RESUMEN
The proposed strategy for the extrusion of printable composite filaments follows the favourable association of biogenic hydroxyapatite (HA) and graphene nanoplatelets (GNP) as reinforcement materials for a poly(lactic acid) (PLA) matrix. HA particles were chosen in the <40 µm range, while GNP were selected in the micrometric range. During the melt-mixing incorporation into the PLA matrix, both reinforcement ratios were simultaneously modulated for the first time at different increments. Cylindrical composite pellets/test samples were obtained only for the mechanical and wettability behaviour evaluation. The Fourier-transformed infrared spectroscopy depicted two levels of overlapping structures due to the solid molecular bond between all materials. Scanning electron microscopy and surface wettability and mechanical evaluations vouched for the (1) uniform/homogenous dispersion/embedding of HA particles up to the highest HA/GNP ratio, (2) physical adhesion at the HA-PLA interface due to the HA particles' porosity, (3) HA-GNP bonding, and (4) PLA-GNP synergy based on GNP complete exfoliation and dispersion into the matrix.
RESUMEN
The successful regeneration of large-size bone defects remains one of the most critical challenges faced in orthopaedics. Recently, 3D printing technology has been widely used to fabricate reliable, reproducible and economically affordable scaffolds with specifically designed shapes and porosity, capable of providing sufficient biomimetic cues for a desired cellular behaviour. Natural or synthetic polymers reinforced with active bioceramics and/or graphene derivatives have demonstrated adequate mechanical properties and a proper cellular response, attracting the attention of researchers in the bone regeneration field. In the present work, 3D-printed graphene nanoplatelet (GNP)-reinforced polylactic acid (PLA)/hydroxyapatite (HA) composite scaffolds were fabricated using the fused deposition modelling (FDM) technique. The in vitro response of the MC3T3-E1 pre-osteoblasts and RAW 264.7 macrophages revealed that these newly designed scaffolds exhibited various survival rates and a sustained proliferation. Moreover, as expected, the addition of HA into the PLA matrix contributed to mimicking a bone extracellular matrix, leading to positive effects on the pre-osteoblast osteogenic differentiation. In addition, a limited inflammatory response was also observed. Overall, the results suggest the great potential of the newly developed 3D-printed composite materials as suitable candidates for bone tissue engineering applications.
RESUMEN
Additive manufacturing or 3D printing technologies might advance the fabrication sector of personalised biomaterials with high-tech precision. The selection of optimal precursor materials is considered the first key-step for the development of new printable filaments destined for the fabrication of products with diverse orthopaedic/dental applications. The selection route of precursor materials proposed in this study targeted two categories of materials: prime materials, for the polymeric matrix (acrylonitrile butadiene styrene (ABS), polylactic acid (PLA)); and reinforcement materials (natural hydroxyapatite (HA) and graphene nanoplatelets (GNP) of different dimensions). HA was isolated from bovine bones (HA particles size < 40 µm, <100 µm, and >125 µm) through a reproducible synthesis technology. The structural (FTIR-ATR, Raman spectroscopy), morphological (SEM), and, most importantly, in vitro (indirect and direct contact studies) features of all precursor materials were comparatively evaluated. The polymeric materials were also prepared in the form of thin plates, for an advanced cell viability assessment (direct contact studies). The overall results confirmed once again the reproducibility of the HA synthesis method. Moreover, the biological cytotoxicity assays established the safe selection of PLA as a future polymeric matrix, with GNP of grade M as a reinforcement and HA as a bioceramic. Therefore, the obtained results pinpointed these materials as optimal for future composite filament synthesis and the 3D printing of implantable structures.
RESUMEN
Calcium phosphates (CPs) used as biomaterials have been intensively studied in recent years. In most studies, the determination of the chemical composition is mandatory. Due to the versatility and possibilities of performing qualitative and quantitative compositional analyses, energy dispersive spectrometry (EDS) is a widely used technique in this regard. The range of calcium phosphates is very diverse, the first method of approximating the type of compound being EDS microanalysis, by assessing the atomic Ca/P ratio. The value of this ratio can be influenced by several factors correlated with instrumental parameters and analysed samples. This article highlights the influence of the electron beam acceleration voltage (1 kV-30 kV) and of the particle size of calcium phosphate powders on the EDS analysis results. The characterised powders were obtained from bovine bones heat-treated at 1200 °C for 2 h, which have been ground and granulometrically sorted by mechanical vibration. The granulometric sorting generated three types of samples, with particle sizes < 20 µm, < 40 µm and < 100 µm, respectively. These were morphologically and dimensionally analysed by scanning electron microscopy (SEM) and compositionally by EDS, after the spectrometer was calibrated with a standard reference material (SRM) from NIST (National Institute of Standards and Technology). The results showed that the adjusting of acceleration voltage and of the powder particle size significantly influences the spectrum profile and the results of EDS analyses, which can lead to an erroneous primary identification of the analysed calcium phosphate type.
