Interpretation of the vibrational spectra of glassy polymers using coarse-grained simulations

The structure and vibrational density of states (VDOS) of polymer glasses are investigated using numerical simulations based on the classical Kremer-Grest bead-spring model. We focus on the roles of chain length and bending stiffness, the latter being set by imposing three-body angular potentials along chain backbones. Upon increasing the chain length and bending stiffness, structural reorganisation leads to volumetric expansion of the material and build-up of internal stresses. The VDOS has two dominant bands: a low frequency one corresponding to inter- and intra-chain non-bonding interactions and a high frequency one corresponding principally to vibrations of bonded beads that constitute skeletal chain backbones. Upon increasing the steepness of the angular potential, vibrational modes associated with chain bending gradually move from the low-frequency to the high-frequency band. This redistribution of modes is reflected in a reduction of the so-called Boson peak upon increasing chain stiffness. Remarkably, the finer structure and the peaks of the high-frequency band, and their variations with stiffness, can, for short chains, be explained using an analytical solution derived for a model triatomic molecule. For longer chains, the qualitative evolution of the VDOS with chain stiffness is similar, although the distinct peaks observed for short chains become increasingly smoothed-out. Our findings can be used to guide a systematic approach to interpretation of Brillouin and Raman scattering spectra of glassy polymers in future work, with applications in polymer processing diagnostics.Comment: To appear in Macromolecule

Parameter-free predictions of the viscoelastic response of glassy polymers from non-affine lattice dynamics

We study the viscoelastic response of amorphous polymers using theory and simulations. By accounting for internal stresses and considering instantaneous normal modes (INMs) within athermal non-affine theory, we make parameter-free predictions of the dynamic viscoelastic moduli obtained in coarse-grained simulations of polymer glasses at non-zero temperatures. The theoretical results show very good correspondence with rheology data collected from molecular dynamics simulations over five orders of magnitude in frequency, with some instabilities that accumulate in the low-frequency part on approach to the glass transition. These results provide evidence that the mechanical glass transition itself is continuous and thus represents a crossover rather than a true phase transition. The relatively sharp drop of the low-frequency storage modulus across the glass transition temperature can be explained mechanistically within the proposed theory: the proliferation of low-eigenfrequency vibrational excitations (boson peak and nearly-zero energy excitations) is directly responsible for the rapid growth of a negative non-affine contribution to the storage modulus.Comment: 10 pages, 7 figure

Castor A and Castor B resolved in a simultaneous Chandra and XMM-Newton observation

We present a simultaneous Chandra and XMM-Newton observation of the Castor sextett, focusing on Castor A and Castor B, two spectroscopic binaries with early-type primaries. Of the present day X-ray instruments only Chandra can isolate the X-ray lightcurves and spectra of A and B. We compare the Chandra observation with XMM-Newton data obtained simultaneously. Albeit not able to resolve Castor A and Castor B from each other, the higher sensitivity of XMM-Newton allows for a quantitative analysis of their combined high-resolution spectrum. He-like line triplets are used to examine the temperature and the density in the corona of Castor AB. The temporal variability of Castor AB is studied using data collected with the European Photon Imaging Camera onboard XMM-Newton. Strong flare activity is observed, and combining the data acquired simultaneously with Chandra and XMM-Newton each flare can be assigned to its host. Our comparison with the conditions of the coronal plasma of other stars shows that Castor AB behave like typical late-type coronal X-ray emitters supporting the common notion that the late-type secondaries within each spectroscopic binary are the sites of the X-ray production.Comment: accepted for publication in A&

Nutritional Approaches to Achieve Weight Loss in Nonalcoholic Fatty Liver Disease.

Nonalcoholic fatty liver disease (NAFLD) can range in spectrum from simple hepatic steatosis to nonalcoholic steatohepatitis (NASH), which is characterized by lipotoxicity, hepatocellular ballooning, and inflammation and can progress to cirrhosis. Weight loss is the cornerstone treatment for NAFLD and NASH. Various randomized controlled trials have shown that weight loss of ≥5-10% leads to significant improvements in hepatic steatosis. Diets high in sodium and fructose have been implicated in the pathogenesis of NAFLD. Although some clinical studies suggest that an isocaloric high-fructose diet does not worsen NAFLD, these clinical studies are often short in duration. More recently, the Dietary Approaches to Stop Hypertension diet, a sodium-restricted diet, has been associated with less prevalence of NAFLD and has been shown to improve NAFLD. In addition, the Mediterranean diet has been promising in improving hepatic steatosis, and a larger randomized controlled trial is currently enrolling subjects. For those who are unable to pursue weight loss through dietary approaches, bariatric surgery has been shown to improve hepatic steatosis and steatohepatitis. This method has been variable in improving hepatic fibrosis. In conclusion, weight loss is crucial to the improvement of NAFLD and NASH, and patients should attempt various diets in an attempt to achieve weight loss