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  • Physics  (13)
  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1539-1558 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Using recently developed quantitative FTIR methods, the gauche and trans conformer compositions have been measured for polyethylene terephthalate (PET) samples exposed to benzene and acetone. The kinetics of the primary and secondary isomerization stages of the solvent-induced crystallization process have been studied and compared with the thermally crystallized system. The Arrhenius activation energies of isomerization in the primary stage in which Fickian diffusion behavior is followed for the benzene- and acetone-induced PET systems are 8.2 ± 0.4 and 7.7 ± 0.4 kcal/mol, respectively.
    Additional Material: 15 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2067-2083 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Reversible and irreversible spectral changes are observed on heating of solvent-cast films of poly(ethylene terephthalate) (PET) between 30 and 230°C. The irreversible changes are due to the gauche-trans isomerization of the ethylene glycol segments and the corresponding changes in the symmetry and resonance characteristics of the aromatic rings. On the other hand, there are thermally reversible spectral changes. These reversible effects are primarily observed for the modes of the aromatic ring and the trans ethylene glycol segment. These reversible spectral changes include intensity variations and frequency shifts and are found to be linearly dependent on the measurement temperature. These reversible changes arise from changes in intermolecular and intramolecular forces as the temperature changes.
    Additional Material: 14 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2365-2378 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A series of kinetic measurements using FT-IR have been carried out in order to clarify the mechanism of the gauche-trans isomerization process and the time-temperature-transformation relationships in poly(ethylene terephthalate). Two-stage isomerization isotherms are distinguished on the logarithmic scale of annealing time: a primary transformation stage with an activation energy of 40 kcal/mol characterized by a sigmoidal curve, followed by a linear secondary process. The activation energies of the secondary transformation obey an equation of the Arrhenius type InaT = B(1/T - 1/Tm) where 160 〈 T 〈 260°C ≈ Tm and can be used to describe the effects of annealing time and temperature on the isomerization process of PET in the secondary transformation region. On the basis of these analyses, the morphology and microstructure of PET in these temperature regimes of the isomerization process are proposed.
    Additional Material: 9 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 615-626 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The mechanical performances of fiberglass reinforced plastics (FRP) are quite different when the glass fibers are treated with vinyl (VS) and methacryl (γ-MPS) functional silane coupling agents. We have studied the structural basis for this difference on the molecular level using Fourier transform infrared spectroscopy (FT-IR). A high-surface-area silica powder is used to study the coupling agent/matrix interface. Both VS and γ-MPS can react with styrene at the interface. However, when E-glass fiber is used as a substrate, only γ-MPS polymerizes in the coupling agent interphase which consists of many layers of coupling agent molecules while the major portion of the VS does not polymerize in the interphase. The effect of glass surfaces, with and without a coupling agent, on the curing of the polyester resin has also been studied. Silane coupling agents participate in the curing of the polyester resin while untreated E-glass fiber surfaces inhibit the polymerization resulting in different structures from the bulk matrix.
    Additional Material: 12 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 1931-1943 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Fourier-transform (FT) infrared spectroscopy has been applied to the study the hydrothermal degradation of various coupling agents on E-glass fibers. The coupling agents studied include γ-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, and cyclohexyltrimethoxysilane. The amount of coupling agents on E-fibers was measured as a function of immersion time in water at 80°C. Structural changes were also followed by obtaining FT-IR difference spectra of the coupling agent on the glass fiber surface. Silanes desorb quite differently depending on the organofunctional groups. The resistance to desorption is strongly influenced by the organization of the silane interphase as well as the solubility of the silane in water.
    Additional Material: 11 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 2277-2295 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Recently developed data processing techniques have been applied to determine the complete spectra of the trans and gauche isomers of PET and to use these spectra to determine the conformational composition of PET samples isothermally crystallized from the glassy state between 75 and 240°C. A linear correlation was found between normalized absorbance of conformational bands and density measurements, with the trans bands showing a positive slope and the gauche bands a negative slope. Extrapolation of the results from trans bands to zero percent of trans yields the density of the pure gauche isomer, 1.326 ± 0.002 g/cm3. Similarly, from the gauche bands the density of 100% crystalline trans is found to be 1.510 ± 0.014 g/cm3. Meanwhile, the density of the amorphous trans is calculated to be 1.430 ± 0.003 g/cm3. From these values and the combined density and infrared measurements, the content of trans isomers in the amorphous phase is calculated. It is found that the content of amorphous trans is a function of both annealing temperature and time. It is observed that the amorphous trans content decreases as the crystalline trans content increases. At high crystallinity, the amorphous trans content approaches zero. These amorphous trans isomers are associated with the extended units making up the interlamellar links. The loss of these extended trans interlamellar links is reflected in the mechanical properties of PET.
    Additional Material: 14 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 701-718 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The molecular structures of partially cured polyaminopropylsilsesquioxane and aminopropyltriethoxysilane in water have been studied using Fourier-transform infrared, laser Raman, and quasielastic laser light-scattering spectroscopy. A multiply hydrogen-bonded structure is proposed for the intramolecularly interacting amine and silanol groups on the basis of isotope exchange experiment and conformational energy calculations. Conformational restrictions are rather low for the proposed structure, which is thus suitable for the partially cured solid where there are slight perturbations by the surrounding amine and silanol groups. The O.…N distance was experimentally determined to be in the range 2.70-2.67 Å and estimated theoretically as 2.49-2.45 Å. The aminosilane in very dilute solution is found to be mostly monomeric. The isolated monomer-oligomer transition lies around 0.15% by weight and this transition influences the amount of silane uptake by glass fibers. It is also proposed that this phenomenon may be general for surface treatments by silane coupling agents. Hydrolyzed aminosilane oligomers exist in part as submicron aggregates which can be broken up by the addition of an alcohol. The neutralized aminosilane hydrolyzes very slowly although it dissolves in water instantaneously. Micelle formation is also proposed.
    Additional Material: 15 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 845-859 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Fourier-transform infrared spectroscopy was used to characterize the thermal polymerization of the acetylene-terminated (AT) resin, bis[4-(3-ethynylphenoxy)phenyl]sulfone. Spectral processing techniques (including the method of factor analysis) were utilized in the analysis of the infrared data. The degree of cure was quantitatively monitored as the resin was thermally polymerized. Factor analysis indicated that only one reaction product is spectroscopically distinguishable. Further band analysis indicated the formation of predominantly trans conjugated polyene structures. No evidence for cyclotrimerization was found.
    Additional Material: 11 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 18 (1980), S. 233-237 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Molecular structural changes of a vinyl functional silane coupling agent on E-glass fibers, induced during the immersion test in hot water, have been studied using Fourier transform infrared spectroscopy. The amount of the coupling agent on the glass fibers is reduced by hydrolytic degradation. Silanol groups formed by the hydrolysis of the siloxane groups have been detected in the FT-IR difference spectrum in the range 930-840 cm-1 due to the SiO stretching mode of the SiOH groups. Heat treatment produces partial reformation of the siloxane bonds.
    Additional Material: 4 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 17 (1979), S. 799-810 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Infrared measurements of the dichroic ratio of atactic polystyrene absorption bands provide a valuable method of determination of the overall orientation of chains as well as the particular orientation of the trans conformational segments. The orientation process produces the alignment of the chains as well as an increase in the amount of trans conformational segments. A linear relationship is observed between birefringence and dichroic ratio for the absorption bands characteristic of overall orientation. A value of 35° ± 3° is obtained for the angle between the normal to the plane of the benzene ring and the chain axis from both infrared and birefringence determinations.
    Additional Material: 11 Ill.
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