We report a joint analysis of positron annihilation lifetime spectroscopy (PALS), dielectric spectroscopy (BDS), and nuclear magnetic resonance (NMR) on cis-trans-1,4-poly(butadiene) (c-t-1,4-PBD). Phenomenological analysis of the orthopositronium lifetime τ(3)-T dependence by linear fitting reveals four characteristic PALS temperatures: T(b1)(G)=0.63T(g)(PALS), T(g)(PALS), T(b1)(L)=1.22T(g)(PALS), and T(b2)(L)=1.52T(g)(PALS). Slight bend effects in the glassy and supercooled liquid states are related to the fast or slow secondary β process, from neutron scattering, respectively, the latter being connected with the trans-isomers. In addition, the first bend effect in the supercooled liquid coincides with a deviation of the slow effective secondary β(eff) relaxation related to the cis-isomers from low-T Arrhenius behavior to non-Arrhenius one and correlates with the onset of the primary α process from BDS. The second plateau effect in the liquid state occurs when τ(3) becomes commensurable with the structural relaxation time τ(α)(T(b2)). It is also approximately related to its crossover from non-Arrhenius to Arrhenius regime in the combined BDS and NMR data. Finally, the combined BDS and NMR structural relaxation data, when analyzed in terms of the two-order parameter (TOP) model, suggest the influence of solidlike domains on both the annihilation behavior and the local and segmental chain mobility in the supercooled liquid. All these findings indicate the influence of the dynamic heterogeneity in both the primary and secondary relaxations due to the cis-trans isomerism in c-t-1,4-PBD and their impact into the PALS response.
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Chemistry
January 2025
Universite Claude Bernard Lyon 1, ICBMS, Bâtiment Lederer, 1 Rue Victor Grignard, F-69622, Villeurbanne, FRANCE.
In this article we describe research on the synthesis and characterization of a family of "Janus" amphiphiles composed of disaccharide head groups and alkaloid units joined together via a methylene linker, and bearing a lateral aliphatic chain of varying length. The condensed phases formed by self-organization of the products as a function of temperature were characterized by differential scanning calorimetry, thermal polarized light microscopy, and small angle X-ray scattering, allied with computational modelling and simulations. Structural studies on heating specimens from the solid showed that some homologues exhibited lamellar, columnar and bicontinuous mesophases, whereas the same homologues revealed different phase sequences on cooling from the amorphous liquid.
View Article and Find Full Text PDFAdv Mater
January 2025
Institute of Materials Physics, University of Münster, Wilhelm-Klemm-Str. 10, 48149, Münster, Germany.
As a phase change material (PCM), antimony exhibits a set of desirable properties that make it an interesting candidate for photonic memory applications. These include a large optical contrast between crystalline and amorphous solid states over a wide wavelength range. Switching between the states is possible on nanosecond timescales by applying short heating pulses.
View Article and Find Full Text PDFJ Phys Chem B
January 2025
Research Center for Advanced Science and Technology, The University of Tokyo, 4-6-1 Komaba, Meguro-ku, Tokyo 153-8904, Japan.
As a liquid is supercooled toward the glass transition point, its dynamics slow significantly, provided that crystallization is avoided. With increased supercooling, the particle dynamics become more spatially heterogeneous, a phenomenon known as dynamic heterogeneity. Since its discovery, this characteristic of metastable supercooled liquids has garnered considerable attention in glass science.
View Article and Find Full Text PDFNat Mater
January 2025
Department of Fundamental Engineering, Institute of Industrial Science, The University of Tokyo, Tokyo, Japan.
Supercooled liquids display sluggish dynamics, often attributed to their structural characteristics, yet the underlying mechanism remains elusive. Here we conduct numerical investigations into the structure-dynamics relationship in model glass-forming liquids, with a specific focus on an elementary particle rearrangement mode known as the 'T1 process'. We discover that the ability of a T1 process to preserve glassy structural order before and after is pivotal towards determining a liquid's fragility-whether it exhibits super-Arrhenius-like or Arrhenius-like behaviour.
View Article and Find Full Text PDFProc Natl Acad Sci U S A
January 2025
Department of Materials Science and Engineering, Stanford University, Stanford, CA 94305.
A central paradigm of nonequilibrium physics concerns the dynamics of heterogeneity and disorder, impacting processes ranging from the behavior of glasses to the emergent functionality of active matter. Understanding these complex mesoscopic systems requires probing the microscopic trajectories associated with irreversible processes, the role of fluctuations and entropy growth, and the timescales on which nonequilibrium responses are ultimately maintained. Approaches that illuminate these processes in model systems may enable a more general understanding of other heterogeneous nonequilibrium phenomena, and potentially define ultimate speed and energy cost limits for information processing technologies.
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