperature influenced the availability and range of the SWs depending on the D-lactide presence. We postulate the need for an individual approach for polylactide powders in determining the SW as a temperature range free of any thermal events. We also characterized other core powder characteristics, such as the residual solvent content, morphology, particle size distribution, powder flowability, and thermal conductivity, as key properties for successful laser sintering. The microspheres were close to spheres, and the size of the microspheres was below 100 µm. The residual solvent content decreased with the increase of the annealing temperature. The thermal conductivities were 0.073 and 0.064 W/mK for PLA and PLLA microspheres, respectively, and this depended on the spherical shape of the microspheres. The wide angle X-ray diffraction (WAXD) studies proved that an increase in the conditioning temperature caused a slight increase in the crystallinity degree for PLLA microspheres and a clear increase in crystallization for the PLA microspheres.

Comparison of the influence of conditioning temperature of microspheres made of medical grade poly(L-lactide) (PLLA) and polylactide with 4wt.% of D-lactide content (PLA), on its thermal and structural properties is presented. The microspheres were fabricated by solid-in-oil-in-water method for application in additive manufacturing. The microspheres were annealed below glass transition temperature (Tg), above Tg but below onset of cold crystallization, and at two temperatures selected from the range of cold crystallization corresponding to crystallization of α’ and α form of poly(L-lactide) respectively, i.e., at 40°C, 70°C, 90°C and 120°C, in order to verify the influence of conditioning temperatures on sinterability of microspheres set as sintering window (SW). Based on differential scanning calorimetry measurements SW of microspheres were evaluated with consideration of existence of cold crystallization and reorganization of crystal polymorph. The results indicate that the conditioning temperature influence on availability and range of SW that depending on the D-lactide presence. We postulate the need for an individual approach for polylactide powders in determining the SW as a temperature range free of any thermal events. Moreover, other core powder characteristic, such as residual solvent content, morphology, particle size distribution, powder flowability and thermal conductivity, as a key property for successful laser sintering, are characterized. The microspheres are close to sphere and the size of microspheres are below 100 µm. Residual solvents content decreases with the increase of annealing temperature. The thermal conductivity is 0.073 W/mK and 0.064 W/mK for PLA and PLLA microspheres, respectively, and it depends on the spherical shape of the microspheres. Furthermore, the WAXD studies prove that an increase in the conditioning temperature causes a slight increase in crystallinity degree for PLLA microspheres and clear increase in crystallization for PLA microspheres.