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  • 11
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 188 (1987), S. 217-226 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A phenomenological model is proposed which considers the polymer as an aggregate of units. The units are composed of two distinct phases  -  amorphous and crystalline. The thermal conductivity of a unit is calculated in terms of those of its constituents. In the undrawn state these units are distributed randomly, and the isotropic thermal conductivity of the bulk results. The development of strong anisotropy in thermal conductivity is explained in terms of the preferred orientation of these units. The structural features of this model are similar to those employed for the interpretation of the mechanical properties. The change in orientation of the units was deduced from the experimental data of birefringence. Finally, the results obtained from the composite model for several semicrystalline polymers are compared with the experimental data and other existing calculations. The model is found to give a fair overall description of the thermal conductivity in the cases of polypropylene, polyoxymethylene, low and high density polyethylene, and polychlorotrifluoroethylene.
    Additional Material: 4 Ill.
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  • 12
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 193 (1992), S. 31-41 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Benzoxazole-2-thiol (1)/dibenzoyl peroxide (Bz2O2) was used as photoinitiator for the polymerization of methyl methacrylate (MMA) in bulk and in solution. The study of initiator decomposition was conducted spectrophotometrically. Kinetic studies of the photopolymerization indicated the formation of a complex between 1 and Bz2O2 in the stoichiometric ratio 2:1. The initiation is believed to occur via in situ formation of bis(benzoxazol-2-yl) disulfide in the presence of light.
    Additional Material: 8 Ill.
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  • 13
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 27 (1989), S. 2065-2070 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In the complete absence of a systematic polymer nomenclature, a scheme of nomenclature based on structure is proposed. The problem of naming a “mer” has been solved for an addition polymer by adding “ne” to the monomer name, the justification being on withdrawal of a π bond a monomer becomes a mer. To furnish completeness to the nomenclature, condensation polymers were included in the system. The present nomenclature system of polymers is very arbitrary. Some polymers are not chemically named, some named incorrectly, and there are some fantastic names. After pointing these out, the possible solutions were shown, encompassing a systematic discussion on nearly every type of polymer-linear, branched, or crosslinked-and copolymer (including block or graft), and plastic, fiber, or rubber, and stereospecific polymer. One or more names were proposed for different cases.
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  • 14
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The nature of the local main-chain conformation of polypeptides with charged side chains has been the subject of considerable discussion since Tiffany and Krimm first proposed [(1968) Biopolymers 6, 1379-1381] that, rather than being random, the chain is locally relatively regular, with conformations similar to that of a left-handed threefold helix. Such structures, referred to as “extended-helix” (EH) conformations, have now been studied in a charged poly(L-glutamic acid) system by a combination of Raman spectroscopy and normal-mode analysis. Calculations were done for EH conformations with 3.0 and 2.4 residues/turn, using force fields refined for α-helix, 31-helix, and β-sheet structures. Together with previous results on the α-helix and β-sheet forms, an interesting new correlation emerged: the frequency of the CαC stretch skeletal mode, usually found in the 900-1000 cm-1 region of the Raman spectrum, is essentially linearly correlated with the value of the φ angle. Applying this relationship to the observed frequencies of the α-helix and β-sheet forms of poly(L-glutamic acid), we find that an observed sharp band in the spectrum of crystals of the calcium salt of poly(L-glutamic acid) (which is close to the frequency observed for the charged form in solution) corresponds to an EH conformation very close to that predicted from energy calculations. These studies thus provide very strong support for our proposal that charged polypeptide chains are not random but adopt local conformations of the EH type.
    Additional Material: 3 Ill.
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  • 15
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Fluorescence, CD, absorption, and 1H-nmr studies are reported for complexes of 7-amino-actinomycin D with deoxydinucleotides, deoxytetranucleotides, and poly(dG-dC)· poly(dG-dC). The optical spectra for the 7-amino-actinomycin D complex with pdG-dC, pdG-dC-dG-dC and pdC-dG-dC-dG are similar in shape to the 7-amino-actinomycin D complex with either DNA or poly(dG-dC). The changes in the 1H chemical shifts of the 7-amino-actinomycin D and the pdG-dC resonances that accompany complex formation show that 7-amino-actinomycin D forms a minature intercalated complex with two pdG-dC molecules. The magnitudes of the induced chemical shifts for the 7-amino-actinomycin D complex formation with pdG-dC are similar to, but slightly different from, the induced chemical shifts which are obtained when actinomycin D forms a minature intercalated complex with two pdG-dC molecules. The pdN-dG dinucleotides (N = C, A, or T) form stacked complexes with 7-amino-actinomycin D. The presence of the 7-amino-group results in a larger dimerization constant (in aqueous solution) for 7-amino-actinomycin D [KD(6°C) = 4.4 × 103M-1], as compared to actinomycin D [KD(6°C) = 1.7 × 103M-1]; the chemical shifts which accompany dimer formation indicate that the chromophores stack in an inverted manner. Intercalation of 7-amino-actinomycin D into minature double helices, as well as into calf thymus DNA, poly(dG-dC)·poly(dG-dC), and poly(dA-dC)·poly(dG-dT), results in an enhancement of the relative fluorescence intensity and a shift in both the absorbance and corrected emission spectra.
