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51.
Lung A Stuart LM Bosted PE Andivahis L Alster J Arnold RG Chang CC Dietrich FS Dodge WR Gearhart R Gomez J Griffioen KA Hicks RS Hyde-Wright CE Keppel C Kuhn SE Lichtenstadt J Miskimen RA Peterson GA Petratos GG Rock SE Rokni SH Sakumoto WK Spengos M Swartz K Szalata Z Tao LH 《Physical review letters》1993,70(6):718-721
52.
U. Groß P. Dietrich G. Engler D. Prescher J. Schulze K. Lunkwitz A. Ferse 《Journal of fluorine chemistry》1982,20(1):33-52
The present work studies the changes in polymer structure and the mechanism of the decomposition of polytetrafluoroethylene resin (PTFE) exposed to high energy radiation (electron beam). Spectroscopic and kinetic observations are used to interpret the degradation process. For the first time the decomposition of PTFE has been carried out on a preparative scale and new results obtained by analysing the degradation products. The radiation-induced degradation of PTFE is accompanied by thermal degradation under certain irradiation conditions. This is due to an increase in temperature of the polymer caused by retardation of highly accelerated electrons (heat accumulation effect).The kinetics are discussed in terms of the reactions and recombination of radicals produced by high-energy radiation both in the polymer melt and the polymer surface. These are related to the overall rate of decomposition.The primary radicals formed by decomposition of PTFE in an inert atmosphere (N2, Ar) react to produce perfluorinated alkanes and alkenes. In the presence of reactive gases the decomposition fragments originated will react rapidly; e.g. if oxygen is present in the reactive area the radicals form perflourinated peroxyl and oxyl radicals which finally stabilize themselves by CC-scission to perfluorocarbon acid fluorides and carbonyldifluorides. 相似文献
53.
Malykhina L. V. Prosvirin A. V. Haase W. Galyametdinov Yu. G. 《Russian Chemical Bulletin》2001,50(3):488-493
The reaction of Schiff"s base L with lanthanide alkylsulfates affords liquid crystalline complexes with the general formula L3Ln(CnH2n+1OSO3)3. The liquid crystalline structure and magnetic properties are studied by polarization thermal microscopy, differential scanning calorimetry, X-ray diffraction, and measurement of magnetic susceptibility. The temperatures of the existence of the mesophase and magnetic anisotropy of the complexes with the same lanthanide depend on the chain length of the alkyl fragment in the sulfate anion. 相似文献
54.
Renate Obenaus und Dietrich Mücke 《Fresenius' Journal of Analytical Chemistry》1964,201(6):428-435
Zusammenfassung Es wird eine indirekte Methode zur Bestimmung des spezifischen Kaliumpermanganatverbrauches von Huminsäuren beschrieben. Die Huminsäuren werden mit einer 0,01 m Blei(II)-nitratlösung gefällt und der gebildete Pb-Huminsäure-Niederschlag ausgewogen. Aus dem PbGehalt und dem Kaliumpermanganatverbrauch des Pb-HuminsäureKomplexes ergibt sich der Kaliumpermanganatverbrauch pro Milligramm Huminsäure. Im Gegensatz zu Eisen(III)-chlorid verändert Blei(II)nitrat die Oxydierbarkeit der Huminsäuren nicht, so daß indirekt und direkt bestimmter spezifischer Kaliumpermanganatverbrauch übereinstimmen.Es wurden die spezifischen Kaliumpermanganatverbrauchswerte von zwei Huminsäuren bekannter Oxydierbarkeit (Fluka-Humussäure und Moorwasser-Huminsäure) und von Huminsäuren aus 3 natürlichen Wässern bestimmt. Die Fehlerbereiche der Mittelwerte betragen bei den Modellsubstanzen (je 15 Analysenwerte) ±4% (Huminsäure Fluka) bzw. ±3% (Moorwasser-Huminsäure) und bei den praktischen Analysen ±4% ±11% bzw. ±7% des jeweiligen Mittelwertes.
Wir danken Frl. Roswitha Raspe und Frau Helga Boje für fleißige technische Mitarbeit. 相似文献
Summary An indirect method for the determination of the specific permanganate consumption of humic acids is described. The humic acids are precipitated by 0,01 M lead(II)nitrate and the precipitate of lead-humic acid is weighed. The permanganate consumption per mg humic acid results from the lead-content and the permanganate consumption of the lead-humic acid complex. As opposed to ferric chloride lead(II) nitrate does not change the oxidizability of humic acids; hence, indirectly and directly determined permanganate consumption equal each other. — The values of the specific permanganate consumption of two humic acids of known oxidizability and of three samples of humic acids isolated from natural water-sources are determined. The limit of error of the mean values is between ±3% and ±11%.
