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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 94 (1991), S. 3050-3059 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: This report presents measurements of the frequency dependent dielectric loss ε‘(ω) and quasielastic light scattering of thermal density fluctuations of simple organic glassforming van der Waals liquids BCDE (bis-phenol-C-dimethylether) and BKDE (bis-kresol-C-dimethylether) having glass transition temperatures of Tg=240 K and Tg=261 K, respectively. The dielectric measurements of BCDE were carried out in a temperature range between 250 and 316 K, those of BKDE between 270 and 384 K covering a frequency range from 10−1 to ∼109 Hz in each case. Quasielastic light scattering data were taken between the glass transition temperatures and T(approximately-equal-to)Tg+30 K in a correlation time window of 10−6 s up to 102 s. As main results we have found the following: The relaxation process in the BCDE melt can be described using a Kohlrausch–Williams–Watts (KWW) function with a temperature independent β parameter. Its value was found to be identical either from the light scattering result or from the stretched exponential fit to the Fourier transform of the dielectric loss data.The temperature dependence of the mean relaxation times of the BCDE melt was fitted with a Williams–Landel–Ferry (WLF) equation, or Vogel–Fulcher–Tammann equation, leading to WLF constants close to the universal ones. The BKDE system, however, behaves differently, where the dynamic response in the bulk amorphous state could only be described using a temperature dependent β parameter. This finding was confirmed by either the light scattering method as well as the dielectric relaxation method. Additionally we were able to measure a second dielectrically active process in BCDE only, arising in the high frequency region with an Arrhenius type of activation energy. In the BKDE melt, however, the superposition of different processes causes a temperature dependence of the β parameter when the data is forcefitted with a single KWW function. To correlate the fast process of BCDE (β process) with a possible molecular model of motion we have performed additional 2H-NMR solid echo measurements on both materials around and well below Tg. Thereby a 180° phenyl ring flip motion in BCDE was found in contrast to BKDE. This assignment of the secondary relaxation process is discussed together with the results from other methods.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Woodbury, NY : American Institute of Physics (AIP)
    Applied Physics Letters 59 (1991), S. 1043-1045 
    ISSN: 1077-3118
    Source: AIP Digital Archive
    Topics: Physics
    Notes: Thin films ranging from 400 nm to 4 μm thickness of poly( p-phenylene biphenyltetracarboximide) (BPDA-PDA), prepared by thermal imidization of the precursor poly(amic acid) on substrates, have been investigated by the optical waveguide spectroscopy. These polyimide films, most prominent for potential applications as the interlevel dielectrics in multilevel interconnect technologies owing to their low coefficients of thermal expansion and excellent thermal/mechanical properties, are found to exhibit an extraordinarily large anisotropy in the refractive index, with the measured in-plane refractive index n(parallel)(approximately-equal-to)1.852 and the out-of-plane value n⊥(approximately-equal-to)1.612 at 632.8 nm wavelength, nearly independent of the film thickness. This large optical anisotropy indicates a very strong preference of polymer chains to orient along the film surface, and suggests a considerably larger (by ca. 27%) dielectric constant in the film plane than that along the film thickness. Moreover, there is some evidence for the existence of a very thin polyimide layer of slightly lower density and higher anisotropy adjacent to the substrate.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 1520-5835
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 30 (1992), S. 1321-1327 
    ISSN: 0887-6266
    Keywords: polyimides. stiff, optical and dielectric properties in their films of ; optical anisotropy and chain orientation stiff polyimide thin films ; dielectric properties of stiff polyimide thin films ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Thin films of poly(p-phenylene biphenyltetracarboximide) (BPDA-PDA), prepared by thermal imidization of the precursor poly(amic acid) on substrates, have been investigated by optical waveguide, ultraviolet-visible (UV-VIS), infrared (IR), and dielectric spectroscopies. The polyimide films exhibit an extraordinarily large anisotropy in the refractive indices with the in-plane index n∥ = 1.806 and the out-of-plane index n⊥ = 1.589 at 1064 nm wavelength. No discernible effect of the film thickness on this optical anisotropy is found between films of ca. 2.1 and ca. 7.8 μm thickness. This large birefringence is attributed to the preferential orientation of the biphenyltetracarboximide moieties with their planes parallel to the film surface, coupled with the strong preference of BPDA-PDA chains to align along the film plane. The frequency dispersion of the in-plane refractive index n∥ is consistent with the results calculated by the Lorentz-Lorenz equation from the UV-visible spectrum exhibiting several absorption bands in the 170-500 nm region. The contribution from the IR absorption in the range 7000-400 cm,-1 computed by the Spitzer-Kleinmann dispersion relations from the measured spectra, adds ca. 0.046 to the in-plane refractive index n∥. Tilt-angle-dependent polarized IR results indicate nearly the same increase for the out-of-plane index n⊥. Application of the Maxwell relation then leads to the out-of-plane dielectric constant ε⊥ ≃ 2.7 at 1.2 × 1013 Hz, as compared with the measured value of ca. 3.0 at 106 Hz. Assuming this small difference to remain the same for the in-plane dielectric constants ε∥, we obtain a very large anisotropy in the dielectric properties of these polyimide films with the estimated in-plane dielectric constant ε∥ ≃ 3.4 at 1.2 × 1013 Hz, and ε∥ ≃ 3.7 at 106 Hz. © 1992 John Wiley & Sons, Inc.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 53 (1970), S. 1553-1566 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photosensitized oxidation of methyl substituted phenols with free para-positions starts with an electrophilic attack of position 4 by singlet oxygen. This follows from the course of the reaction using phenols with methyl groups in different positions. The influence of the solvent shows that the hydroperoxide formation from the primary oxygen adduct proceeds via an inter-molecular hydrogen shift. The solvent is the hydrogen donator, whereas the phenoxy radicals resulting from the oxidation of the phenol by the excited sensitizer are the hydrogen acceptors. Finally, the quinones are formed from the hydroperoxides by elimination of water.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
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