In this work, we prepared highly swelling, stimuli-responsive hydrogels capable of the highly efficient adsorption of inorganic pollutants. The hydrogels were based on hydroxypropyl methyl cellulose (HPMC) grafted with acrylamide (AM) and 3-sulfopropyl acrylate (SPA) and were synthesized via the growth (radical polymerization) of the grafted copolymer chains on HPMC, which was activated by radical oxidation. These grafted structures were crosslinked to an infinite network by a small amount of di-vinyl comonomer. HPMC was chosen as a cheap hydrophilic and naturally sourced polymer backbone, while AM and SPA were employed to preferentially bond coordinating and cationic inorganic pollutants, respectively. All the gels displayed a pronounced elastic character, as well as considerably high values of stress at break (several hundred %). The gel with the highest fraction of the ionic comonomer SPA (with an AM/SPA ratio = 0.5) displayed the highest equilibrium swelling ratio (12,100%), the highest volume response to temperature and pH, and the fastest swelling kinetics, but also the lowest modulus. The other gels (with AM/SPA = 1 and 2) displayed several times higher moduli but more modest pH responses and only very modest temperature sensitivity. Cr(VI) adsorption tests indicated that the prepared hydrogels removed this species from water very efficiently: between 90 and 96% in one step. The hydrogels with AM/SPA ratios of 0.5 and 1 appeared to be promising regenerable (via pH) materials for repeated Cr(VI) adsorption.

Reversible Diels–Alder (DA) type networks were prepared from furan and maleimide monomers of different structure and functionality. The factors controlling the dynamic network formation and their properties were discussed. Evolution of structure during both dynamic nonequilibrium and isothermal equilibrium network formation/breaking was followed by monitoring the modulus and conversion of the monomer. The gelation, postgel growth, and properties of the thermoreversible networks from tetrafunctional furan (F4) and different bismaleimides (M2) were controlled by the structure of the maleimide monomer. The substitution of maleimides with alkyl (hexamethylene bismaleimide), aromatic (diphenyl bismaleimide), and polyether substituents affects differently the kinetics and thermodynamics of the thermoreversible DA reaction, and thereby the formation of dynamic networks. The gel-point temperature was tuned in the range T_gel = 97–122 °C in the networks of the same functionality (F4-M2) with different maleimide structure. Theory of branching processes was used to predict the structure development during formation of the dynamic networks and the reasonable agreement with the experiment was achieved. The experimentally inaccessible information on the sol fraction in the reversible network was received by applying the theory. Based on the acquired results, the proper structure of a self-healing network was designed.

This work is focused on the comparison of macro-, micro- and nanomechanical properties of a series of eleven highly homogeneous and chemically very similar polymer networks, consisting of diglycidyl ether of bisphenol A cured with diamine terminated polypropylene oxide. The main objective was to correlate the mechanical properties at multiple length scales, while using very well-defined polymeric materials. By means of synthesis parameters, the glass transition temperature (T_g) of the polymer networks was deliberately varied in a broad range and, as a result, the samples changed their mechanical behavior from very hard and stiff (elastic moduli 4 GPa), through semi-hard and ductile, to very soft and elastic (elastic moduli 0.006 GPa). The mechanical properties were characterized in macroscale (dynamic mechanical analysis; DMA), microscale (quasi-static microindentation hardness testing; MHI) and nanoscale (quasi-static and dynamic nanoindentation hardness testing; NHI). The stiffness-related properties (i.e., storage moduli, indentation moduli and indentation hardness at all length scales) showed strong and statistically significant mutual correlations (all Pearson′s correlation coefficients r > 0.9 and corresponding p-values < 0.001). Moreover, the relations among the stiffness-related properties were approximately linear, in agreement with the theoretical prediction. The viscosity-related properties (i.e., loss moduli, damping factors, indentation creep and elastic work of indentation at all length scales) reflected the stiff-ductile-elastic transitions. The fact that the macro-, micro- and nanomechanical properties exhibited the same trends and similar values indicated that not only dynamic, but also quasi-static indentation can be employed as an alternative to well-established DMA characterization of polymer networks.

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.

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.