Dynamics in polymers with phase separated dynamic bonds: the case of a peculiar temperature dependence.

The topic of polymers with dynamic bonds (stickers) appears as an exciting and promising area of materials science, thanks to their attractive self-healable, recyclable, extremely tough, and super extensible properties. Polymers with phase separated dynamic bonds revealed several unique properties, but mechanisms controlling their viscoelastic properties remain poorly understood. In this work, we present a dynamic analysis of a model polymer system with phase separated hydrogen bonding functionalities. The results confirm that terminal relaxation in these systems is independent of polymer segmental dynamics and is instead controlled by structural relaxations in clusters of stickers. Detailed analysis revealed a surprising result: terminal relaxation time of these systems has weaker temperature dependence than that of structural relaxation in clusters, although the former is slower than the latter. Borrowing ideas from the field of block copolymers, we ascribed this unusual result to an LCST-like behavior for the miscibility of the stickers in the polymer matrix. The presented results and ideas deepen the understanding of the viscoelasticity for polymers with dynamic bonds, enabling intelligent design of functional materials with desired macroscopic properties.

Obtaining Ligand-Free Aqueous Au-Nanoparticles Using Reversible CsPbBr3 ↔ Au@CsPbBr3 Nanocrystal Transformation.

Water-hexane interfacial preparation of photostable Au@CsPbBr3 (Au@CPB) hybrid nanocrystals (NCs) from pure CsPbBr3 (CPB) NCs is reported, with the coexistence of exciton and localized surface plasmon resonance with equal dominance. This enables strong exciton-plasmon coupling in these plasmonic perovskite NCs where not only the photoluminescence is quenched intrinsically due to ultrafast charge separation, but also the light absorption property increases significantly, covering the entire visible region. Using a controlled interfacial strategy, a reversible chemical transformation between CPB and Au@CPB NCs is shown, with the simultaneous eruption of larger-size ligand-free aqueous Au nanoparticles (NPs). An adsorption-desorption mechanism is proposed for the reversible transformation, while the overgrowth reaction of the Au NPs passes through the Au aggregation intermediate. This study further shows that the plasmonic Au@CPB hybrid NCs as well as ligand-free Au NPs exhibit clear surface enhanced Raman scattering (SERS) effect of a commercially available probe molecule. Overall, the beautiful interfacial chemistry delivers two independent plasmonic materials, i.e., Au@CPB NCs and ligand-free aqueous Au NPs, which may find important implications in photocatalytic and biomedical applications.

Unravelling the Mechanism of Viscoelasticity in Polymers with Phase-Separated Dynamic Bonds.

Incorporation of dynamic (reversible) bonds within polymer structure enables properties such as self-healing, shape transformation, and recyclability. These dynamic bonds, sometimes refer as stickers, can form clusters by phase-segregation from the polymer matrix. These systems can exhibit interesting viscoelastic properties with an unusually high and extremely long rubbery plateau. Understanding how viscoelastic properties of these materials are controlled by the hierarchical structure is crucial for engineering of recyclable materials for various future applications. Here we studied such systems made from short telechelic polydimethylsiloxane chains by employing a broad range of experimental techniques. We demonstrate that formation of a percolated network of interfacial layers surrounding clusters enhances mechanical modulus in these phase-separated systems, whereas single chain hopping between the clusters results in macroscopic flow. On the basis of the results, we formulated a general scenario describing viscoelastic properties of phase-separated dynamic polymers, which will foster development of recyclable materials with tunable rheological properties.

Polymers with Dynamic Bonds: Adaptive Functional Materials for a Sustainable Future.

Polymeric materials play critical role in many current technologies. Among them, adaptive polymeric materials with dynamic (reversible) bonds exhibit unique properties and provide exciting opportunities for various future technologies. Dynamic bonds enable structural rearrangements in polymer networks in specific conditions. Replacement of a few covalent bonds by dynamic bonds can enhance polymeric properties, e.g., strongly improve the toughness and the adhesive properties of polymers. Moreover, they provide recyclability and enable new properties, such as self-healing and shape memory effects. We briefly overview new developments in the field of polymers with dynamic bonds and current understanding of their dynamic properties. We further highlight several examples of unique properties of polymers with dynamic bonds and provide our perspectives for them to be used in many current and future applications.

Exploring the Importance of Surface Diffusion in Stability of Vapor-Deposited Organic Glasses.

Stable glasses are formed during physical vapor deposition (PVD), through the surface-mediated equilibration process. Understanding surface relaxation dynamics is important in understanding the details of this process. Direct measurements of the surface relaxation times in molecular glass systems are challenging. As such, surface diffusion measurements have been used in the past as a proxy for the surface relaxation process. In this study, we show that the absence of enhanced surface diffusion is not a reliable predictor of reduced ability to produce stable glasses. To demonstrate, we have prepared stable glasses (SGs) from two structurally similar organic molecules, 1,3-bis(1-naphthyl)-5-(2-naphthyl)benzene (TNB) and 9-(3,5-di(naphthalen-1-yl)phenyl)anthracene (α,α-A), with similar density increase and improved kinetic stability as compared to their liquid-quenched (LQ) counterparts. The surface diffusion values of these glasses were measured both in the LQ and SG states below their glass transition temperatures ( Tgs) using gold nanorod probes. While TNB shows enhanced surface diffusion in both SG and LQ states, no significant surface Tg diffusion is observed on the surface of α,α-A within our experimental time scales. However, isothermal dewetting experiments on ultrathin films of both molecules below Tg indicate the existence of enhanced dynamics in ultrathin films for both molecules, indirectly showing the existence of an enhanced mobile surface layer. Both films produce stable glasses, which is another indication for the existence of the mobile surface layer. Our results suggest that lateral surface diffusion may not be a good proxy for enhanced surface relaxation dynamics required to produce stable glasses, and thus, other types of measurements to directly probe the surface relaxation times may be necessary.

