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  • 11
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 919-927 
    ISSN: 0887-6266
    Keywords: dielectric relaxation ; aromatic polyamides ; rotational barrier ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dielectric relaxation spectroscopy (DRS) is presented for a family of four aromatic polyamides trying to relate the structure of the lateral groups to the molecular mobility. A prominent sub-Tg absorption is always seen followed in some cases by remanent dielectric activity at room temperature and a subsequent increase of the loss permittivity. The low temperature relaxation is analyzed in terms of a Fuoss-Kirkwood equation to obtain the broadness and the strength of these relaxations as well as the activation energy (ranging from 10 to 11 Kcal/mol). The low frequency conductive peak shows in each case a half-width higher (1.30) than those corresponding to a single relaxation time peak (1.144). These values of the half-width are an indication of the complex character of these phenomena. A final discussion of the rotational barriers of the lateral chains rules out that such motions are the only molecular origin for the gamma relaxation. Instead, some kind of motion involving the main chain and where the interchain interactions play a significant role should be considered as responsible for that relaxation. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 919-927, 1997
    Additional Material: 9 Ill.
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  • 12
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 395-402 
    ISSN: 0887-6266
    Keywords: syndiotactic polypropylene ; form-IV ; form II ; kink bands ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The packing of the chains in (T6G2T2G2)n conformation of the form IV of s-PP is revisited on the basis of packing energy and structure factor calculations. According to this analysis, an alternative mode of packing has been suggested. A monoclinic structural model, with the unit cell centered on the C face, is obtained, after small changes of the atomic coordinates in the triclinic structural model as proposed by Chatani et al. The monoclinic model presents a lower packing energy than the triclinic model and a good agreement between the calculated and observed structure factors. The triclinic structural model implies that all the chains are rotated by the same amount around the chain axis with respect to the monoclinic structural model. Since clockwise and counter clockwise rotations are equivalent, the monoclinic structural model may be taken as descriptive of the order in the long range, for the form IV of s-PP, or in other terms, descriptive of an average structure (space group C2, unit cell constants equal to am = 14.17 Å, bm = 5.72 Å, cm = 11.6 Å, and βm = 108.8°). The triclinic structural model for this polymorph, instead (space group P1, unit cell constants equal to at = 5.72 Å, bt = 7.64 Å, ct = 11.60 Å, αt = 73.1°, βt = 88.8°, γt = 112.0°) is probably more properly descriptive of local situation of order (the symmetry, locally, is broken). Analogies between the monoclinic limit ordered structural model for the form IV and the orthorhombic limit ordered structural model for the form II (with chains in the more stable (TTGG)n conformation) of s-PP are also provided. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 395-402, 1998
    Additional Material: 5 Ill.
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  • 13
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Macromolecular Rapid Communications 15 (1994), S. 417-424 
    ISSN: 1022-1336
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 4 Ill.
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  • 14
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Macromolecular Rapid Communications 15 (1994), S. 697-704 
    ISSN: 1022-1336
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 1 Ill.
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  • 15
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: N-Carboxy-(N∊-benzyloxycarbonyl)-L-lysine anhydride (Z-L-lysine NCA) was polymerized in dimethylformamide with triethylamine, diethylamine or hexylamine as initiator, at varying molar ratios of NCA to initiator (M/I ratio). After removal of the protecting Z-group the resulting poly-L-lysine was characterized with 1H NMR and MALDI TOF MS. Both diethylamine- and hexylamine-initiated polymerization yielded poly-L-lysine in which the initiators were incorporated at the carboxylic end of the polymer. This indicates that the NCA polymerization occurred exclusively via nucleophilic attack of the initiator on the monomer. On the other, hand, when triethylamine was used as the initiator, poly-L-lysine was obtained in which no triethylamine-derived end group could be detected by MS. These polymer chains are most likely end-capped with an N-acyl-2,5-dioxopiperazine group at the carboxylic end of the polymer. Incorporation of diethylamine and hexylamine allowed determination of the degree of polymerization (DP) of the obtained polymers by 1H NMR. The DP depended linearly on the M/I ratio, for both diethylamine and hexylamine, with higher DPs for the diethylamine-initiated poly-L-lysine at equal M/I ratio.
    Additional Material: 6 Ill.