Wir danken Frl. Roswitha Raspe und Frau Helga Boje für fleißige technische Mitarbeit. 相似文献
55.
Dietrich Braun 《Angewandte Chemie (International ed. in English)》1976,15(8):451-459
One of the topical problems of macromolecular chemistry is the question of the extent to which macromolecules in solution or in the amorphous solid state can engage in mutual interpenetration. The present article is concerned primarily with recent investigations on cross-linking copolymerization and with inter-and intramolecular reactions of polymers as a contribution to the study of molecular shape. 相似文献
56.
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58.
With the aid of thinlayer chromatography mixtures of tetraorganotin compounds containing no polar groups can be separated and identified if they differ in the number of phenyl groups per molecule or in the nature of their aliphatic residues (alkyl or allyl). For analytical purposes mixtures of 80% hexane and 20% benzene by volume are suitable as mobile phase. For preparative purposes (requiring multiple development) pure hexane or hexane containing 10 to 20% benzene by volume are best suited as mobile phase, where the amount of hexane depends on the problem of separation at hand. The Rf values of the mobile phases vary linearly with the number of the phenyl groups x and decrease with increasing x. The straight lines connecting the Rf values cross at x=4 (tetraphenyltin). Dithizone and silver nitrate are suitable spray reagents for organotin compounds. By spraying the plates with dithizone tetra-, tri-, and di-organotin compounds can be immediately distinguished on the basis of the ensuing colourations. With silver nitrate allyltin compounds and polystannanes can be distinguished from alkyltin compounds; tetra-phenyltin is not coloured by this reagent. 相似文献
59.
Wolfgang Frenzel Annette Rauterberg-Wulff Dietrich Schepers 《Fresenius' Journal of Analytical Chemistry》1995,353(2):123-127
Non-suppressed ion chromatography (NSIC) has been optimized to permit the determination of chloride, nitrate and sulfate in the low mg/l concentration range within 3 min. Using conductometric detection the extraneous (positive) injection peak was found to adversely affect the early eluting chloride signal when samples with high amounts of total cations are analyzed. The serial arrangement of a downstream potentiometric detector with a chloride ion selective electrode, which does not respond to other alterations of the composition of the eluent than the change in chloride concentrations, is shown to be suitable for interference-free, sensitive and reliable chloride evaluation. Application of the proposed system to the determination of chloride in extracts of filter collected airborne particulates revealed (for those samples that could be evaluated by both detection methods) high precision and no systematic deviations between conductometric and potentiometric detection.Dedicated to Professor Dr. Peter Brätter on the occasion of his 60th birthday 相似文献
60.
Boca R Boca M Dlhán L Falk K Fuess H Haase W Jarosciak R Papánková B Renz F Vrbová M Werner R 《Inorganic chemistry》2001,40(13):3025-3033
The spin crossover system, [Fe(bzimpy)(2)](ClO(4))(2).0.25H(2)O, was reinvestigated above room temperature (bzimpy = 2,6-bis(benzimidazol-2-yl)pyridine). The system exhibits an abrupt low-spin to high-spin transition at T(c) = 403 K. Liberation of a fractional amount of water does not affect the spin crossover: the system is perfectly reversible with a hysteresis width of DeltaT = 12 K. The existence of the hysteresis at such high temperature determines that the lowest limit of the solid-state cooperativity parameter is J/k > 403 K despite long iron(II) separations (10 A). The high cooperativeness has been assigned to a perfect pi-stacking of the benzimidazole rings in the crystal lattice at a distance as short as 3.6 A. Variable-temperature IR data and the heat capacity measurements match well the magnetic data. The thermodynamic properties are DeltaH = 17 kJ mol(-)(1), DeltaS = 43 J K(-)(1) mol(-)(1), so that the entropy of the spin transition shows a considerable contribution from the molecular vibrations. A theoretical model has been applied in fitting the magnetic data along the whole hysteresis path. A statistical distribution of the cooperativity parameter led to the feature that angled walls of the hysteresis loop are well reproduced. 相似文献