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International Journal of Bioprinting                       Scaffolds manufacturing by fused deposition modeling













































             Figure 2. Mechanical properties of the P(3HB-co-3HHx)/HA tensile specimens at different raster angles and compared to injection molding (IM). 58


            solidification to prevent high shear stress. The high shear   functional ester groups and with alkyl chains, the presence
            stress promotes chain breakage and reduces molecular   of distinct  functional groups promotes the formation of
            weight,  leading  to  a  diminishment  of  key  mechanical   various kind of crystals that melt at different temperatures,
            properties, as observed in PLA during injection molding. 68,69    resulting in three melting peaks between 108°C and
            In contrast, lower shear rates are necessary in an extrusion   162°C. This behavior in which three melting peaks appear
            process like the filament fabrication. Thus, the samples   in P(3HB-co-3HHx) was also reported by Farrag  et al.
            produced by additive manufacturing are subjected to a less   who proposed that the first melting peak is attributed to
            aggressive process in terms of shear rate. This is also why,   secondary lamellae melting, the second one to the primary
            in the absence of nHA, P(3HB-co-3HHx)-printed samples   lamellae melting, and the last one to the reorganization and
            maintained  greater tensile  strength  than  those  obtained   thickening of lamellae during heating.  Around 50°C, an
                                                                                              70
            by injection. Taking everything into account, the lack of   exothermic peak due to a cold crystallization process can
            depolymerization during 3D printing might compensate   be observed. Moreover, the change of baseline at 0°C–5°C
            for its detrimental induction of porosity.         is linked with the glass transition temperature. All these
                                                               temperatures were not qualitatively modified by the
            3.2 Thermal properties of the P(3HB-co-3HHx)/HA    introduction of nHA, which however has been reported
            nanocomposites                                     in the case of nanocomposites of PLA and nHA by other
            Figure 4 shows the DSC thermograms of P(3HB-co-3HHx)   authors. 71
            and its composites produced after each thermal cycle, i.e.,
            melt blending extrusion process (E), 3D printing filament   The different thermal cycles at which the 3D-printed
            fabrication (F), and 3D part printing (3D). In addition, the   samples were submitted promoted a difference in the
            temperatures at which the thermal transitions occurred   characteristic transition temperatures.  The biggest
            and their enthalpies are summarized in  Table  3. Given   differences emerged for the cold crystallization temperature,
            that P(3HB-co-3HHx) is a copolymer with two kinds of   which was reduced from 52.1°C for P(3HB-co-3HHx) after


            Volume 10 Issue 1 (2024)                       280                        https://doi.org/10.36922/ijb.0156
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