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  • 16
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Macromolecular Chemistry and Physics 198 (1997), S. 3293-3303 
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Two series of aromatic polyamides were prepared from m-phenylenediamine (MPD) and 4,4′-diaminodiphenyl sulfone (DDS) in combination with a set of new halogenated diacyl chlorides, namely, 5-fluoroisophthaloyl chloride, 5-chloroisophthaloyl chloride, 5-bromoisophthaloyl chloride and 5-iodoisophthaloyl chloride. The polymers were synthesized in high yields and in high molecular weight (as determined by gel permeation chromatography) by means of the low temperature condensation method. Noticeable changes in the spectral characteristics of the halogen-modified polyisophthalamides were observed compared to those of the corresponding unmodified polyisophthalamides. Slight improvements were observed for the glass transition temperatures, which increased 5-30°C relative to those of the conventional polyisophthalamides. Moreover, a correlation was found between the size of the halogen substituents and the increase in Tg values. Thermogravimetric analysis showed that the new polymers are almost as thermally resistant as the unmodified ones, while solubility in organic solvents was some-what poorer.
    Additional Material: 4 Ill.
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  • 17
    Electronic Resource
    Electronic Resource
    Chichester [u.a.] : Wiley-Blackwell
    Surface and Interface Analysis 5 (1983), S. 119-131 
    ISSN: 0142-2421
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: A quantitative evaluation of RBS data resulted in data for the parabolic reaction rate constants for the reaction between Al2O3 and NiO at temperatures from 960°C up to 1105°C. The activation energy and the preexponential factor were in good agreement with literature data. The experimental data of this work also permitted a detailed description of reaction mechanisms on a microscopic level. The reaction between Al2O3 and NiO starts with penetration of Al3+ ions along the grain boundaries of NiO, followed by counter-diffusion of Ni2+ ions. A thin spinel layer (NiAl2O4) is formed at the Al2O3/NiO interface, after a relatively short nucleation period. The reaction then proceeds, both by lateral and perpendicular diffusion. In an appendix, the detailed evaluation procedure of the spectra was described.
    Additional Material: 15 Ill.
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  • 18
    Electronic Resource
    Electronic Resource
    Chichester [u.a.] : Wiley-Blackwell
    Surface and Interface Analysis 19 (1992), S. 397-402 
    ISSN: 0142-2421
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: In order to understand better the protection mechanism of aqueous CrO3, the surface of untreated and treated wood, before and after weathering, was studied by XPS. For comparison, the reaction of CrO3 with filter paper, used as a model compound for cellulose, and with lignin powder was studied as well.Owing to differences in the O/C ratio and the shape of the C 1s signal, cellulose and lignin can be distinguished from each other with the aid of XPS. The low O/C ratio and the high C1 (C—C, C—H) contribution found for the surface of wood show that the upper layer is enriched with ligin and extractives. Weathering of wood starts with the degradation of lignin, and the appearance of cellulose on the surface increases the O/C ratio and shifts the maximum of the C 1s signal to the C2 (C—O—C, C—OH) position.Aqueous CrO3 oxidizes lignin powder and possibly also cellulose. The effect on wood, as observed with XPS, is small. The protection, however, is very clear; the increase of the O/C ratio of CrO3-treated wood during weathering is much slower than the increase for untreated wood. After weathering, the C 1s signal still resembles the C 1s signal of lignin, so the CrO3 protects the lignin from degradation.
    Additional Material: 8 Ill.
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  • 19
    ISSN: 0142-2421
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The virtual interface width in AES sputter depth profiles of amorphous anodic oxide coatings on aluminium is investigated. Even when the physical film-substrate interface is relatively sharp, considerable deterioration of the depth resolution may be caused by sputter-induced roughness if sputtering conditions or the sample quality are not chosen properly. The effects of the oxide film thickness, choice of sputter angle and initial substrate roughness on the appearance of the interface width are investigated. A systematic study of the influence of Zalar rotation on the depth resolution is presented. It is concluded that long sputter times, due to film thickness or grazing sputter angles, and initial surface roughness cause a deterioration of the depth resolution. Zalar rotation generally improves the depth resolution for amorphous films, and is particularly indicated for the analysis of very rough samples. The sputter rate of amorphous films however, is insensitive to the use of Zalar rotation.
    Additional Material: 2 Ill.
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  • 20
    ISSN: 0142-2421
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The solid state reaction of Al2O3—NiO reaction couples was investigated by means of Rutherford backscattering spectrometry. NiO films on the alumina substrates were obtained by vapour-deposition of Ni and subsequent oxidation at 800°C in air. Substrates of about the same surface roughness, thus providing equal contact areas for the reaction couples, were used. The materials were characterized by scanning electron microscopy. In spite of the different structure and a grain size that varied within a factor of 10, of the Al2O3 materials, no obvious difference in the spectra based on the used reaction couples could be detected. Suggested substantial contribution to the reaction from surface diffusion and grain boundary diffusion along the substrate grain boundaries could therefore be rejected.
    Additional Material: 8 Ill.
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