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.

• Keywords
• low viscosity, melt mixing, processing temperature, thermoplastic starch,
• Publication type
• Journal Article MeSH

Morphology, macro-, and micromechanical properties of novel poly(urethane-urea)/silica nanocomposites were analyzed by electron microscopy, dynamic mechanical thermal analysis, and microindentation. The studied nanocomposites were based on a poly(urethane-urea) (PUU) matrix filled by nanosilica, and were prepared from waterborne dispersions of PUU (latex) and SiO2. The loading of nano-SiO2 was varied between 0 (neat matrix) and 40 wt% in the dry nanocomposite. The prepared materials were all formally in the rubbery state at room temperature, but they displayed complex elastoviscoplastic behavior, spanning from stiffer elastomeric type to semi-glassy. Because of the employed rigid and highly uniform spherical nanofiller, the materials are of great interest for model microindentation studies. Additionally, because of the polycarbonate-type elastic chains of the PUU matrix, hydrogen bonding in the studied nanocomposites was expected to be rich and diverse, ranging from very strong to weak. In micro- and macromechanical tests, all the elasticity-related properties correlated very strongly. The relations among the properties that related to energy dissipation were complex, and were highly affected by the existence of hydrogen bonding of broadly varied strength, by the distribution patterns of the fine nanofiller, as well as by the eventual locally endured larger deformations during the tests, and the tendency of the materials to cold flow.

• Keywords
• aqueous polyurethane dispersion, mechanical properties, microindentation, nanocomposites, polyurethanes, silica,
• Publication type
• Journal Article 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.

• Keywords
• microindentation, micromechanical properties, poly(ε-caprolactone), polymer blends, structure–properties relations, thermoplastic starch,
• Publication type
• Journal Article MeSH