Soft Matter
October 2024
We investigated the dynamics of nanocomposites prepared through mixing poly(methyl methacrylate) grafted FeO nanoparticles (PMMA--FeO) with poly(methyl acrylate) (PMA). A key feature here different from previous dynamics measurements of polymer nanocomposites is the different chemistry between the matrix polymer and the polymer grafts, which introduces chemical heterogeneity. Transmission electron microscopy shows clear evidence of nanoparticle clustering due to the poor miscibility between the bulk PMA and the bulk PMMA.
View Article and Find Full Text PDFRecent experimental studies have revealed a lack of universality in the extensional behavior of linear polymers, which is not envisioned by classical molecular theories. These surprising findings, particularly the sharp contrast between polymer melts and solutions, have catalyzed the development of new theoretical ideas, including the concept of friction reduction in highly stretched polymer melts. By presenting evidence from rheology and small-angle neutron scattering, this work shows that deformation-induced demixing, which is due to the viscoelastic asymmetry in binary mixtures, contributes to the observed nonuniversality.
View Article and Find Full Text PDFPolymers under nanoconfinement can exhibit large alterations in dynamics from their bulk values due to an interface effect. However, understanding the interface effect remains a challenge, especially in the ultrafine nanoconfinement region. In this work, we prepare new geometries with ultrafine nanoconfinement ∼10nm through controlled distributions of the crystalline phases and the amorphous phases of a model semi-crystalline polymer, i.
View Article and Find Full Text PDFPhys Rev Lett
February 2024
We unravel hydrogen bonding dynamics and their relationship with supramolecular relaxations of monohydroxy alcohols (MAs) at intermediate times. The rheological modulus of MAs exhibits Rouse scaling relaxation of G(t)∼t^{-1/2} switching to G(t)∼t^{-1} at time τ_{m} before their terminal time. Meanwhile, dielectric spectroscopy reveals clear signatures of new supramolecular dynamics matching with τ_{m} from rheology.
View Article and Find Full Text PDFAn associative polymer carries many stickers that can form reversible associations. For more than 30 years, the understanding has been that reversible associations change the shape of linear viscoelastic spectra by adding a rubbery plateau in the intermediate frequency range, at which associations have not yet relaxed and thus effectively act as crosslinks. Here, we design and synthesize new classes of unentangled associative polymers carrying unprecedentedly high fractions of stickers, up to eight per Kuhn segment, that can form strong pairwise hydrogen bonding of ∼20k_{B}T without microphase separation.
View Article and Find Full Text PDFRheo-dielectric spectroscopy is employed to investigate the effect of external shear on Debye-like relaxation of a model monohydroxy alcohol, i.e., the 2-ethyl-1-hexanol (2E1H).
View Article and Find Full Text PDFThe relaxation dynamics of polystyrene (PS)/silica nanocomposites after a large step deformation are studied by a combination of small-angle scattering techniques and rheology. Small-angle X-ray scattering measurements and rheology show clear signatures of nanoparticle aggregation that enhances the mechanical properties of the polymer nanocomposites (PNCs) in the linear viscoelastic regime and during the initial phase of stress relaxation along with accelerated relaxation dynamics. Small-angle neutron scattering experiments under the zero-average-contrast condition reveal, however, smaller structural anisotropy in the PNCs than that in the neat polymer matrix, as well as accelerated anisotropy relaxation.
View Article and Find Full Text PDF