Raman spectroscopic insights into the glass transition of poly(methyl methacrylate).

Poly(methyl methacrylate) (PMMA) is a very versatile polymer which is used as a glass substitute or as an economical alternative to polycarbonate for many types of important applications, due to its particular physical properties. In this study we deal with the Raman spectroscopic characterization of the glass transition of PMMA, the value of the glass transition temperature being generally a decisive parameter for determining the application of polymers. The information obtained by two-dimensional correlation spectroscopy (2DCOS) analysis and perturbation-correlation moving-windows spectroscopy (PCMW2D) analysis of the temperature dependent depolarized Raman spectra enabled us to recognize that the glass transition of PMMA is ruled by intermolecular interactions which influence the vibrational modes of the molecular groups associated with ν(C[double bond, length as m-dash]O), δa(C-H) of α-CH3 and/or O-CH3, ν(C-O-C), ν(C-COO), and ν(C-C-O). This information was employed for the temperature dependent study of the Raman shift and of the full width at half maximum of the Raman peaks obtained through anisotropic and isotropic Raman spectra, of the depolarization ratio, of the Raman spectroscopic noncoincidence effect, and of the Raman peak intensities represented by Arrhenius-type plots, all results supporting the outcomes of this work. The comparison with results obtained by differential scanning calorimetry and with published results in molecular dynamics studies was also part of this work. As the main result, one can highlight the peak associated with the ν(C-O-C) stretching mode at around 812 cm-1 as the one which presents the better outcome for explaining the glass transition from the molecular point of view.

Vibrational entropy of disorder in Cu3Au with different degrees of short-range order.

L12 ordered Cu3Au and fcc-disordered samples with different degrees of short-range order were synthesised by annealing and/or quenching experiments. Low-temperature heat capacities were determined by relaxation calorimetry. From these data the vibrational entropy of disorder was derived. The calorimetric results show that the vibrational entropy does not depend on the degree of short-range order. The calorimetric investigations were complemented by density functional calculations with different functionals simulating various atomic configurations by super cells of different size. Using super cells containing 32 atoms, the computed entropies show only small variations with the change of short-range order in good agreement with the calorimetric results. Using, however, super cells with only 8 atoms, the results depend strongly on the chosen atomic configuration at variance with the calorimetric data. This result is important for investigating substances with larger molecules (e.g., silicate solid solutions) because such investigations are typically limited on super cells containing only a few sites on which substitution takes place.

Oxygen nonstoichiometry and ionic transport properties of La0.4Sr0.6CoO3-delta .

Homogeneous samples of La0.4Sr0.6CoO3-delta were obtained by the glycine nitrate process. The oxygen nonstoichiometry was determined from oxygen exchange measurements as a function of oxygen partial pressure (10(-4) bar < PO2 < 10(-2) bar) and temperature (300 degrees C < T< 900 degrees C). The chemical diffusion coefficient D was obtained from oxygen exchange measurements applying a stepwise variation of the oxygen partial pressure of the ambient atmosphere of a disk-shaped sample. The amount of oxygen absorbed or desorbed by the perovskite was analyzed as a function of time. Chemical diffusion data were evaluated using simplified and exact fitting procedures taking into account the surface exchange coefficient. Alternatively, galvanostatic polarization measurements were performed in a PO2-range between 10(-4) and 10(-2) bar to yield D and the ionic conductivity sigma(i) from the long time solution of the diffusion equation. Values for D from polarization measurements at T= 775 degrees C and from oxygen exchange measurements at T= 725 degrees C are in good agreement with each other. D and sigma(1) increase with increasing PO2 (10(-4) to 10(-2) bar). The ionic conductivity shows a maximum at 3-delta approximately 2.82 and decreases with decreasing oxygen content indicating the possible formation of vacancy ordered structures.