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61.
The structure and conformational stability of ethyl pseudohalides CH3CH2 — XCN (X = O, S, Se) were investigated using ab initiocalculations at the MP2 level of theory with a triple- basis set augmented with polarization and diffusion functions. Full optimization was performed on the minimum energy structures as well as on the transition state forms. The relative stabilities of rotational conformers were calculated at the MP4 level using MP2 optimized reference geometries. The nature of all considered stationary points was verified by calculation of the harmonic vibrational frequencies. The calculated bond lengths, bond angles, dipole moments, and rotational constants of optimized global minima structures agree very well with the corresponding experimental data obtained from microwave spectroscopic studies. Also, available experimental frequencies are in good accord with the theoretical values. For ethyl cyanate CH3CH2 — OCN, the antiperiplanar (trans) form is predicted to be more stable than the synclinal (gauche) form, and the synperiplanar (cis) form corresponds to the transition state. For both ethyl thiocyanate CH3CH2 — SCN and ethyl selenocyanate CH3CH2 — SeCN, the gaucheform is the global minimum while the trans-conformer is a local minimum and the cis-form is a transition state. 相似文献
62.
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 Tg. 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. 相似文献
63.
Iwan Jerjen Vincent Revol Andreas J. Brunner Philipp Schuetz Christian Kottler Rolf Kaufmann Thomas Luethi Giovanni Nicoletti Claus Urban Urs Sennhauser 《Polymer Testing》2013
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. 相似文献
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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. 相似文献
67.
Abstract Solids like layer silicates (kaolinite and montmorillonite) as well as ZnO are in use in pharmacy. They are pressure treated and subsequently analyzed by means of ESR spectroscopy. The structural changes indicated by Fe3+ ions and paramagnetic defects are reponsible for the enhanced chemical activity of the pressurized systems. Especially active Fe-O-species are formed which can react with intercacalated organic molecules. The most probable first step of such reactions will be a solid state single electron transfer. Spin probes and spin traps were used to prove this statements. The activation of the drug delivery systems by mechanical treatments is of importance for the stability of the drugs incorporated. 相似文献
68.
Dr. James Biggs Dr. Karsten Danielmeier Dr. Julia Hitzbleck Dr. Jens Krause Tom Kridl Dr. Stephan Nowak Dr. Enrico Orselli Dr. Xina Quan Dirk Schapeler Will Sutherland Dr. Joachim Wagner 《Angewandte Chemie (International ed. in English)》2013,52(36):9409-9421
We present the development and applications of dielectric elastomers. For the last 10 years the significance of this class of polymers has risen as more applications seem possible and first products have been commercialized. 相似文献
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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). 相似文献