Confined intra-molecular clustering in orientated polyethylene after annealing

Deuterated polyethylene tracer molecules with small amount of branches (12 C2H5- branches per 1000 backbone carbon atoms) were blended with a hydrogenated polyethylene matrix to form a homogenous mixture. The conformational evolution of the deuterated chains in a stretched semi-cry stall me film was observed via online small angle neutron scattering measurements during annealing at high temperatures close to the melting point. Because the sample was annealed at a temperature closely below its melting point, the crystalline lamellae were only partially molten and the system could not fully relax. The global chain dimensions were preserved during annealing. Recrystallization of released polymeric chain segments allows for local phase separation thus driving the deuterated chain segments into the confining interlamellar amorphous layers giving rise to an interesting intra-molecular clustering effect of the long deuterated chain. This clustering is deduced from characteristic small angle neutron scattering patterns. The confined phase separation has its origin in primarily the small amount of the branches on the deuterated polymers which impede the crystallization of the deuterated chain segments.

Vacuum-deposited submonolayer thin films of a three-ring bent-core compound

Submonolayer thin films of a three-ring bent-core (that is, banana-shaped) compound, m-bis(4-n-octyloxystyryl)benzene (m-OSB), were prepared by the vacuum-deposition method, and their morphologies, structures, and phase behavior were investigated by atomic force microscopy (AFM) and transmission electron microscopy (TEM). The films have island shapes ranging from compact elliptic or circular patterns at low temperatures (below 40 degreesC) to branched patterns at high temperatures (above 60 degreesC). This shape evolution is contrary to the prediction based on the traditional diffusion-limited aggregation (DLA) theory. AFM observations revealed that two different mechanisms governed the film growth, in which the compact islands were formed via a dewetting-like behavior, while the branched islands diffusion-mediated. It is suggested m-OSB forms a two-dimensional, liquid crystal at the low-temperature substrate that is responsible for the unusual formation of compact islands. All of the monolayer islands are unstable and apt to transform to slender bilayer crystals at room temperature. This phase transition results from the peculiar molecular shape and packing of the bent-core molecules and is interpreted as escaping from macroscopic net polarization by the formation of an antiferroelectric alignment.

Probing the kinetics of single molecule protein folding

We propose an approach to integrate the theory, simulations, and experiments in protein-folding kinetics. This is realized by measuring the mean and high-order moments of the first-passage time and its associated distribution. The full kinetics is revealed in the current theoretical framework through these measurements. In the experiments, information about the statistical properties of first-passage times can be obtained from the kinetic folding trajectories of single molecule experiments ( for example, fluorescence). Theoretical/simulation and experimental approaches can be directly related. We study in particular the temperature-varying kinetics to probe the underlying structure of the folding energy landscape. At high temperatures, exponential kinetics is observed; there are multiple parallel kinetic paths leading to the native state. At intermediate temperatures, nonexponential kinetics appears, revealing the nature of the distribution of local traps on the landscape and, as a result, discrete kinetic paths emerge. At very low temperatures, exponential kinetics is again observed; the dynamics on the underlying landscape is dominated by a single barrier.

Surface morphology evolution of a thin polymeric supramolecular film by tuning interactions

A polymeric supramolecule consisting of symmetric polystyrene-block-poly(4-vinylpytidine) (PS-b-P4VP), dodecylbenzenesulfonic acid (DBSA), and 3-pentadecylphenol (PDP) was formed by proton transfer and hydrogen bonding. The surface morphology,of a thin film of the polymeric supramolecule has been investigated. The spherical PS microdomains embedded in a P4VP(DBSA)(1.0)(PDP)(1.0) matrix are observed for the as-cast film because the weight fraction, f(comb), of the P4VP(DBSA) (1.0)(PDP)(1.0) blocks is much higher than that of PS as a result of the non-covalent interactions of P4VP and DBSA and DBSA and PDR Upon annealing the PS-b-P4VP(1:1)(DBSA)(1.0)(PDP)(1.0) film at high temperatures, the hydrogen bonding between the DBSA and PDP diminishes, which leads to a change of overall morphology from an ordered sphere to a pitted structure.

