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  • Physics  (104)
  • LUNAR AND PLANETARY EXPLORATION
  • 1970-1974  (105)
  • 1973  (105)
  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 11 (1973), S. 2031-2043 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Farol-Weissenberg rheogoniometer has been used to follow molecular weight changes during the degradation of certain poly-α-esters in the melt state. By observing the change in melt viscosity at low shear rates it had been shown that the decomposition of the poly(isopropylidene carboxylate) is substantially first-order with respect to the molecular weight of the residual polymer. The derived kinetic parameters are in good agreement with those previously obtained by other techniques. This provides a substantial piece of supporting evidence for the view that degradation takes place predominantly by intramolecular ester interchange involving the formation of 1,1,4,4,-tetramethylglycollide. The introduction of β-chlorine atoms into the polymer structure leads to a more complex degradation pattern. Thus the presence of a single β chlorine atom per repeat unit, as in poly(3-chloro-2-methyl-2-hydroxypropionic acid) leads to a substantially similar dependence on molecular weight with the added complication of progressive crosslinking which becomes more apparent in later stages of the reaction. This crosslinking reaction plays an increasingly important part as the extent of chlorination of the polymer is increased. In addition, the presence of chlorine leads to an increased sensitivity of the degradation reaction to the presence of oxygen.
    Additional Material: 6 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 11 (1973), S. 2991-2997 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly-3-methyl-1-butene has been synthesized by Et2AlCl/tBuCl initiator at -130°C. A cast film of this material gave three well defined crystalline phases, α, β, and γ, characterized by infrared spectroscopy. The γ polymorph could not be obtained independently of the other two. Synthesis and/or manipulative procedures that would consistently give only one of the polymorphs are still unavailable. Evidently, the three crystalline phases have very similar lattice energies, and the subtle factors that determine the ultimate nature of the crystal lattice are not yet understood.
    Additional Material: 4 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 1817-1828 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The heat capacity of polyhexene-1 was measured between 20 and 300°K. The apparatus, an adiabatic calorimeter giving results with a random error of 0.2-0.4%, is briefly described. The characterization of the sample by x-ray diffraction patterns established that it was amorphous at all temperatures. Gold foil was incorporated with the sample to increase the apparent thermal diffusivity and so to decrease the time needed for the measurements. The glass transition temperature was found to be 215.5 ± 1°K. On the Cp curve, no subglass anomaly was detected, unlike the results of experiments described elsewhere. The calculation of Cv is discussed, and an explanation is given for the choice of the number of intramolecular vibrational modes per monomer which are assumed to contribute to Cv. A linear continuum model with characteristic temperature θ1 = 736°K allows us to fit the experimental curve over a temperature range of 140°K.
    Additional Material: 6 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 929-938 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: By means of an extrusion technique, a uniformly oriented macrolattice based on an alternating sequence of polystyrene and polybutadiene lamellae has been obtained. This is confirmed by the techniques of low-angle x-ray diffraction, electron microscopy, and electron diffraction. Layer thicknesses and spacings have been derived, and good quantitative agreement exists between the values obtained by the different methods. In addition, the electron micrographs exhibit many singular features which are of potential importance both in their own right and for the macroscopic properties.
    Additional Material: 8 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 1941-1948 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An expression for the flow field resulting from a time-dependent force with time-dependent point of action is derived from the linearized Navier-Stokes equations. The result is written as a sum of terms, the first of which is the “slow-change limit” corresponding to a stationary force acting at a stationary position. The application to the steady rotation of a dumbbell shows that this sum corresponds to a series expansion in powers of (L2|Ω|/v)1/2 where 2L is the length of the dumbbell, Ω is its angular velocity, and v is the kinematic viscosity of the liquid. It is pointed out that the results obtained are relevant to the problem of rotatory Brownian motion and to that of non-Newtonian viscosity.
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 2273-2282 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The relevance of diamagnetic susceptibility as a tool for the structure analysis of solid high polymers is stressed in the light of some new examples. The present results complement previous data and offer new aspects on the diamagnetic investigations of longchain hydrocarbons, especially polyethylene (PE). The molecular susceptibility is proportional to the average number of repeat units in the chain. The proportionality factor defines an intermolecular constant μk which characterizes different physical states. This was found to be 2.5 × 10-6 for the liquid and 3.5 × 10-6 cgs for the crystalline state of paraffins and polyethylene (solution-crystallized). For melt-crystallized material, μk, approaches the typical value of the liquid paraffin in agreement with previous results. Such a low μk is probably related to the increased disorder of the paracrystalline lattice domains, in contrast to the more ordered microparacrystallites in the so-called “single crystals,” where μk = 3.5 × 10-6. In single crystals of branched PE, μk approaches 2.5 × 10-6 with increasing branching ratio. Like paraffins in the gaseous state, molten PE, with chains longer than 1000 Å, has μk = 0. If the solution-crystallized material is molten for 10 min and thereafter cooled, μk retains the original value 3.5 × 10-6 cgs characteristic of the crystalline state. Hence, solution-crystallized polyethylene apparently possesses a kind of “memory.” Such a “memory” can, nevertheless, be partly destroyed when molten PE is stirred for 10 min and then quenched. Aggregates of solution-precipitated crystals with 3% branching concentration give μk = 2.9 ± 0.2 × 10-6 in good agreement with x-ray diffraction data. Finally, experimental details on the magnetic measurements are critically discussed, and various aspects of improvements for further investigations are also described.
