Poly(3-hydroxybutyrate) (PHB) and Polycaprolactone (PCL) Based Blends for Tissue Engineering and Bone Medical Applications Processed by FDM 3D Printing.

In the presented work, poly(3-hydroxybutyrate)-PHB-based composite blends for bone medical applications and tissue engineering are prepared and characterized. PHB used for the work was in two cases commercial and, in one case, was extracted by the chloroform-free route. PHB was then blended with poly(lactic acid) (PLA) or polycaprolactone (PCL) and plasticized by oligomeric adipate ester (Syncroflex, SN). Tricalcium phosphate (TCP) particles were used as a bioactive filler. Prepared polymer blends were processed into the form of 3D printing filaments. The samples for all the tests performed were prepared by FDM 3D printing or compression molding. Differential scanning calorimetry was conducted to evaluate the thermal properties, followed by optimization of printing temperature by temperature tower test and determination of warping coefficient. Tensile test, three-point flexural test, and compression test were performed to study the mechanical properties of materials. Optical contact angle measurement was conducted to determine the surface properties of these blends and their influence on cell adhesion. Cytotoxicity measurement of prepared blends was conducted to find out whether the prepared materials were non-cytotoxic. The best temperatures for 3D printing were 195/190, 195/175, and 195/165 °C for PHB-soap/PLA-SN, PHB/PCL-SN, and PHB/PCL-SN-TCP, respectively. Their mechanical properties (strengths ~40 MPa, moduli ~2.5 GPa) were comparable with human trabecular bone. The calculated surface energies of all blends were ~40 mN/m. Unfortunately, only two out of three materials were proven to be non-cytotoxic (both PHB/PCL blends).

Synthesis of Bio-Based Thermoset Mixture Composed of Methacrylated Rapeseed Oil and Methacrylated Methyl Lactate: One-Pot Synthesis Using Formed Methacrylic Acid as a Continual Reactant.

Methacrylated vegetable oils are promising bio-based polymerizable precursors for potential material application in several fields, such as coating technologies or 3D printing. The reactants' availability for their production is an enormous advantage, but the modified oils also exhibit high apparent viscosity values and poor mechanical properties. This work focuses on a way to produce oil-based polymerizable material precursors in a mixture with a viscosity modifier in a one-batch process. The required methacrylic acid for the modification of epoxidized vegetable oils can be obtained as a secondary product of the methacrylation of methyl lactate forming a polymerizable monomer along with the acid. This reaction results in a yield of over 98% of methacrylic acid. Epoxidized vegetable oil can be added into the same batch using acid for oil modification which results in the one-pot mixture of both methacrylated oil and methyl lactate. The structural verifications of products were provided via FT-IR, 1H NMR, and volumetric methods. This two-step reaction process produces a thermoset mixture with a lower apparent viscosity of 142.6 mPa·s in comparison with methacrylated oil exhibiting a value of 1790.2 mPa·s. Other physical-chemical properties of the resin mixture such as storage modulus (E' = 1260 MPa), glass transition temperature (Tg = 50.0 °C), or polymerization activation energy (17.3 kJ/mol) are enhanced in comparison with the methacrylated vegetable oil. The synthesized one-pot mixture does not require additional methacrylic acid due to the use of the one formed in the first step of the reaction, while the eventual thermoset mixture exhibits enhanced material properties compared to the methacrylated vegetable oil itself. Precursors synthesized in this work may find their purpose in the field of coating technologies, since these applications require detailed viscosity modifications.

Evaluation of the Properties of PHB Composite Filled with Kaolin Particles for 3D Printing Applications Using the Design of Experiment.

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.

Effects of Differing Monomer Compositions on Properties of P(3HB-co-4HB) Synthesized by Aneurinibacillus sp. H1 for Various Applications.

Films prepared from poly(3-hydroxybutyrate-co-4-hydroxybutyrate) copolymers produced by Aneurinibacillus sp. H1 using an automatic film applicator were homogeneous and had a defined thickness, which allowed a detailed study of physicochemical properties. Their properties were compared with those of a poly (3-hydroxybutyrate) homopolymer film prepared by the same procedure, which proved to be significantly more crystalline by DSC and XRD. Structural differences between samples had a major impact on their properties. With increasing 4-hydroxybutyrate content, the ductility and release rate of the model hydrophilic active ingredient increased significantly. Other observed properties, such as the release of the hydrophobic active substance, the contact angle with water and ethylene glycol, or the surface morphology and roughness, were also affected by the composition. The identified properties predetermine these copolymers for wide use in areas such as biomedicine or smart biodegradable packaging for food or cosmetics. The big advantage is the possibility of fine-tuning properties simply by changing the fermentation conditions.

FDM 3D Printed Composites for Bone Tissue Engineering Based on Plasticized Poly(3-hydroxybutyrate)/poly(d,l-lactide) Blends.

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.

Printability, Mechanical and Thermal Properties of Poly(3-Hydroxybutyrate)-Poly(Lactic Acid)-Plasticizer Blends for Three-Dimensional (3D) Printing.

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.

Effect of Selected Commercial Plasticizers on Mechanical, Thermal, and Morphological Properties of Poly(3-hydroxybutyrate)/Poly(lactic acid)/Plasticizer Biodegradable Blends for Three-Dimensional (3D) Print.

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".