Dynamic Heterogeneity in Fully Miscible Blends of Polystyrene with Oligostyrene

Binary blends of polystyrene with oligostyrene are perfectly miscible (χ=0) yet dynamically heterogeneous. This is evidenced by independent probing of the dipole relaxation perpendicular to the backbone by dielectric spectroscopy and molecular dynamics. The self-concentration model with a single intra-molecular length scale qualitatively describes the slower segmental dynamics. A quantitative comparison based on MD however, requires a composition-dependent length scale. The pertinent dynamic length scale that best describes the slow segmental dynamics in miscible blends relates to both intra- and inter-molecular contributions

Nondestructive high-throughput screening of nanopore geometry in porous membranes by imbibition

A fluid dynamic model for imbibition into closed-end, axisymmetric pores having diameters that change as a function of the pore depth is presented. Despite the fact that liquid invasion into nonbranched closed-end pores is characterized by a wealth of different transient and/or metastable nonequilibrium stages related to precursor film formation, we show that a simple hydraulic model accounting for geometry- and air compression-induced deviations from classical Lucas-Washburn dynamics precisely describes the imbibition dynamics except at the late stage. The model was validated by laser interferometry experiments with submillisecond temporal resolution. Imbibition of three simple liquids (isopropanol, ethanol, and hexane) into self-ordered anodic alumina membranes containing arrays of parallel closed-end nanopores characterized by slight conicity was studied. The model provides an improved description of nanoscale fluid dynamics and allows geometric characterization of nanoporous membranes by their imbibition kinetics accounting for the back pressure of the compressed gas. Thus, a precise calibration of porous membranes with simple liquids becomes possible, and changes in the mean pore diameter as a function of the pore depth can be assessed.Fil: Cencha, Luisa Guadalupe. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Física del Litoral. Universidad Nacional del Litoral. Instituto de Física del Litoral; ArgentinaFil: Huber, Patrick. Hamburg University Of Technology;Fil: Kappl, Michael. Max-planck-institut Für Polymerforschung;Fil: Floudas, George. Panepistimion Ioanninon;Fil: Steinhart, Martin. Max-planck-institut Für Polymerforschung;Fil: Berli, Claudio Luis Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; ArgentinaFil: Urteaga, Raul. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Física del Litoral. Universidad Nacional del Litoral. Instituto de Física del Litoral; Argentin

Building Bridges by Blending: Morphology and Mechanical Properties of Binary Tapered Diblock/Multiblock Copolymer Blends

This work explores the scope and limitations of enhancing the poor mechanical properties of diblock copolymers by blending with tapered multiblock copolymers of styrene (S) and isoprene (I), P(I‐co‐S)n. Blending of different tapered diblock copolymers (n = 1; Mn = 80 and 240 kg mol⁻¹, 50 wt% polyisoprene (PI) units, lamellar morphologies) affords brittle materials with low elongation at break. An increasing degree of phase separation from (i) miscible P(I‐co‐S)/P(I‐co‐S)n copolymer blends, to (ii) partially miscible and (iii) finally immiscible blends is studied. The effect of miscibility on the mechanical properties is studied for two diblock copolymers (Mn = 80 and 240 kg mol⁻¹, domain spacing of 38 and 77 nm, respectively), blended with a series of multiblock copolymers P(I‐co‐S)n (n = 2–5; domain spacing of 42 to 20 nm) of similar molecular weight. Increasing disparity in the domain spacing results in partially miscible and finally immiscible blends. Immiscibility causes lower elongation at break, albeit superior tensile properties compared to the pure tapered diblock copolymers are maintained. The study shows that the addition of a minor fraction of multiblock copolymers to diblock copolymers is a versatile method toward improved mechanical properties, while retaining an ordered nanophase‐separated morphology

An analysis and evaluation of the WeFold collaborative for protein structure prediction and its pipelines in CASP11 and CASP12

Every two years groups worldwide participate in the Critical Assessment of Protein Structure Prediction (CASP) experiment to blindly test the strengths and weaknesses of their computational methods. CASP has significantly advanced the field but many hurdles still remain, which may require new ideas and collaborations. In 2012 a web-based effort called WeFold, was initiated to promote collaboration within the CASP community and attract researchers from other fields to contribute new ideas to CASP. Members of the WeFold coopetition (cooperation and competition) participated in CASP as individual teams, but also shared components of their methods to create hybrid pipelines and actively contributed to this effort. We assert that the scale and diversity of integrative prediction pipelines could not have been achieved by any individual lab or even by any collaboration among a few partners. The models contributed by the participating groups and generated by the pipelines are publicly available at the WeFold website providing a wealth of data that remains to be tapped. Here, we analyze the results of the 2014 and 2016 pipelines showing improvements according to the CASP assessment as well as areas that require further adjustments and research

P(VDF-TrFE) Copolymer Dynamics as a Function of Temperature and Pressure in the Vicinity of the Curie Transition

We report on the phase behavior and the respective dynamics in random P(VDF-TrFE) copolymers using standard and temperature-modulated differential scanning calorimetry, X-ray diffraction, and a combination of temperature- and pressure-dependent dielectric spectroscopy measurements. Depending on the copolymer composition, the coexistence of three/four weakly ordered phases was identified in the vicinity of the Curie transition (Tc). With respect to the dynamics, we demonstrate that the segmental dynamics associated with the relaxation of constrained amorphous VDF segments at the crystal/amorphous "phase"can be used as a marker of the Curie transition. The corresponding segmental relaxation freezes at about 50 K above the lower liquid-to-glass temperature associated with the freezing of amorphous segments away from the interface. Pressure-dependent dielectric measurements provided quantitative insight into (i) the molecular origin of the segmental processes (by employing the pressure sensitivity of relaxation times and the pressure coefficient of the respective Tg's), (ii) the nature of the phase transition at Tc, and (iii) information about the stability of phases under the variation of temperature and pressure (through the T-P phase diagram). We show that Tc increases linearly with pressure and is accompanied by small volume changes, implying a weakly first-order thermodynamic transition. Furthermore, pressure stabilizes the ferroelectric phase over a broader temperature range. This could extend the operating temperature range of ferroelectric devices based on P(VDF-TrFE) copolymers. </p

Pressure Effects on the Dynamic Heterogeneity of Miscible Poly(vinyl acetate)/Poly(ethylene oxide) Blends

The poly­(vinyl acetate) (PVAc) segmental dynamics is studied as a function of composition, temperature, and pressure in thermodynamically miscible blends with poly­(ethylene oxide) (PEO) by dielectric spectroscopy. In the PVAc-rich blends all short-range correlations are dominated by the PVAc component. An invariant frequency dispersion is found when the spectra at each blend composition are compared under isochronal conditions. The self-concentration model with a fixed PVAc self-concentration of ∼0.22 qualitatively describes the temperature dependence of the PVAc segmental dynamics both at atmospheric and at elevated pressures