Intra-Cycle Elastic Nonlinearity of Nitrogen-Doped Carbon Nanotube/Polymer Nanocomposites under Medium Amplitude Oscillatory Shear (MAOS) Flow

This study seeks to unravel the effect of carbon nanotube’s physical and chemical features on the final electrical and rheological properties of polymer nanocomposites thereof. Nitrogen-doped carbon nanotubes (N-CNTs) were synthesized over two different types of catalysts, i.e., Fe and Ni, employing chemical vapor deposition. Utilizing this technique, we were able to synthesize N-CNTs with significantly different structures. As a result, remarkable differences in the network structure of the nanotubes were observed upon mixing the N-CNTs in a polyvinylidene fluoride (PVDF) matrix, which, in turn, led to drastically different electrical and rheological properties. For instance, no enhancement in the electrical conductivity of poorly-dispersed (N-CNT)Ni/PVDF samples was observed even at high nanotube concentrations, whereas (N-CNT)Fe/PVDF nanocomposites exhibited an insulative behavior at 1.0 wt%, a semi-conductive behavior at 2.0 wt%, and a conductive behavior at 2.7 wt%. In terms of rheology, the most substantial differences in the viscoelastic behavior of the systems were distinguishable in the medium amplitude oscillatory shear (MAOS) region. The stress decomposition method combined with the evaluation of the elastic and viscous third-order Chebyshev coefficients revealed a strong intra-cycle elastic nonlinearity in the MAOS region for the poorly-dispersed systems in small frequencies; however, the well-dispersed systems showed no intra-cycle nonlinearity in the MAOS region. It was shown that the MAOS elastic nonlinearity of poorly-dispersed systems stems from the confinement of N-CNT domains between the rheometer’s plates for small gap sizes comparable with the size of the agglomerates. Moreover, the intra-cycle elastic nonlinearity of poorly-dispersed systems is frequency-dependent and vanished at higher frequencies. The correlation between the microstructure and viscoelastic properties under large shear deformations provides further guidance for the fabrication of high-performance 3D-printed electrically conductive nanocomposites with precisely controllable final properties for engineering applications.

Small and Medium Amplitude Oscillatory Shear Rheology of Model Branched Polystyrene (PS) Melts

Linear and nonlinear rheological properties of model comb polystyrenes (PS) with loosely to densely grafted architectures were measured under small and medium amplitude oscillatory shear (SAOS and MAOS) flow. This comb PS set had the same length of backbone and branches but varied in the number of branches from 3 to 120 branches. Linear viscoelastic properties of the comb PS were compared with the hierarchical model predictions. The model underpredicted zero-shear viscosity and backbone plateau modulus of densely branched comb with 60 or 120 branches because the model does not include the effect of side chain crowding. First- and third-harmonic nonlinearities reflected the hierarchy in the relaxation motion of comb structures. Notably, the low-frequency plateau values of first-harmonic MAOS moduli scaled with M w − 2 (total molecular weight), reflecting dynamic tube dilution (DTD) by relaxed branches. Relative intrinsic nonlinearity Q0 exhibited the difference between comb and bottlebrush via no low-frequency Q0 peak of bottlebrush corresponding to backbone relaxation, which is probably related to the stretched backbone conformation in bottlebrush.

Nonlinear electrical and rheological spectroscopies identify structural and supramolecular relaxations in a model peptide

Nonlinear dielectric and medium-amplitude oscillatory shear experiments resolve nearby relaxations that linear spectroscopies could not separate unambiguously.