Search results for " transition"

Pressure-induced cooperative spin transition in ironII 2D coordination polymers: room-temperature visible spectroscopic study.

2011

For the 2D coordination polymers [Fe(3-Fpy)(2)M(II)(CN)(4)] (M(II) = Ni, Pd, Pt), the pressure-induced spin crossover behavior has been investigated at 298 K by monitoring the distinct optical properties associated with each spin state. Cooperative first-order spin transition characterized by a piezohysteresis loop ca. 0.1 GPa wide was observed for the three derivatives. Application of the mean field regular solution theory has enabled estimation of the cooperative parameter, Γ(p), and the enthalpy, ΔH(HL)(p), associated with the spin transition for each derivative. These values, found in the intervals 6.8-7.9 and 18.6-20.8 kJ mol(-1), respectively, are consistent with those previously repo…

Relaxations Below Glass Transition Temperature in Bread and Its Components

1999

ABSTRACT Dry glassy bread, cooked gluten, and gelatinized wheat starch-sucrose mixtures were prepared. Dielectric properties were studied as a function of temperature at different frequencies ranging from 100 to 1,000 kHz. Both bread and starch samples exhibited a tan δ peak at -53°C at 10 kHz, which is associated with a secondary relaxation characterized by an activation energy of 50 kJ/mol. The gluten sample did not show any relaxation in the temperature range studied. The magnitude of the relaxation peak was sensitive to the sucrose concentration of the starch sample. The higher the sucrose content, the greater the amplitude of the peak. Such an effect is attributed to a greater β-relaxa…

Dynamical heterogeneities in glass-forming materials

1996

ABSTRACTCooperative dynamics around the glass transition leads to complex motional behavior of the individual molecules, resulting in non-exponential relaxation. The nature of this non-exponentiality is clarified theoretically as well as experimentally. The non-exponentiality may be due to heterogeneous relaxation (superposition of exponential processes with different rate constants) or homogeneous relaxation (identical intrinsically non-exponential processes). A precise definition of both limits is given. It is shown that the type of relaxation, i.e. to which degree heterogeneous and homogeneous contributions are present, reflects geometrical properties of the dynamics. The heterogeneous c…

Computer simulations of undercooled fluids and the glass transition

2000

Abstract Two model studies are presented that attempt to describe the static and dynamic properties of glass-forming fluids via molecular dynamics simulations: The first model is an atomistically realistic model of SiO 2 , the second model provides a coarse-grained description of polymer liquids, i.e., typical `fragile' glassformers, while SiO 2 is the prototype of a `strong glassformer'. For both models, attention is given to the questions as to which range of temperatures are properties in equilibrium, and whether such simulations can help to interpret experiments and/or check theoretical predictions. While in the simulation of SiO 2 using the potential of van Beest, Kramer and van Santen…

Thermal properties of e-beam cured epoxy/thermoplastic matrices for advanced composite materials

2007

The aim of this work is to investigate the possibility to improve the thermal behaviour of epoxy based systems, cured by ionizing radiation, in order to produce matrices for advanced carbon fibres composites. Blends of two epoxy monomers, difunctional and trifunctional, have been polymerized by e-beam irradiation and the dynamic mechanical thermal properties have been investigated. The increase of the concentration of the trifunctional epoxy monomer in the blend causes a marked increase of the Tg, but strongly decreases the reactivity. Subsequently, blends of the same epoxy monomers with a high Tg thermoplastic toughening agent have been considered and their reactivity and the thermal prope…

Stereoselective synthesis of unsaturated and functionalized L-NHBoc amino acids, using Wittig reaction under mild phase-transfer conditions.

2012

The stereoselective synthesis of a new amino acid phosphonium salt was described by quaternization of melting triphenylphosphine with the γ-iodo NHBoc-amino ester, derived from L-aspartic acid. The deprotection of the carboxylic acid function to afford the phosphonium salt with a free carboxylic acid group was achieved by a palladium-catalyzed desallylation reaction. This phosphonium salt was used in the Wittig reaction with aromatic or aliphatic aldehydes and trifluoroacetophenone, under solid-liquid phase-transfer conditions in chlorobenzene and in the presence of K(3)PO(4) as weak base, to afford the corresponding unsaturated amino acids without racemization. Thus, the reaction with subs…

1985

Surface and bulk ordering in thin films of a symmetrical diblock copolymer

2013

Amphiphilic diblock copolymers have the ability to adapt their surface's molecular composition to the hydrophilicity of their environment. In the case of about equal volume fractions of the two polymer blocks, the bulk of these polymers is known to develop a laminar ordering. We report here our investigation of the relationship between bulk ordering and surface morphology/chemical composition in thin films of such an amphiphilic diblock copolymer. Upon annealing in vacuum, the expected lamella ordering in the bulk of the film is observed and we find the morphology of the film surface to be defined by the thickness of the as-deposited film: If the as-deposited thickness matches the height of…

1982

Single Particle Motion of Hard-Sphere-Like Polymer Micronetwork Colloids Up to the Colloid Glass Transition

1997

Polymer micronetwork spheres swollen in a good solvent can be regarded as colloids which require no special stabilisation to avoid aggregation. Their interactions can be timed by changing the degree of internal crosslinking. The phase behaviour and the static structure factor demonstrate that crosslink density of 1:10 (inverse number of monomer units between crosslinks) is sufficient to achieve hard sphere behaviour. We designed a host-tracer system consisting of core-shell micronetwork spheres (core: polystyrene; shell: poly-t-butylacrylate) in a host of refractive-indexmatched poly-t-butylacrylate micronetwork colloids. Employing a crosslink density of 1:10 and tuning the polydispersity s…