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  • 1980-1984  (11)
  • 1
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 88 (1984), S. 6100-6103 
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Journal of thermal analysis and calorimetry 25 (1982), S. 391-397 
    ISSN: 1572-8943
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Der Einfluß der Probengeometrie auf den Schmelzpunkt isotherm geschmolzenen kristallinen Polyäthylens wurde untersucht. Die Peakpositionen in den mit einem Perkin-Eimer DSC erhaltenen Diagrammen wurden als scheinbare Schmelzpunkte (Tm) benutzt. Bei konstantem Probengewicht (etwa 0.05 mg) wurde für Im ein Anstieg um 1.7 K beobachtet, wenn die Schichtdicke der Probe von 1 auf 8 μm erhöht wurde. An Experimenten werden auch die mit dem Schmelzvorgang bei Polymerproben zusammenhängenden Wärmeübergangsprobleme aufgezeigt. Diese Arbeit macht deutlich, daß eine Verminderung des Probengewichts allein zur Verminderung der Aufheizgeschwindigkeitsabhängigkeit der Polymerproben nicht ausreichend ist. Es soll vielmehr eine gleichzeitige Vergrößerung der Probenträgerkontaktfläche und Verringerung der Probenschichtdicke angestrebt werden.
    Abstract: Резюме Исследовано влияние геометрии образца на точку плавления изот ермически плавленного кристал лизационного полиэт илена. Положения пиков терм ограмм, полученных с помощью ДСК (фирмы Пе ркин-Эльмер), были использованы как каж ущиеся точки плавленияТпл. При по стоянном весе образц а (около 0.05 мг), но при увеличении е го толщины от 1 до 8 ммк, наблюдалос ь увеличениеТпл. на 1.7 К Представлены экспер именты, показывающие пробле мы переноса тепла, свя занные с плавлением образцов полимера. Исследования показы вают, что одна попытка понизить зависимость скорост и нагрева образцов полимера од новременно уменьшая вес образца, является недостаточ ной. Скорее должна преследовать ся цель одновременно го увеличения поверхно стного контакта печи с образцом и уменьшен ие толщины образца.
    Notes: Abstract We have examined the influence which sample geometry has on the melting point of isothermally melt crystallized polyethylene. The peak positions of curves obtained using a Perkin-Elmer DSC were used as the apparent melting points (Tm). With a constant sample weight (ca. 0.05 mg), we observed an increase of 1.7 K for Tm when the sample thickness was increased from 1 to 8 μm. Experiments which demonstrate the heat transfer problems related to the melting of polymer samples are also presented. This work indicates that, if one is attempting to reduce the heating rate dependence of polymer samples, reduction of sample weight alone is not suffiicient. Rather one should aim at increasing the sample pan contact area and reducing the sample thickness simultaneously.
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 28 (1983), S. 3603-3606 
    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
    Additional Material: 2 Tab.
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  • 4
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 27 (1982), S. 3591-3595 
    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: Oligomers are potentially useful as well characterized models for studying the chemical and physical properties of their long chain homologues. These model compounds are often available only as mixtures which must be separated. This separation may be accomplished using chromatographic techniques, i.e., GPC. Polydispersity (Mw/Mn) is often used as a criteria for the extent to which separation has been achieved. Values of polydispersity of 1.01-1.03 are considered indicative of very narrow fractions in the high polymer area. A purpose of this paper is to show that such low values of polydispersity are misleading when applied to oligomers containing 2-20 repeat units. Further, the existence of a single “sharp” melting endotherm is not necessarily proof that one has separated out a single molecular weight component. An intimate mixture of different molecular weight oligomers can give a single narrow endotherm.
    Additional Material: 2 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 19 (1981), S. 1237-1243 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polyethylene single crystals were grown from 0.1% solutions in xylene at 80 and 87°C. Oriented mats were made from each preparation and the small-angle x-ray scattering (SAXS) profiles obtained. Following treatment of the raw data for main-beam position and width, background scatter, and the Lorentz factor, five Bragg reflections were resolved. A one-dimensional lattice was used as a model for the oriented mats of single crystals. This model contains three parameters. An additional parameter Gx was also introduced to demonstrate the general effect of a broadening factor on the model. The effect of each parameter on the calculated diffraction pattern was examined. From this examination it was found that by assuming that the broadening functions are zero we can determine directly from the number of observable peaks the maximum possible thickness of the amorphous surface. Further, we find that the thickness of the amorphous layer must be less than the maximum value calculated if Gx is assigned values greater than zero. A “best-fit” diffraction pattern was generated in order to estimate how much smaller the surface thickness can be such that one can still resolve five diffraction maxima. The range of amorphous surface thicknesses found from the calculated diffraction profile is 12-20 Å. This is in good agreement with complementary studies performed on the same crystal preparations.
