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  • 1
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Macromolecules 25 (1992), S. 6510-6515 
    ISSN: 1520-5835
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Polymer bulletin 9 (1983), S. 593-597 
    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary Dilatometric measurements of n-Tetracosane from 330 K up to 420 K are reported. These experiments show evidence for a small kink in the specific volume — temperature curve. The correct statistical interpretation of the measured data yield a discret transition temperature above the melting point at about 378 K in close agreement with the results from other experimental methods.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Polymer bulletin 3 (1980), S. 135-142 
    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary A homologous series of cycloalkanes from (CH2)14 up to (CH2)96 as model systems for tight folding in CH2-chain molecules was investigated by infrared spectroscopy. In comparison with the corresponding spectra of the nalkanes we found two additional new absorption bands at 700 cm−1 and 1442 cm−1 which can be assigned to a characteristic fold vibration. The already known fold band in the wagging region at about 1344 cm−1 could also be found in all cycloalkane spectra. A numerical decomposition of the bands enables the calibration of the fold concentration. The Davydov splitting of the (CH2)-rocking and (CH2)-bending vibration in the melt crystallized form of the molecules (CH2)72 and (CH2)96 show the occurence of a orthorhombic subcell of the larger rings whereas the smaller rings and the larger ones in the solution crystallized form only crystallize in a monoclinic form.
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 1435-1536
    Keywords: Condis phase ; high temperature transition of polyethylene ; cluster-entropy hypothesis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract On the basis of atomistic calculations a rotator model of the high temperature Condis phase of polyethylene is proposed. Its cooperative statistical treatment (using CEH for the lateral packing of chains) explains the first order transition from the all-trans crystal as well as the transition dataT t ,ΔS t ,ΔV t . We found that the normal melting (i. e. at pressures below the triple point) is also governed by the onset of the Condis phase.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    Colloid & polymer science 260 (1982), S. 378-393 
    ISSN: 1435-1536
    Keywords: Amorphous polymers ; biopolymers ; fibrils ; meander model ; superstructur
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Assuming bundles (of shortrange ordered macromolecules, folding back and forth statistically), their equilibrium superstructure and diameter are described on the basis of cluster-entropy-hypothesis (CEH). As primary blocks in the bulk polymer and in thin films coupled meander cubes are most probable, which are linked via their cube diagonals serving as axis of statistical rotation and aggregate to coarse grains. Magnetic birefringence, SANS and elctronmicroscopy are used as further methods to determine the cube side length. Applying the same concept to myosin-, collagen-, and elastin-aggregates, these can be interpreted as equilibrium meander fibrils, additionally stabilized by specific interactions and by the length of the molecules.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Springer
    Colloid & polymer science 259 (1981), S. 267-278 
    ISSN: 1435-1536
    Keywords: n-alkanes ; polyethylene ; high pressure ; melting ; meander model
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Zusammenfassung Aus druckdilatometrischen Messungen ann-Alkanen und an linearem Polyäthylen und aus Literaturergebnissen erhält man lineare Abhängigkeiten des spezifischen Volumens, der Umwandlungsentropie, der Umwandlungsenthalpie und der reziproken Umwandlungstemperatur von 1/n, wobein die Anzahl der C-Atome pro Molekül ist. Für den Grenzfalln→∞ führt die Extrapolation stets zu den Werten des Polyäthylens. Die Unterschiede zwischen den Eigenschaften dern-Alkane und des Polyäthylens lassen sich auf den Einfluß der Kettenenden zurückführen. Nimmt man für diese Kettenenden Entropie- und Enthalpiebeiträge an, wie sie durch ein molekulares Modell nahegelegt werden, so kann dien-Abhängigkeit der oben genannten Größen, einschließlich ihrer Druckabhängigkeit, quantitativ erklärt werden.
    Notes: Summary Results from high pressure dilatometry onn-alkanes and linear polyethylene and literature data yield a linear relation between specific volume, entropy and enthalpy of fusion, the reciprocal melting temperature and 1/n, wheren denotes the number of C-atoms per molecule. Extrapolating towards infiniten one always obtains polyethylene data. The differences in the properties ofn-alkanes and polyethylene can be ascribed to the influence of the chain ends. Assuming entropy and enthalpy contributions from these chain ends as made probable by a molecular model one can quantitatively explain then-dependence of the above mentioned quantities including their pressure dependence.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Springer
    Colloid & polymer science 255 (1977), S. 285-289 
    ISSN: 1435-1536
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Summary Low angle neutron scattering studies on amorphous polymers using labelled chains yield information on the scattering behaviour of these molecules. Until now, the scattering data of polymer chains were interpreted exclusively in terms of the random coil model. This work shows that the meander model with adjacent refolding within the bundle predicts a scattering behaviour of a labelled chain in agreement with the experimental results.