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 1841-1848 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The application of laser-Raman spectroscopy to the analysis of copolymers of glycidyl methacrylate (GMA) with methyl methacrylate (MMA) and styrene is discussed. For both copolymer systems the line near 1451 cm-1, assigned to the methylene bending mode, was found to be a useful reference. Lines characteristic of each monomer were identified. The intensities of these lines were found to be linearly related to the composition of the copolymers when normalized against the 1451 cm-1 reference. The line near 1730 cm-1, assigned to the carbonyl stretching mode, was also found to be a useful reference for the copolymers of methyl methacrylate and glycidyl methacrylate.
    Additional Material: 9 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 11 (1973), S. 1079-1093 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal degradation of poly(isopropylidene carboxylate) has been studied over the temperature range 200-800°C by using the kinetic and analytical techniques described in Part I of this series. Over a wide range of temperature, tetramethyl glycollide, acetone, carbon monoxide, and, to a lesser extent, methacrylic acid are observed when the products are rapidly swept away from the reaction zone. As decomposition temperature is increased, tetramethyl glycollide takes on the role of an intermediate, the more stable products carbon monoxide and acetone being formed from it. At the highest temperature examined, carbon monoxide begins to predominate, and its formation is accompanied by formation of small amounts of a carbonaceous residue. When the reaction products are allowed to remain in the reaction zone, which is possible at the lower end of the temperature range, methacrylic acid becomes the major product. This is interpreted as a dual decomposition route, involving the tetramethyl glycollide intermediate. Kinetic studies have shown that the decomposition is a first-order process and that the first-order rate constant k is related to temperature (T) by the expression: \documentclass{article}\pagestyle{empty}\begin{document}$$ k = 4.1 \times 10^7 e^{{{ - 27,200} \mathord{\left/ {\vphantom {{ - 27,200} {RT}}} \right. \kern-\nulldelimiterspace} {RT}}} {\rm sec}^{ - {\rm 1}} $$\end{document} The results are interpreted in terms of an intramolecular ester interchange process involving tetramethyl glycollide as the primary decomposition product.
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  • 9
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 11 (1973), S. 1069-1077 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The various types of polyester degradation known to occur at elevated temperature are briefly summarized with particular reference to features of potential diagnostic value. Although little is known of poly-α-ester degradation in particular, examination of work on other linear polyesters indicates the spectrum of analytical and kinetic information that will be needed to characterize the degradation of poly-α-esters of various structures. On the basis of this review, an apparatus has been designed which enables kinetic information to be simultaneously obtained by thermogravimetry, gas evolution analysis, and rheological studies of the residual polymer melt. In addition a gas sampling procedure enables twin-column gas-liquid chromatographic analysis to be carried out on the degradation products. Samples of the chromatographically separated degradation products are collected in a microcollector cell for infrared and mass spectrometric analysis. Other refinements include in-line filament and Curie-point pyrolysis techniques.
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  • 10
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 11 (1973), S. 2343-2355 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal degradation of two β-chlorinated versions of poly(isopropylidene carboxylate) has been studied by the combined thermogravimetric and gas evolution techniques described previously. Poly(3-chloro-2-methyl-2-hydroxypropionic acid) was found to decompose by a predominantly first-order process which was characterized by kinetic parameters similar to those obtained for poly(isopropylidene carboxylate). These are interpreted in terms of an intramolecular ester-exchange process. As the reaction proceeds intermolecular elimination of hydrogen chloride leads to crosslinking and ultimately to the formation of a carbonaceous char. This process is much more marked in the randomly β-chlorinated analog of poly(isopropylidene carboxylate). With this polymer, drastic deviation from first-order behavior is observed in thermogravimetric results, even in the early stages of reaction. Gas evolution analysis, being more influenced by degradation fragments having an appreciable vapor pressure, yields reasonable first-order data and indicates that the intramolecular interchange mechanism is still an important process. In general, the introduction of β-chlorine atoms is seen to reduce the rate of thermal decomposition of poly-α-esters.
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