We modified native wheat starch using 15, 30, and 60 min of acid hydrolysis (AH). The non-modified and AH-modified starches were converted to highly homogeneous thermoplastic starches (TPSs) using our two-step preparation protocol consisting of solution casting and melt mixing. Our main objective was to verify if AH can decrease the processing temperature of TPS. All samples were characterized in detail by microscopic, spectroscopic, diffraction, thermomechanical, rheological, and micromechanical methods, including in situ measurements of torque and temperature during the final melt mixing step. The experimental results showed that (i) AH decreased the average molecular weight preferentially in the amorphous regions, (ii) the lower-viscosity matrix in the AH-treated starches resulted in slightly higher crystallinity, and (iii) all AH-modified TPSs with a less viscous amorphous phase and higher content of crystalline phase exhibited similar properties. The effect of the higher crystallinity predominated at a laboratory temperature and low deformations, resulting in slightly stiffer material. The effect of the lower viscosity dominated during the melt mixing, where the shorter molecules acted as a lubricant and decreased the in situ measured processing temperature. The AH-induced decrease in the processing temperature could be beneficial for energy savings and/or possible temperature-sensitive admixtures for TPS systems.

• Klíčová slova
• low viscosity, melt mixing, processing temperature, thermoplastic starch,
• Publikační typ
• časopisecké články MeSH

This work describes the preparation of highly homogeneous thermoplastic starches (TPS's) with the addition of 0, 5, or 10 wt.% of maltodextrin (MD) and 0 or 3 wt.% of TiO2 nanoparticles. The TPS preparation was based on a two-step preparation protocol, which consisted in solution casting (SC) followed by melt mixing (MM). Rheology measurements at the typical starch processing temperature (120 °C) demonstrated that maltodextrin acted as a lubricating agent, which decreased the viscosity of the system. Consequently, the in situ measurement during the MM confirmed that the torque moments and real processing temperatures of all TPS/MD systems decreased in comparison with the pure TPS. The detailed characterization of morphology, thermomechanical properties, and local mechanical properties revealed that the viscosity decrease was accompanied by a slight decrease in the system homogeneity. The changes in the real processing temperatures might be quite moderate (ca 2-3 °C), but maltodextrin is a cheap and easy-to-add modifier, and the milder processing conditions are advantageous for both technical applications (energy savings) and biomedical applications (beneficial for temperature-sensitive additives, such as antibiotics).

• Klíčová slova
• lower processing temperature, lower viscosity, maltodextrin modification, thermoplastic starch,
• Publikační typ
• časopisecké články MeSH

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.

• Klíčová slova
• microindentation, micromechanical properties, poly(ε-caprolactone), polymer blends, structure–properties relations, thermoplastic starch,
• Publikační typ
• časopisecké články MeSH