Electrorheological Source of Nonlinear Dielectric Effects in Molecular Glass-Forming Liquids.

We have measured the dielectric relaxation spectra of eight glass-forming liquids in the presence of electric direct current (dc)-bias fields ranging from 100 to 500 kV/cm. For every sample, we observe two distinct field-induced effects: a reduction in the relaxation amplitude and an increase in the primary structural relaxation time that is associated with viscous flow. Whereas amplitude change is typical of the well-known dielectric saturation, the field-induced increase in viscosity is a source of nonlinear behavior that has been recognized only recently. We find that this electrorheological behavior occurs in all polar liquids of this study, and its magnitude is correlated with the field-induced change in thermodynamic entropy. It constitutes a significant source of nonlinear dielectric behavior, which occurs for both dc and alternating current fields.

Dynamics of glass-forming liquids. XIX. Rise and decay of field induced anisotropy in the non-linear regime.

For glycerol and three monohydroxy alcohols, we have measured the non-linear dielectric effects resulting from the application and removal of a high dc bias electric field. The field effects are detected by virtue of a small amplitude harmonic field, from which time resolved changes in the dielectric loss are derived. The changes in permittivity are dominated by modifications of the time constants (rather than amplitudes) which display two contributions: a heating-like decrease of relaxation times that originates from the time dependent field when the bias is switched on and off and a slowing down of the dynamics resulting from the field induced reduction of configurational entropy. As observed for the electro-optical Kerr effect, the rise of the entropy change is slower than its decay, a feature that we rationalize on the basis of the quadratic dependence of the entropy change on polarization. For glycerol, the observed steady state level of the field induced shift of the glass transition temperature (+84 mK) matches the expectation based on the entropy change and its impact on dynamics via the Adam-Gibbs relation (+88 mK). For the alcohols, these non-linear effects rise and decay on the time scales of the prominent dielectric Debye process, underscoring the relation of these features to polarization anisotropy, opposed to mechanical or enthalpy relaxation which are orders of magnitude faster in these systems. A model is discussed which captures the observed magnitudes as well as time dependences in a near quantitative fashion. It is demonstrated that the high bias field modifies the response of polarization to the ac field, including a temporary change in the low field susceptibility.

Dynamics of glass-forming liquids. XVIII. Does entropy control structural relaxation times?

We study the dielectric dynamics of viscous glycerol in the presence of a large bias field. Apart from dielectric saturation and polarization anisotropy, we observe that the steady state structural relaxation time is longer by 2.7% in the presence of a 225 kV/cm dc-field relative to the linear response counterpart, equivalent to a field induced glass transition (Tg) shift of +84 mK. This result compares favorably with the 3.0% time constant increase predicted on the basis of a recent report [G. P. Johari, J. Chem. Phys. 138, 154503 (2013)], where the field induced reduction of the configurational entropy translates into slower dynamics by virtue of the Adam-Gibbs relation. Other models of field dependent glass transition temperatures are also discussed. Similar to observations related to the electro-optical Kerr effect, the rise time of the field induced effect is much longer than its collapse when the field is removed again. The orientational relaxation time of the plastic crystal cyclo-octanol is more sensitive to a bias field, showing a 13.5% increase at a field of 150 kV/cm, equivalent to an increase of Tg by 0.58 K.

Nonlinear Dielectric Behavior of a Secondary Relaxation: Glassy D-Sorbitol.

We have studied the nonlinear dielectric behavior of a glass-forming liquid, D-sorbitol, with particular attention to its exceptionally intense Johari-Goldstein (JG) type secondary relaxation. It is found that this ß-relaxation displays significant nonlinear dielectric effects, but these differ qualitatively from their α-process counterparts. High fields increase the amplitudes of the secondary modes (rather than reducing their time constants), consistent with a field induced increase of fictive temperatures. This result implies that the amplitudes of the secondary modes fluctuate in the glassy state, consistent with MD simulations reported for a liquid displaying a JG relaxation. The nonlinear features of this secondary process are reminiscent of those found for the excess wing regime, suggesting that these two contributions to dynamics have common origins.

Limitations of heterogeneous models of liquid dynamics: very slow rate exchange in the excess wing.

For several molecular glass formers, the nonlinear dielectric effects (NDE's) are investigated for the so-called excess wing regime, i.e., for the relatively high frequencies between 10(2) and 10(7) times the peak loss frequency. It is found that significant nonlinear behavior persists across the entire frequency window of this study, and that its magnitude traces the temperature dependence of the activation energy. A time resolved measurement of the dielectric loss at fields up to 480 kV/cm across tens of thousands of periods reveals that it takes an unexpectedly long time for the steady state NDE to develop. For various materials and at different temperatures and frequencies, it is found that the average structural relaxation with time scale τα governs the equilibration of these fast modes that are associated with time constants τ which are up to 10(7) times shorter than τα. It is argued that true indicators of structural relaxation (such as rate exchange and aging) of these fast modes are slaved to macroscopic softening on the time scale of τα, and thus many orders of magnitude slower than the time constant of the mode itself.