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.