    Additional Material: 5 Ill.
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  • 16
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 11 (1967), S. 1603-1611 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Graft copolymerization of natural rubber and MMA was carried out in the presence of Bz2O2 or AIBN as thermal initiator and hydrogen peroxide or benzophenone as photosensitizer. From the overall copolymerization product, the rubber-PMMA graft copolymer fraction was isolated from unreacted rubber and free PMMA fractions and composition characterization of the separated fractions was done by determination of rubber unsaturation. The efficiency of grafting under different conditions has been calculated and compared.
    Additional Material: 1 Ill.
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  • 17
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 183 (1982), S. 1093-1099 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: N-Vinylcarbazole (NVC) is polymerised in the presence of pyridine at 60°C by using azodiisobutyronitrile (AIBN) and benzoyl peroxide (Bz2O2) as initiators and the results are compared with those obtained when benzene is used as the solvent. In the AIBN-initiated system using pyridine as the solvent the rates of polymerisation follow an usual linear relationship with respect to monomer concentration and a square root dependence with respect to the initiator concentration. In the Bz2O2-initiated system, however, deviations from these ideal behaviours are observed when benzene and pyridine, respectively, are used as the solvent. Initiation occurs through the complexation of the monomer with Bz2O2 and degradative transfer is thought to be mainly responsible for this unusual kinetic behaviour.
    Additional Material: 1 Ill.
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  • 18
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 1593-1604 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Photopolymerization of methyl methacrylate (MMA) in bulk and in solution was studied using the combination benzil (BZL)/triethylamine (TEA) as photoinitiator. The initiation was found to occur through photoreduction of the ketone in presence of an amine via exciplex formation. A kinetic study of the polymerization showed that both carbonyl groups of benzil are involved in exciplex interaction, resulting in diradical formation. An analysis of the initiator dependent termination process revealed that primary radical termination is predominant in the particular system compared to the degradative initiator transfer. A kinetic scheme was designed to account for the various wastage reactions occurring in the polymerization system.
    Additional Material: 9 Ill.
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  • 19
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 1009-1015 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The existing models of high density polyethylene (HDPE) fail to tackle effectively the development of mechanical anisotropy on drawing at different temperatures. This paper is concerned with the theoretical interpretation of the anisotropic elastic properties of HDPE by applying the composite model proposed by the authors. The model takes into account the change in orientation and crystallinity on drawing. As far as the orientational changes on drawing are concerned, it is seen that the pseudo affine deformation law tan θ = φ(n) · tan θ′ with φ(n) = n-3/2 is applicable at -60°C only. It is further found that the two parameter analytical form of φ(n) reproduces the correct orientational changes on drawing for the entire temperature range from -60 to 100°C. The agreement of the calculated values of E0 and E90 over the entire temperature range at all drawing ratios is quite satisfactory.
    Additional Material: 4 Ill.
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  • 20
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A unified study of the optical and mechanical properties of polyoxymethylene (POM) is attempted in the framework of the composite model for a wide range of temperature (-60 to 120°C) which covers a region well below and above the γ-relaxation temperature. It was found that the existing two phase models for semicrystalline polymers are not adequate for interpreting the mechanical properties of POM over a wide temperature and drawing ratio range. The composite model takes into consideration the effects due to the change in crystallinity and orientation on drawing. The elastic moduli of the composite units are also calculated in terms of those of its constituents. The orientational changes on drawing were directly computed from the birefringence data. It was observed that the general agreement of the calculated and experimental values of the elastic moduli over the entire temperature and drawing ratio range is quite satisfactory.
    Additional Material: 3 Ill.
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