Structure relaxation after temperature jumps in homogeneous polystyrene/poly(styrene-co-bromostyrene) blends

Concentration fluctuations in polymer blends and their change after a temperature jump were studied by time-dependent small angle X-ray scattering experiments. Measurements were conducted on homogeneous mixtures of polystyrene and a partially brominated derivative. Structure factors in thermal equilibrium show the form given by the random phase approximation, thus enabling a direct determination of the-parameter and the mean radius of gyration. TheT-dependence of can be understood as the result of superposed enthalpic contributions and a free volume term. In theT-jump experiments, samples were quenched to temperatures near T_g. Relaxation occurs on the time scale of minutes and is nonexponential, becoming slower with time. Initial relaxation rates increase with increasing scattering vectorsq in accordance with theoretical predictions.     

Formation of a [2 + 2]-heterotetranuclear macrocycle from reaction of a platina-homoditopic ligand with iron(II)

Reaction of 4'-(2-propyn-1-oxy)-2,2':6',2'-terpyridine (HC triple bond CCH2Oterpy) with trans-[PtI2(PEt3)2] regioselectively metallates the alkyne to give trans-[Pt(C triple bond CCH2Oterpy)2(PEt3)2] which, when treated with Fe(II), gives a [2 + 2]-metallocycle.     

Submicroscopic Defects in Metals and their Influence on HVEM In-situ Experiments

Recent high-voltage electron microscopy has provided evidence that substantial submicroscopic changes may occur in specimens examined in the HVEM under conditions where no visible radiation damage occurs. These are the introduction of vacancies by plastic deformation, rapid accumulation of invisible vacancy clusters by electron irradiation, and radiation-induced contamination and refining of materials. These processes are analysed in terms of defect interactions and the consequences for in-situ experiments are discussed.     

A scale value for the balance inside a historical opera house

In the framework of opera house acoustics, the term "balance" refers to the acoustical competition between the singer on the stage and the orchestra in the pit. The mechanism allowing the operatic singers to be heard over the orchestra has to do with their skill in enhancing the vocal emission by a peculiar use of the formant frequencies. This vital factor is sensed by the listeners and, apart from the obvious sound power ratio of the stage and the pit sources, is the main cue that helps to formulate a subjective impression of the balance. To achieve its objective qualification, two calibrated sound sources can be placed on the stage and in the pit, respectively, and their sound level difference is measured at the listeners' seats. The scope of this work is to investigate the relationship between the subjective impression and the objective indicator of the balance and to develop a scale value for the parameter in the case of a historical opera house. For this scope a set of acoustical data from the Teatro Comunale in Ferrara will be used to create synthetic sound fields with controlled conditions of the balance between the stage and the pit. This methodology employs an anechoic piece for soprano (with piano accompaniment) and is implemented in a dead room equipped with an acoustical rendering system. The sound fields are used to investigate the appropriate balance values by means of listening tests. The results of the scaling exercise show that a suitable range of values can be extracted and that the sound from the stage and the pit is perceived as balanced when the loudness difference between the two is comprised within -2.0 dBA and +2.3 dBA.     

Detection of stress whitening in plastics with the help of X-ray dark field imaging

The processing of thermoplastics can induce a wide range of defects such as stress whitening, cavitation and porosity, which can adversely affect the reliability of the final products. Hence, fast and effective non-destructive detection methods for such defects are highly important for quality assurance on production lines. In this paper, X-ray dark field imaging is presented as a new non-destructive testing method that allows the visualization of stress whitening or cavitation efficiently. The performance of the method is demonstrated for the case of an injection-moulded polyvinylidene fluoride part that exhibits stress whitening. Whereas the stress whitening could not be detected by conventional X-ray imaging, it was localized by an X-ray dark field image acquired within a few minutes. Once the precise location of the stress whitening was known, it was possible to verify the result by local micro X-ray computed tomography and by a micro section image.     

Dielectric properties of selected laterally fluoro-substituted 4,4′′-dialkyl,dialkoxy and alkyl-alkoxy [1:1′;4′:1′′]terphenyls

Measurements of the complex permittivity, ε*?=?ε′ – iε″, within the frequency range 200 Hz to 10 MHz for 15 laterally fluoro-substituted terphenyls have been conducted. In most cases the substances exhibited the nematic phase over a broad temperature range. All substances were characterised by negative dielectric anisotropy, and are potentially useful for vertical alignment mode systems. The static permittivity tensor components have been analysed in relation to the dipole structure of the molecules. Dielectric relaxation processes observed in the liquid crystalline (LC) and solid rotator (R) phases (obtained by slow cooling of the samples) are characterised by calculation of the relaxation times and activation barriers. The rotation motions around the short axes are typical for LC phases, whereas rotations about the long axes, accompanied in some cases by internal motions, are present in the R phase.     

Phase diagram and dielectric relaxation studies of n-octyl-isothiocyanato-biphenyl (8BT) in the crystalline E phase under high pressure

The pressure-temperature phase diagram of n-octyl-isothiocyanato-biphenyl (8BT) in the pressure range up to 250 MPa (2.5 kbar) and the temperature range 250-400 K was established with the aid of DTA. At 1 atm the substance exhibits exclusively CrE polymorphism. At pressures above 190 MPa, the clearing line splits showing an additional phase which is not yet identified. Dielectric relaxation measurements on the CrE phase of 8BT were performed in the pressure range 0.1-120 MPa and the temperature range 304-345 K. A Debye-type relaxation process was observed in the frequency range 100 Hz-1 MHz. The longitudinal relaxation time τ, characterizing the molecular reorientations around the short axis, was analysed with respect to the pressure and temperature, yielding the activation volume, Δ^# V = RT(? ln τ/?p)_T, and activation enthalpy, Δ^# H = R(? ln τ/? T^-1)_p, respectively. The results are compared with analogous data obtained recently for similar compounds having other liquid crystalline phases (N, SmA).     

Synthesis of cyclic norspermidine derivative of protohemin IX

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Spectral properties of coumarin derivatives in various environments

The structural and spectral properties of coumarin derivatives in complex environments were investigated within the time-dependent density functional theory (TD DFT). Absorption spectra calculations were obtained at TD PBE0/6-31+G(d,p) level of theory for coumarin47 in the gas-phase and in various polar and non-polar organic solvents. The geometries of coumarins 6, 30, 47 and 522 in the gas phase and in inclusion complexes with the β-cyclodextrin (βCD) were determined by PM3 and DFT (HCTH/6-31G) calculations. Encapsulation of coumarin in βCD and associated changes in electronic structure produced either a red or blue shift in the absorption spectra of coumarins. A proposed cavity model for βCD-coumarin complex in water solution allowed identification of various contributions to the overall shift in the absorption spectra of coumarin upon complex formation in a solvent environment