The influence of elongation-induced concentration fluctuations on segmental friction in polymer blends.

Recent 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. In the case of polystyrene/oligostyrene blends, demixing increases the effective glass transition temperature of the long chain, leading to an apparent friction enhancement. On the other hand, the opposite case is found for the polystyrene/poly(α-methylstyrene) blend. These results highlight the important influence of deformation-induced concentration fluctuations on polymer segmental friction.

Dynamics of polylactic acid under ultrafine nanoconfinement: The collective interface effect and the spatial gradient.

Polymers 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.e., the polylactic acid. The broadband dielectric spectroscopy measurements show that ultrafine nanoconfinement leads to a large elevation in the glass transition temperature and a strong increment in the polymer fragility index. Moreover, new relaxation time profile analyses demonstrate a spatial gradient that can be well described by either a single-exponential decay or a double-exponential decay functional form near the middle of the film with a collective interface effect. However, the dynamics at the 1-2 nm vicinity of the interface exhibit a power-law decay that is different from the single-exponential decay or double-exponential decay functional forms as predicted by theories. Thus, these results call for further investigations of the interface effect on polymer dynamics, especially for interfaces with perturbed chain packing.

Hydrogen Bonding Exchange and Supramolecular Dynamics of Monohydroxy Alcohols.

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. Interestingly, the characteristic time τ_{m} follows an Arrhenius-like temperature dependence over exceptionally wide temperatures and agrees well with the hydrogen bonding exchange time from nuclear magnetic resonance measurements. These observations demonstrate the presence of Rouse modes and active chain swapping of MAs at intermediate times. Moreover, detailed theoretical analyses point out explicitly that the hydrogen bonding exchange truncates the Rouse dynamics of the supramolecular chains and triggers the chain-swapping processes, supporting a recently proposed living polymer model.

Dynamics of Associative Polymers with High Density of Reversible Bonds.

An 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. We experimentally show that reversible bonds significantly slow down the polymer dynamics but nearly do not change the shape of linear viscoelastic spectra. This behavior can be explained by a renormalized Rouse model that highlights an unexpected influence of reversible bonds on the structural relaxation of associative polymers.

Molecular Mechanism of the Debye Relaxation in Monohydroxy Alcohols Revealed from Rheo-Dielectric Spectroscopy.

Rheo-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). Shear deformation leads to strong acceleration in the structural relaxation, the Debye relaxation, and the terminal relaxation of 2E1H. Moreover, the shear-induced reduction in structural relaxation time, τ_{α}, scales quadratically with that of Debye time, τ_{D}, and the terminal flow time, τ_{f}, suggesting a relationship of τ_{D}^{2}∼τ_{α}. Further analyses reveal τ_{D}^{2}/τ_{α} of 2E1H follows Arrhenius temperature dependence that applies remarkably well to many other monohydroxy alcohols with different molecular sizes, architectures, and alcohol types. These results cannot be understood by the prevailing transient chain model, and suggest a H-bonding breakage facilitated sub-supramolecular reorientation as the origin of Debye relaxation of monohydroxy alcohols, akin to the molecular mechanism for the terminal relaxation of unentangled "living" polymers.

Relaxation dynamics of deformed polymer nanocomposites as revealed by small-angle scattering and rheology.

The 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. In addition, the degrees of anisotropy reduction and relaxation dynamics acceleration increase with increasing nanoparticle loading. These results are in sharp contrast to the prevailing viewpoint of enhanced molecular deformation as the main mechanism for the mechanical enhancement in PNCs. Furthermore, the observed acceleration of stress relaxation and reduction in structural anisotropy point to two types of nonlinear effects in the relaxation dynamics of PNCs at large deformation.