We compare viscoelastic properties of several polystyrene solutions and melts with the same number of entanglements. It is demonstrated that the modulus and time can be shifted such that the linear viscoelastic properties are identical provided the number of entanglements are identical. However the nonlinear properties in strong extensional flow are different with polymer solutions showing markedly stronger extensional hardening than the corresponding melts. While increased chain extensibility for solutions may provide part of the explanation, it is demonstrated that other mechanisms are needed for a full explanation for the differences between solutions and melts.

Understanding the rheological properties of two-dimensional (2D) materials in suspension is critical for the development of various solution processing and manufacturing techniques. 2D carbides and nitrides (MXenes) constitute one of the largest families of 2D materials with >20 synthesized compositions and applications already ranging from energy storage to medicine to optoelectronics. However, in spite of a report on clay-like behavior, not much is known about their rheological response. In this study, rheological behavior of single- and multilayer TiCT in aqueous dispersions was investigated. Viscous and viscoelastic properties of MXene dispersions were studied over a variety of concentrations from colloidal dispersions to high loading slurries, showing that a multilayer MXene suspension with up to 70 wt % can exhibit flowability. Processing guidelines for the fabrication of MXene films, coatings, and fibers have been established based on the rheological properties. Surprisingly, high viscosity was observed at very low concentrations for solutions of single-layer MXene flakes. Single-layer colloidal solutions were found to exhibit partial elasticity even at the lowest tested concentrations (<0.20 mg/mL) due to the presence of strong surface charge and excellent hydrophilicity of MXene, making them amenable to fabrication at dilute concentrations. Overall, the findings of this study provide fundamental insights into the rheological response of this quickly growing 2D family of materials in aqueous environments as well as offer guidelines for processing of MXenes.

Since its inception, the tube model of polymer dynamics has undergone several modifications to account for observed experimental trends. One trend that has yet to be captured by a modified version of the tube model is the observed experimental difference between concentrated polymer solutions and polymer melts. We compare the nonlinear extensional rheology of a series of polystyrene solutions with wide concentration range between 10% and 100% (melt) in order to determine the key missing physics that can account for dilution effects. All the solutions studied have the same number of entanglements per chain, and are diluted in the same solvent (oligomeric styrene). We show that the difference in nonlinear rheological behavior between polystyrene melts reported by Bach et al.

We compare the linear and nonlinear rheological response of three entangled polystyrene solutions with the same concentration of polymer, but diluted using different solvents. The three solutions have exactly the same physical tube model parameters when normalized to the same time scale. Although the three solutions behave identically in small amplitude oscillatory shear flow, they behave markedly different in large strain extensional flow. The experimental observations presented here directly demonstrate that the tube model and its governing parameters are insufficient to describe the nonlinear rheological behavior of entangled polymer solutions. We introduce a new hypothesis that relates the observed nonlinear behavior of three different polymer solutions to the existence of nematic interactions between polymer–solvent and polymer–polymer molecules.

Supramolecular polymers are used in many applications such as adhesives, coatings, cosmetics, and printing. Characterizing the dynamics of such polymers is essential for tailoring user defined properties in products and applications. We present both linear and nonlinear rheological results for a model system of pure poly(n-butyl acrylate), PnBA, homopolymer and four PnBA-poly(acrylic acid), PnBA-PAA, copolymers with different number of AA side groups. The copolymers are synthesized via hydrolysis of the pure PnBA homopolymer. Therefore, all polymers studied have the same backbone length. The number of AA side groups (hydrogen bonding groups) after hydrolysis is determined from NMR measurements. We show that using the theoretical dependency * To whom correspondence should be addressed 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 of modulus and reptation time on the packing length, we can account for the changes in linear viscoelasticity due to transformation of nBA side groups to AA along the backbone. Assuming superposition holds and subtracting out the linear chain rheology from LVE, the hydrogen bonding contribution to LVE is exposed. Hydrogen bonding affects linear viscoelasticity at frequencies below the inverse reptation time. More specifically, the presence of hydrogen bonds causes G and G as a function of frequency to shift to a power law scaling of 0.5. Furthermore, the magnitude of G and G scales linearly with the number of hydrogen bonding groups. The nonlinear extensional rheology shows extreme strain hardening. The magnitude of extensional stress has a strongly nonlinear dependence on the number of hydrogen bonding groups. These results are aimed at uncovering the molecular influence of hydrogen bonding on linear and nonlinear rheology to aid future molecular synthesis and model development.