    Additional Material: 5 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 19 (1981), S. 1577-1591 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A set of isothermally melt-crystallized polyethylene samples was examined using small-angle x-ray scattering (SAXS). Time and temperature of crystallization were the variable parameters used to create the set of samples. Following background subtraction, desmearing, and application of the Lorentz factor to the raw SAXS data it is possible to see many orders of reflection. This suggests that much higher degrees of order are present in isothermally melt-crystallized samples than had previously been thought possible. A combination of SAXS and DSC data indicates that there is no evidence for isothermal thickening in these samples. This study, coupled with data obtained from PE single crystals, produced information concerning the extrapolation of single-crystal data to fit bulk systems. In addition, the equilibrium melting point T0m determined is somewhat lower than previously claimed. This study also suggests that the surface energy of the mature crystals is always lower than that of the nucleated state and/or the nucleation factor Kσen increases with decreasing supercooling.
    Additional Material: 11 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 19 (1981), S. 1923-1924 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 1 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 19 (1981), S. 487-497 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The width at half-height of SAXS discrete diffraction peaks has been used to compute the number of polyethylene lamellae in a stack. The dependence of this width on diffraction order reflects the nature and magnitude of lattice fluctuations. Within the literature there have been conflicting reports on this order dependence and hence on the nature of the lattice fluctuations. Previous studies have neglected the effects of instrumental broadening. These present studies show that instrumental effects can account for some 40% of the observed first-order peak width and drastically change the ratio of peak widths as a function of order. These studies, carried out on isothermally grown polyethylene single-crystal mats, also demonstrate the importance of the functions chosen to represent the various broadening factors. A mat was made up consisting of randomly stacked lamella with two distinct fold periods. The scattering from this mixed mat could not be described by either of the prevailing theories.
    Additional Material: 4 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1687-1693 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The fold periods and longitudinal acoustic modes [LAMs] for isothermally crystallized polyethylene (PE) single crystals were determined in the dried state and in the presence of decalin and silicone oil. Upon swelling with decalin, the fold period increased by 7% while the LAM peak frequency decreased by approximately 1 cm-1. Several possible explanations for the change in LAM frequency are discussed but the exact interpretation is open to question. No change in fold period was observed upon soaking a dried crystal mat in silicone oil. This fold period invariance along with the fact that silicone oil has no effect on the melting point of PE crystals indicates that there is no significant interaction between the oil and the methylene groups on the crystal surface. The effect of suspending crystals (which have never been dried down) in silicone oil should only be to increase the average interlamellar distance and, therefore, to reduce any interlamellar forces. It is shown that the LAM peak frequency for crystals suspended in silicone oil is the same as that for the dried crystals, indicating that interlamellar forces do not exert a significant perturbing influence on the LAM of polyethylene crystals.
    Additional Material: 2 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 22 (1982), S. 766-776 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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: A general criterion for craze formation is presented. Crazes are deformation zones that are common to both glassy and semicrystalline polymers. Crazes are composed primarily of fibrils. This paper attempts to describe the process that transforms unoriented glassy and semicrystalline polymeric solids into a fibrous state. The criterion for crazing discussed is a local phase transition. The transition occurs at the draw temperature. Unoriented solid-phase macromolecules, at local high-stress regions, undergo a transition to the elastomeric phase. Rapid extension and accompanying resolidification produce the fibrous morphology of craze fibrils. Cavitation of the deforming rubber phase ocurs because the local length increase is riot compensated for by an overall area decrease. Craze formation in glassy polymers has long been suspected to involve a local solid-to-rubber phase change. To relate crazes in glassy and semicrystalline polymers, one can assume that a solid-to-rubber phase change is required to produce craze fibrils in semicrystalline polymers. The transient melt phase would undergo rapid elongation, causing the formation of extended chain crystallites. These subsequently nucleate the remaining melt, which then crystallizes epitaxially as lamellae. Crystallization during flow would, therefore, be the mechanism of fiber formation.
    Additional Material: 8 Ill.
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