This paper explores the influence of selected commercial plasticizers structure, which are based on esters of citric acid, on mechanical and thermal properties of Poly(3-hydroxybutyrate)/Poly(lactic acid)/Plasticizer biodegradable blends. These plasticizers were first tested with respect to their miscibility with Poly(3-hydroxybutyrate)/Poly(lactic acid) (PHB/PLA) blends using a kneading machine. PHB/PLA/plasticizer blends in the weight ratio (wt %) of 60/25/15 were then prepared by single screw and corotating meshing twin screw extruders in the form of filament for further three-dimensional (3D) printing. Mechanical, thermal properties, and shape stability (warping effect) of 3D printed products can be improved just by the addition of appropriate plasticizer to polymeric blend. The goal was to create new types of eco-friendly PHB/PLA/plasticizers blends and to highly improve the poor mechanical properties of neat PHB/PLA blends (with majority of PHB) by adding appropriate plasticizer. Mechanical properties of plasticized blends were then determined by the tensile test of 3D printed test samples (dogbones), as well as filaments. Measured elongation at break rapidly enhanced from 21% for neat non-plasticized PHB/PLA blends (reference) to 328% for best plasticized blends in the form of filament, and from 5% (reference) to 187% for plasticized blends in the form of printed dogbones. The plasticizing effect on blends was confirmed by Modulated Differential Scanning Calorimetry. The study of morphology was performed by the Scanning Electron Microscopy. Significant problem of plasticized blends used to be also plasticizer migration, therefore the diffusion of plasticizers from the blends after 15 days of exposition to 110 °C in the drying oven was investigated as their measured weight loss. Almost all of the used plasticizers showed meaningful positive softening effects, but the diffusion of plasticizers at 110 °C exposition was quite extensive. The determination of the degree of disintegration of selected plasticized blend when exposed to a laboratory-scale composting environment was executed to roughly check the “biodegradability”.

This paper investigates the effect of plasticizer structure on especially the printability and mechanical and thermal properties of poly(3-hydroxybutyrate)-poly(lactic acid)-plasticizer biodegradable blends. Three plasticizers, acetyl tris(2-ethylhexyl) citrate, tris(2-ethylhexyl) citrate, and poly(ethylene glycol)bis(2-ethylhexanoate), were first checked whether they were miscible with poly(3-hydroxybutyrate)-poly(lactic acid) (PHB-PLA) blends using a kneading machine. PHB-PLA-plasticizer blends of 60-25-15 (wt.%) were then prepared using a corotating meshing twin-screw extruder, and a single screw extruder was used for filament preparation for further three-dimensional (3D) fused deposition modeling (FDM) printing. These innovative eco-friendly PHB-PLA-plasticizer blends were created with a majority of PHB, and therefore, poor mechanical properties and thermal properties of neat PHB-PLA blends were improved by adding appropriate plasticizer. The plasticizer also influences the printability of blends, which was investigated, based on our new specific printability tests developed for the optimization of printing conditions (especially printing temperature). Three-dimensional printed test samples were used for heat deflection temperature measurements and Charpy and tensile-impact tests. Plasticizer migration was also investigated. The macrostructure of 3D printed samples was observed using an optical microscope to check the printing quality and printing conditions. Tensile tests of 3D printed samples (dogbones), as well as extruded filaments, showed that measured elongation at break raised, from 21% for non-plasticized PHB-PLA reference blends to 84% for some plasticized blends in the form of filaments and from 10% (reference) to 32% for plasticized blends in the form of printed dogbones. Measurements of thermal properties (using modulated differential scanning calorimetry and oscillation rheometry) also confirmed the plasticizing effect on blends. The thermal and mechanical properties of PHB-PLA blends were improved by the addition of appropriate plasticizer. In contrast, the printability of the PHB-PLA reference seems to be slightly better than the printability of the plasticized blends.

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Tissue engineering is a current trend in the regenerative medicine putting pressure on scientists to develop highly functional materials and methods for scaffolds’ preparation. In this paper, the calibrated filaments for Fused Deposition Modeling (FDM) based on plasticized poly(3-hydroxybutyrate)/poly(d,l-lactide) 70/30 blend modified with tricalcium phosphate bioceramics were prepared. Two different plasticizers, Citroflex (n-Butyryl tri-n-hexyl citrate) and Syncroflex (oligomeric adipate ester), both used in the amount of 12 wt%, were compared. The printing parameters for these materials were optimized and the printability was evaluated by recently published warping test. The samples were studied with respect to their thermal and mechanical properties, followed by biological in vitro tests including proliferation, viability, and osteogenic differentiation of human mesenchymal stem cells. According to the results from differential scanning calorimetry and tensile measurements, the Citroflex-based plasticizer showed very good softening effect at the expense of worse printability and unsatisfactory performance during biological testing. On the other hand, the samples with Syncroflex demonstrated lower warping tendency compared to commercial polylactide filament with the warping coefficient one third lower. Moreover, the Syncroflex-based samples exhibited the non-cytotoxicity and promising biocompatibility.

In the presented work, poly(3-hydroxybutyrate)-PHB-based composites for 3D printing as bio-sourced and biodegradable alternatives to synthetic plastics are characterized. The PHB matrix was modified by polylactide (PLA) and plasticized by tributyl citrate. Kaolin particles were used as a filler. The mathematical method “Design of Experiment” (DoE) was used to create a matrix of samples for further evaluation. Firstly, the optimal printing temperature of the first and upper layers was determined. Secondly, the 3D printed samples were tested with regards to the warping during the 3D printing. Testing specimens were prepared using the determined optimal printing conditions to measure the tensile properties, impact strength, and heat deflection temperature (HDT) of the samples. The results describe the effect of adding individual components (PHB, PLA, plasticizer, and filler) in the prepared composite sample on the resulting material properties. Two composite samples were prepared based on the theoretical results of DoE (one with the maximum printability and one with the maximum HDT) to compare them with the real data measured. The tests of these two composite samples showed 25% lower warping and 8.9% higher HDT than was expected by the theory.