Effect of Water-Soluble Polymers on the Rheology and Microstructure of Polymer-Modified Geopolymer Glass-Ceramics.

This work explores the effects of rigid (0.1, 0.25, and 0.5 wt. %) and semi-flexible (0.5, 1.0, and 2.5 wt. %) all-aromatic polyelectrolyte reinforcements as rheological and morphological modifiers for preparing phosphate geopolymer glass-ceramic composites. Polymer-modified aluminosilicate-phosphate geopolymer resins were prepared by high-shear mixing of a metakaolin powder with 9M phosphoric acid and two all-aromatic, sulfonated polyamides. Polymer loadings between 0.5-2.5 wt. % exhibited gel-like behavior and an increase in the modulus of the geopolymer resin as a function of polymer concentration. The incorporation of a 0.5 wt. % rigid polymer resulted in a three-fold increase in viscosity relative to the control phosphate geopolymer resin. Hardening, dehydration, and crystallization of the geopolymer resins to glass-ceramics was achieved through mold casting, curing at 80 °C for 24 h, and a final heat treatment up to 260 °C. Scanning electron microscopy revealed a decrease in microstructure porosity in the range of 0.78 µm to 0.31 µm for geopolymer plaques containing loadings of 0.5 wt. % rigid polymer. Nano-porosity values of the composites were measured between 10-40 nm using nitrogen adsorption (Brunauer-Emmett-Teller method) and transmission electron microscopy. Nanoindentation studies revealed geopolymer composites with Young's modulus values of 15-24 GPa and hardness values of 1-2 GPa, suggesting an increase in modulus and hardness with polymer incorporation. Additional structural and chemical analyses were performed via thermal gravimetric analysis, Fourier transform infrared radiation, X-ray diffraction, and energy dispersive spectroscopy. This work provides a fundamental understanding of the processing, microstructure, and mechanical behavior of water-soluble, high-performance polyelectrolyte-reinforced geopolymer composites.

Isocyanate- and solvent-free synthesis of melt processible polyurea elastomers derived from urea as a monomer.

Polyurea elastomers are utilized for a myriad of applications ranging from coatings and foams to dielectric materials for capacitors and actuators. However, current synthetic methods for polyureas rely on highly reactive isocyanates, solvents, and catalysts, which collectively pose serious safety considerations. This report details the synthesis and characterization of melt processible, poly(tetramethylene oxide) (PTMO)-based segmented polyurea elastomers utilizing an isocyanate-, solvent-, and catalyst-free approach. Dynamic mechanical analysis and differential scanning calorimetry suggested microphase separation between the hard and soft segments. Tensile analysis revealed high strain at break for all segmented copolymers between 340 and 770%, and tunable modulus between 0.76 and 29.5 MPa. Dielectric spectroscopy revealed that the composition containing 20 wt% hard segment offered the highest permittivity at 10.6 (1 kHz, 300 K) of the segmented copolymers, indicating potential as a dielectric elastomer.