    Notes: Zusammenfassung Neutronenkleinwinkelmessungen an Polymerschmelzen, die markierte Ketten enthalten, können, Aussagen über deren Streuverhalten liefern. Bisher wurde das Streuverhalten einer einzelnen Polymerkette ausschließlich mit dem Knäuelmodell interpretiert. Diese Arbeit zeigt, daß die Streuung einer markierten Kette im Mäandermodell mit engen Rückfaltungen im Bündel die experimentellen Ergebnisse ebenfalls beschreiben kann.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    Colloid & polymer science 270 (1992), S. 639-651 
    ISSN: 1435-1536
    Keywords: n/i-transition ; LC-polymers ; meander model
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The purpose of this study is to examine the application of the meander model to the understanding of transition properties in the isotropic-nematic (paper I), and in the isotropic-smectic or — lamellar (paper II) phase transitions in polymers. This paper deals with the phase transitionwithin the stable meander structure which will take place if the entropy of cube rotation is counterbalanced by a reduction of interfacial energy that may be realized by a parallel arrangement of the anisotropic meander cubes within the coarse grains (i/n-transition). But no change in the short-range order within the cubes will be assumed. Considering the free energy in the meander model, the only relevant term for this transition is Δg rot which is derived, minimized to equilibrium, and discussed. By this procedure, the transition temperature, the heat and volume of transition, as well as their temperature dependences are deduced. The most important parameter is the excess volumev e per chain of cube side length, caused by crossed-chains at the cube-interfaces, which can be determined by atomistic calculations. This model theory is compared with experimental data [15] on one low molecular weight LC and two LC side chain polymers, as well as on the hypothetici/n-transition of polyethylene.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    Springer
    Colloid & polymer science 260 (1982), S. 248-257 
    ISSN: 1435-1536
    Keywords: phase transition ; dislocation theory of melting ; cluster-entropy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Abstract As a model for the melting of densely packed atomic crystals (as well as for the “true” melting of molecular and polymer crystals) the formation of tilt boundaries by dislocation loops inside a “melt-grain” with parallel glide planes is proposed. The dislocation arrangement is allowed to fluctuate in time and in space (from grain to grain). Taking lines of atoms (atomic dislocations) perpendicular to the tilt boundaries as statistical elements, and using the cluster-entropy-hypothesis (CEH), a cooperative treatment of the melt-transition and of the defect-contribution to the thermal properties as well as an estimate of the activation energy of the viscosity are achieved.
    Notes: Zusammenfassung Für das Schmelzen dichtgepackter Atomkristalle (und auch für die „eigentliche“ Schmelzumwandlung von Molekül- und Polymerkristallen) wird die Bildung von Wänden aus Versetzungsringen in einem „Schmelzkorn“ paralleler Gleitebenen vorgeschlagen. Diese Versetzungsstruktur kann zeitlich und räumlich (von Korn zu Korn) fluktuieren. Mit Atomreihen senkrecht zu den Versetzungswänden (Atomversetzungen) als statistischen Elementen und aufgrund der Cluster-Entropie-Hypothese (CEH) gelingt eine kooperative Behandlung der Schmelzumwandlung und des Defektanteils der thermischen Eigenschaften sowie eine Abschätzung der Aktivierungsenergie der Viskosität.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    Springer
    Colloid & polymer science 252 (1974), S. 871-879 
    ISSN: 1435-1536
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Zusammenfassung Diese Arbeit gibt am Beispiel des Polyäthylens eine Methode an, mit der Defekte in Polymerkristallen berechnet werden können. Das Verfahren wurde am Idealkristall überprüft und dann zur Berechnung von Kinken im Kristall verwendet. Es ergaben sich zwei stabile Kinklagen an jedem Gitterplatz. Die Defektenergie für die Kinken beträgt ca. 8,5 kcal/mol. DieReneker-Kinke (Renekerdefekt) im Kristall führt mit 13,5 kcal/mol zu einer wesentlich höheren Defektenergie. Blockanordnungen von Kinken erniedrigen die Defektenergie beträchtlich. Die Energieabsenkung pro Kinke beträgt für einen flächenhaften Block ungefähr 4 kcal/mol, für lineare Blöcke etwa 2 kcal/mol.
    Notes: Summary A method to calculate defects in polymer crystals is introduced and applied to the polyethylene crystal. It is tested for the ideal crystal and is then used to investigate defects (kinks,Reneker defects, kink blocks). Two stable kink positions have been determined at a lattice point. The defect energy of the kinks is about 8.5 kcal/mole. TheReneker defect has been found to have a remarkably higher defect energy of about 13.5 kcal/mole in the crystal. It has been verified that block arrangements of kinks decrease the defect energy per kink. The amount of decrease is about 4 kcal/mole per kink for planar kink blocks and is about 2 kcal/mole per kink for linear kink blocks.
    Type of Medium: Electronic Resource
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