Biodegradable Thermoplastic Starch/Polycaprolactone Blends with Co-Continuous Morphology Suitable for Local Release of Antibiotics

We report a reproducible preparation and characterization of highly homogeneous thermoplastic starch/pol(ε-caprolactone) blends (TPS/PCL) with a minimal thermomechanical degradation and co-continuous morphology. These materials would be suitable for biomedical applications, specifically for the local release of antibiotics (ATB) from the TPS phase. The TPS/PCL blends were prepared in the whole concentration range. In agreement with theoretical predictions based on component viscosities, the co-continuous morphology was found for TPS/PCL blends with a composition of 70/30 wt.%. The minimal thermomechanical degradation of the blends was achieved by an optimization of the processing conditions and by keeping processing temperatures as low as possible, because higher temperatures might damage ATB in the final application. The blends’ homogeneity was verified by scanning electron microscopy. The co-continuous morphology was confirmed by submicron-computed tomography. The mechanical performance of the blends was characterized in both microscale (by an instrumented microindentation hardness testing; MHI) and macroscale (by dynamic thermomechanical analysis; DMTA). The elastic moduli of TPS increased ca four times in the TPS/PCL (70/30) blend. The correlations between elastic moduli measured by MHI and DMTA were very strong, which implied that, in the future studies, it would be possible to use just micromechanical testing that does not require large specimens.     

Orientation of Poly(ε-caprolactone) in Its Poly(vinyl chloride) Blends Crystallized under Strain: The Role of Strain Rate

The blends of high and low molecular weights poly(ε-caprolactone) (PCL) with poly(vinyl chloride (PVC) were prepared. The samples before and after the crystallization of PCL were uniaxially stretched to different draw ratios. The orientation features of PCL in a stretched crystalline PCL/PVC blend and crystallized from the amorphous PCL/PVC blends under varied strains were studied by wide-angle X-ray diffraction (WAXD). It was found that a uniaxial stretching of crystalline PCL/PVC blend with high molecular weight PCL results in the c-axis orientation along the stretching direction, as is usually done for the PCL bulk sample. For the stretched amorphous PCL/PVC blend samples, the crystallization of high molecular weight PCL in the blends under a draw ratio of λ = 3 with a strain rate of 6 mm/min leads to a ring-fiber orientation. In the samples with draw ratios of λ = 4 and 5, the uniaxial orientation of a-, b-, and c-axes along the strain direction coexist after crystallization of high molecular weight PCL. With a draw ratio of λ = 6, mainly the b-axis orientation of high molecular weight PCL is identified. For the low molecular weight PCL, on the contrary, the ring-fiber and a-axis orientations coexist under a draw ratio of λ = 3. The a-axis orientation decreases with the increase of draw ratio. When the λ reaches 5, only a poorly oriented ring-fiber pattern has been recognized. These results are different from the similar samples stretched at a higher strain rate as reported in the literatures and demonstrate the important role of strain rate on the crystallization behavior of PCL in its blend with PVC under strain.     

Temperature and Infill Density Effects on Thermal,Mechanical and Shape Memory Properties of Polylactic Acid/Poly(ε-caprolactone) Blends for 4D Printing

Polylactic acid (PLA)/poly(ε-caprolactone) (PCL) blends have exhibited good shape memory properties and degradable characteristics in various 4D printing fields such as biomedicine, flexible electronics, and soft robotics, where the service temperature fluctuates easily by environment temperature and polymer characteristics. In this work, printed PLA/PCL 4D samples with different infill densities were prepared by material extrusion printing of pre-extruded filaments and characterized under different temperatures. The results show that the microstructures of printed samples are not influenced by printing process and have similar unique orientation as that of filaments. The thermal properties are stable and show obvious phase transition temperatures, while the mechanical properties decrease slightly in low temperature region and then decrease rapidly when temperature is over 60 °C. The increase in infill density can further improve the storage modulus more than 40% and have no significant influence on the thermal properties. The printed samples also exhibit good shape memory performances with fast recovery speeds less than 22 s. Furthermore, a two-step model is provided to predict the effective modulus of printed PLA/PCL samples and agrees well with experimental data. The results prove that temperature and infill density have different influences on the thermal, mechanical and shape memory properties of PLA/PCL blends.     

New Segmented Poly(Thiourethane-Urethane)s Based on Poly(ε-Caprolactone)Diol Soft Segment: Synthesis and Characterization

New segmented poly(thiourethane-urethane)s (SPTURs) were synthesized by the reaction of 1,1′-methanediylbis (4-isocyanatocyclohexane) (Desmodur W^®, HMDI) and poly(ε-caprolactone)diol (PCL) and (methanediyldibenzene-4,1-diyl)dimethanethiol as nonconventional polymer chain extender. FTIR spectroscopy was used for the structural analysis of obtained polymers. The molecular weight distribution was examined by GPC chromatography. Based on the measured contact angles, free surface energy parameters were calculated. Thermal properties of polymers were examined by DSC and TGA, while viscoelastic properties were measured by DMTA. The tensile, adhesive and optical properties were also investigated for the obtained polymers. It was shown that SPTURs were transparent or partially transparent solids with high molar masses up to 84,300 Da. These polymers showed a good resistance to hydrolysis during incubation in Optylite^® physiological saline over 8 weeks. Obtained polymers possessed a tensile strength of up to 43.26 MPa, hardness of up to 96.25/59.00 Sh A/D and adhesion to copper of 14.66 MPa. The surface properties of the obtained polymers show that all obtained SPTURs were hydrophilic (CAs for water between 64.07° and 73.12°) with calculated SFE up to 46.69 mN/m.