Simulation of glassy state relaxations in polymers: A static analysis of methyl group and methoxy group rotation in poly(vinyl methyl ether)

We show that the simple quasi-static technique, also called the adiabatic mapping technique, can be used to determine the energetics of rotation of methyl and methoxy groups in amorphous poly(vinyl methyl ether) even though the latter process is too slow to be amenable to direct molecular dynamics simulation. For the methyl group rotation, we find that the mean and standard deviation of the simulated rotational barrier heights agree well with experimental data from quasi-elastic neutron scattering. In the case of the methoxy groups we find that just 4% of the groups contribute more than 90% of the observed dielectric relaxation strength. The groups which make the most contribution are those which, by virtue of their particular conformation and local environment, have two alternative positions of similar energy.

The 2dF-SDSS LRG and QSO survey: the star formation histories of luminous red galaxies

We present a detailed investigation into the recent star formation histories of 5697 luminous red galaxies (LRGs) based on the H delta (4101 angstrom), and [O II] (3727 angstrom) lines and the D4000 index. LRGs are luminous (L > 3L*) galaxies which have been selected to have photometric properties consistent with an old, passively evolving stellar population. For this study, we utilize LRGs from the recently completed 2dF-SDSS LRG and QSO Survey (2SLAQ). Equivalent widths of the H delta and [O II] lines are measured and used to define three spectral types, those with only strong H delta absorption (k+a), those with strong [O II] in emission (em) and those with both (em+a). All other LRGs are considered to have passive star formation histories. The vast majority of LRGs are found to be passive (similar to 80 per cent); however, significant numbers of k+a (2.7 per cent), em+a (1.2 per cent) and em LRGs (8.6 per cent) are identified. An investigation into the redshift dependence of the fractions is also performed. A sample of SDSS MAIN galaxies with colours and luminosities consistent with the 2SLAQ LRGs is selected to provide a low-redshift comparison. While the em and em+a fractions are consistent with the low-redshift SDSS sample, the fraction of k+a LRGs is found to increase significantly with redshift. This result is interpreted as an indication of an increasing amount of recent star formation activity in LRGs with redshift. By considering the expected lifetime of the k+a phase, the number of LRGs which will undergo a k+a phase can be estimated. A crude comparison of this estimate with the predictions from semi-analytic models of galaxy formation shows that the predicted level of k+a and em+a activities is not sufficient to reconcile the predicted mass growth for massive early types in a hierarchical merging scenario.

Mathematical Morphology: Star/Galaxy Differentiation & Galaxy Morphology Classication

We present an application of Mathematical Morphology (MM) for the classification of astronomical objects, both for star/galaxy differentiation and galaxy morphology classification. We demonstrate that, for CCD images, 99.3 +/- 3.8% of galaxies can be separated from stars using MM, with 19.4 +/- 7.9% of the stars being misclassified. We demonstrate that, for photographic plate images, the number of galaxies correctly separated from the stars can be increased using our MM diffraction spike tool, which allows 51.0 +/- 6.0% of the high-brightness galaxies that are inseparable in current techniques to be correctly classified, with only 1.4 +/- 0.5% of the high-brightness stars contaminating the population. We demonstrate that elliptical (E) and late-type spiral (Sc-Sd) galaxies can be classified using MM with an accuracy of 91.4 +/- 7.8%. It is a method involving fewer 'free parameters' than current techniques, especially automated machine learning algorithms. The limitation of MM galaxy morphology classification based on seeing and distance is also presented. We examine various star/galaxy differentiation and galaxy morphology classification techniques commonly used today, and show that our MM techniques compare very favourably.

Measuring and predicting the dynamics of linear monodisperse entangled polymers in rapid flow through an abrupt contraction. A small angle neutron scattering study

Small-angle neutron scattering measurements on a series of monodisperse linear entangled polystyrene melts in nonlinear flow through an abrupt 4:1 contraction have been made. Clear signatures of melt deformation and subsequent relaxation can be observed in the scattering patterns, which were taken along the centerline. These data are compared with the predictions of a recently derived molecular theory. Two levels of molecular theory are used: a detailed equation describing the evolution of molecular structure over all length scales relevant to the scattering data and a simplified version of the model, which is suitable for finite element computations. The velocity field for the complex melt flow is computed using the simplified model and scattering predictions are made by feeding these flow histories into the detailed model. The modeling quantitatively captures the full scattering intensity patterns over a broad range of data with independent variation of position within the contraction geometry, bulk flow rate and melt molecular weight. The study provides a strong, quantitative validation of current theoretical ideas concerning the microscopic dynamics of entangled polymers which builds upon existing comparisons with nonlinear mechanical stress data. Furthermore, we are able to confirm the appreciable length scale dependence of relaxation in polymer melts and highlight some wider implications of this phenomenon.

Synthesis of soluble phosphate polymers by RAFT and their in vitro mineralization

Soluble linear (non-cross-linked) poly(monoacryloxyethyl phosphate) (PMAEP) and poly(2-(methacryloyloxy)ethyl phosphate) (PMOEP) were successfully synthesized through reversible addition-fragmentation chain transfer (RAFT)-mediated polymerization and by keeping the molecular weight below 20 K. Above this molecular weight, insoluble (cross-linked) polymers were observed, postulated to be due to residual diene (cross-linkable) monomers formed during purification of the monomers, MOEP and MAEP. Block copolymers consisting of PMAEP or PMOEP and poly(2-(acetoacetoxy) ethyl methacrylate) (PAAEMA) were successfully prepared and were immobilized on aminated slides. Simulated body fluid studies revealed that calcium phosphate (CaP) minerals formed on both the soluble polymers and the cross-linked gels were very similar. Both the PMAEP polymers and the PMOEP gel showed a CaP layer most probably brushite or monetite based on the Ca/P ratios. A secondary CaP mineral growth with a typical hydroxyapatite (HAP) globular morphology was found on the PMOEP gel. The soluble PMOEP film formed carbonated HAP according to Fourier transform infrared (FTIR) spectroscopy. Block copolymers attached to aminated slides showed only patchy mineralization, possibly due to the ionic interaction of negatively charged phosphate groups and protonated amines.