Crystal nucleation mechanism in melts of short polymer chains under quiescent conditions and under shear flow

We present a molecular dynamics simulation study of crystal nucleation from undercooled melts of n-alkanes, and we identify the molecular mechanism of homogeneous crystal nucleation under quiescent conditions and under shear flow. We compare results for n-eicosane(C20) and n-pentacontahectane(C150), i.e. one system below the entanglement length and one above. Under quiescent conditions, we observe that entanglement does not have an effect on the nucleation mechanism. For both chain lengths, the chains first align and then straighten locally. Then the local density increases and finally positional ordering sets in. At low shear rates the nucleation mechanism is the same as under quiescent conditions, while at high shear rates the chains align and straighten at the same time. We report on the effects of shear rate and temperature on the nucleation rates and estimate the critical shear rates, beyond which the nucleation rates increase with the shear rate. We show that the viscosity of the system is not affected by the crystalline nuclei.Comment: 9 page

Venus cusp observations during 1969 - Synopsis of results

Venus cusp observations during 196

Dynamic Glass Transition in Two Dimensions

The question about the existence of a structural glass transition in two dimensions is studied using mode coupling theory (MCT). We determine the explicit d-dependence of the memory functional of mode coupling for one-component systems. Applied to two dimensions we solve the MCT equations numerically for monodisperse hard discs. A dynamic glass transition is found at a critical packing fraction phi_c^{d=2} = 0.697 which is above phi_c^{d=3} = 0.516 by about 35%. phi^d_c scales approximately with phi^d_{\rm rcp} the value for random close packing, at least for d=2, 3. Quantities characterizing the local, cooperative 'cage motion' do not differ much for d=2 and d=3, and we e.g. find the Lindemann criterion for the localization length at the glass transition. The final relaxation obeys the superposition principle, collapsing remarkably well onto a Kohlrausch law. The d=2 MCT results are in qualitative agreement with existing results from MC and MD simulations. The mean squared displacements measured experimentally for a quasi-two-dimensional binary system of dipolar hard spheres can be described satisfactorily by MCT for monodisperse hard discs over four decades in time provided the experimental control parameter Gamma (which measures the strength of dipolar interactions) and the packing fraction phi are properly related to each other.Comment: 14 pages, 15 figure

Assessing the physical stability of archival cellulose acetate films by monitoring plasticizer loss

Cellulose acetate film plasticized with diethyl phthalate was subjected to artificial aging regimes and the loss of plasticizer determined by means of Thermogravimetric Analysis and Fourier-transform Infrared Spectroscopy. Alterations in the strain hardening capability of the films was monitored by Dynamic Mechanical Analysis, and the connection between flexibility, strain hardening and the degree of plasticization investigated as a means of monitoring the physical condition of archival cellulose acetate film. It was found that the higher the plasticizer content the greater the ability to strain harden, and therefore the least vulnerable to mechanical damage from archival handling. The correlation between the critical plasticizer content and the working properties of cellulose acetate film provides a means of assessing stability, and highlights artifacts at risk from physical damage

Studies on the Weak Itinerant Ferromagnet SrRuO3 under High Pressure to 34 GPa

The dependence of the Curie temperature Tc on nearly hydrostatic pressure has been determined to 17.2 GPa for the weak itinerant ferromagnetic SrRuO3 in both polycrystalline and single-crystalline form. Tc is found to decrease under pressure from 162 K to 42.7 K at 17.2 GPa in nearly linear fashion at the rate dTc/dP = -6.8 K/GPa. No superconductivity was found above 4 K in the pressure range 17 to 34 GPa. Room-temperature X-ray diffraction studies to 25.3 GPa reveal no structural phase transition but indicate that the average Ru-O-Ru bond angle passes through a minimum near 15 GPa. The bulk modulus and its pressure derivative were determined to be B =192(3) GPa and B' = 5.0(3), respectively. Parallel ac susceptibility studies on polycrystalline CaRuO3 at 6 and 8 GPa pressure found no evidence for either ferromagnetism or superconductivity above 4 K

Onset of slow dynamics in difluorotetrachloroethane glassy crystal

Complementary Neutron Spin Echo and X-ray experiments and Molecular Dynamics simulations have been performed on difluorotetrachloroethane (CFCl2-CFCl2) glassy crystal. Static, single-molecule reorientational dynamics and collective dynamics properties are investigated. The orientational disorder is characterized at different temperatures and a change in nature of rotational dynamics is observed. We show that dynamics can be described by some scaling predictions of the Mode Coupling Theory (MCT) and a critical temperature $T_{c}$ is determined. Our results also confirm the strong analogy between molecular liquids and plastic crystals for which $\alpha$-relaxation times and non-ergodicity parameters are controlled by the non trivial static correlations as predicted by MCT

Exploring the Oxygen Order in Hg-1223 and Hg-1201 by 199Hg MAS NMR

We demonstrate the use of a high-resolution solid-state fast (45 kHz) magic angle spinning (MAS) NMR for mapping the oxygen distribution in Hg-based cuprate superconductors. We identify observed three peaks in 199Hg spectrum as belonging to the different chemical environments in the HgO? layer with no oxygen neighbors, single oxygen neighbor, and two oxygen neighbors. We discuss observed differences between Hg-1201 and Hg-1223 materials.Comment: 4 pages, 2 figures included. Submitted to NATO Advanced Research Workshop Proceedings (Miami January 2004