Nanocluster-containing mesoporous magnetoceramics from hyperbranched organometallic polymer precursors

Pyrolysis of hyperbranched poly[1,1'-ferrocenylene(methyl)silyne] (5) yields mesoporous, conductive, and magnetic ceramics (6). Sintering at high temperatures (1000-1200 degrees C) under nitrogen and argon converts 5 to 6N and 6A, respectively, in similar to 48-62% yields. The ceramization yields of 5 are higher than that (similar to 36%) of its linear counterpart poly[1,1'-ferrocenylene(dimethyl)silylene] (1), revealing that the hyperbranched polymer is superior to the linear one as a ceramic precursor. The ceramic products 6 are characterized by SEM, XPS, EDX, XRD, and SQUID. It is found that the ceramics are electrically conductive and possess a mesoporous architecture constructed of tortuously interconnected nanoclusters. The iron contents of 6 estimated by EDX are 36-43%, much higher than that (11%) of the ceramic 2 prepared from the linear precursor 1. The nanocrystals in 6N are mainly alpha-Fe2O3 whereas those in 6A are mainly Fe3Si. When magnetized by an external field at room temperature, 6A exhibits a high-saturation magnetization (M-s similar to 49 emu/g) and near-zero remanence and coercivity; that is, 6A is an excellent soft ferromagnetic material with an extremely low hysteresis loss.

Lateral habits of single crystals of metallocene-catalyzed low molecular weight short chain branched polyethylene from the melt

The lateral habits of low molecular weight short chain branched polyethylene single crystals from the melt were studied. Three crystallization temperatures (102, 104 and 106 degrees C) were selected for single crystal growth. It was found that the lateral habits of single crystals were asymmetric at all the crystallization temperatures selected. The electron diffraction patterns and tilting series experiments evidenced that there existed chain tilting in all the lamellae. It was the chain tilting that lead to the asymmetry of the growth rate and of lateral habits of the single crystals about the b-axis. The lateral habits substantially changed from the growth at 102 degrees C where the truncated lozenge single crystals formed with straight (110) faces to the growth at 104 degrees C where the lenticular single crystals appeared. This change occurred at 20 degrees C lower than that in a low molecular weight linear polyethylene with the same molecular weight. Furthermore, kinetics theory analysis evidenced that the change of lateral habits from truncated lozenge to lenticular shape resulted from the transition of growth regime. The results were the same as that of high molecular weight linear polyethylene but different to that of low molecular weight linear polyethylene. It may be attributed by the existence of short branched chains. (C) 2000 Elsevier Science Ltd. All rights reserved.

Observation of twisting growth of branched polyethylene single crystals formed from the melt

The twisting growth of a branched polyethylene single crystal formed from the melt was observed directly by means of transmission electron and atomic force miscroscopy. The surface stress asymmetry arising from the asymmetry of the surface-fold structure and, chain tilting resulted in the twisting growth of the single crystals. The handedness of the twisting lamellae was consistent With the chain-tilting direction. When multilayer lamellae piled up in a thicker film, the lamellar twist would be inevitably causing screw dislocations.

Studies on the PTC/NTC effect of carbon black filled low density polyethylene composites

The positive temperature coefficient (PTC) and negative temperature coefficient (NTC) effect of carbon black (CB) filled low density polyethylene (LDPE) composites was studied using electrical resistivity spectra, DSC, tensile mechanical analysis (TMA) and small-angle X-ray scattering (SAXS) techniques. The three LDPEs used have a similar crystallinity and different melting index (MI). The experimental results indicate that the CB has no significant effect on the crystallinity and the long spacing of crystalline domains of LDPE. Based upon the TMA and dynamic elastic modulus spectra, it can be concluded that the PTC effect is related to the thermal expansion of the polymer matrix, and the NTC effect is caused by a decrease of the elastic modulus of the polymer at high temperatures. The NTC effect can be reduced by enhancing either the elastic modulus or the interaction between carbon black and matrix. (C) 1997 Elsevier Science Ltd.

A study of the dependence of ferrocene diffusion on chain length in polymer electrolytes

The diffusion rates of ferrocene have been estimated in five kinds of poly(ethylene glycol) solution, containing the electrolyte LiClO4, by using non-steady-state chronoamperometry. The D-app of ferrocene increases with increasing temperature, and the dependency of D-app on temperature obeys the Williams-Landel-Ferry equation. The D-app of ferrocene decreases with increasing polymer chain length. Both the chain length and temperature dependence conform to a simple free volume model. A relation between current and polymer chain length is suggested at room and high temperatures.