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  • 1
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Macromolecules 10 (1977), S. 1128-1140 
    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
    Copenhagen : International Union of Crystallography (IUCr)
    Applied crystallography online 16 (1983), S. 519-523 
    ISSN: 1600-5767
    Source: Crystallography Journals Online : IUCR Backfile Archive 1948-2001
    Topics: Geosciences , Physics
    Notes: A method is described which provides an efficient way of analysing degrees of anisotropy in small-angle scattering. It is applied to isotopic mixtures of polyethylene crystallized from solution, and to the same system which has been annealed (heat treated). The degree of orientation of the lamellar crystallites is measured separately. The results can then be given in terms of molecular dimensions along and at right angles to the lamellar normals. It is found that each molecule is probably restricted to one lamella, and that its dimension along the lamellar normal increases on annealing.
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  • 3
    Electronic Resource
    Electronic Resource
    Copenhagen : International Union of Crystallography (IUCr)
    Applied crystallography online 18 (1985), S. 365-365 
    ISSN: 1600-5767
    Source: Crystallography Journals Online : IUCR Backfile Archive 1948-2001
    Topics: Geosciences , Physics
    Notes: In the paper by Sadler [J. Appl. Cryst. (1983). 16, 519–523] a factor of 2 was omitted in error in equation (10), which should read: 〈z2〉 = 〈a〉 + 〈b〉[1 + 2/〈P2(γ)〉]/3. The results in Table 1 were derived correctly from the data.
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Colloid & polymer science 242 (1970), S. 1081-1092 
    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 Eine Vielfalt von Techniken, umfassend Abbau, Kleinwinkelstreuung und Messung der Kristallinität, wurden auf Polyäthylenkristalle angewendet, die kristallographischen Kontakt zwischen den Lamellen aufweisen. Die Ergebnisse wurden im Rahmen eines Modells analysiert, wie es in der vorausgegangenen Veröffentlichung vorgeschlagen und in der vorliegenden Arbeit konkretisiert wird. Dieses Modell verlangt, daß im wesentlichen kurze Moleküle-1-3mal so lang, wei es die Schichtdicke verlangt-diese Kristalle aufbauen, so daß viele Enden in Lamellenoberflächen zu leigen kommen. Als eine Folge der Anwesenheit endlicher Molekulargewichte müssen diese Oberflächen rauch sein gemäß den ungleichen Längen für die Lamellenübergänge. Diese Rauhigkeit erlaubt eine Kuppelung der Schichten, welche die beobachteten kristallographischen Kontakte herbeiführen. IR-Experimente zeigen, daß die Enden in der Oberfläche liegen, G. P. C.-Analyse von salpetersäureabgeätztem Material mißt die Oberflächenrauhigkeit, wie sie durch die Fluktuation der Faltentiefen entsteht. Kontinuierliche Variation der Schichtdicken mit Kristallisationstemperature, beobachtet durch Röntgenstreuung, kann den Änderungen des Anteils an Molekülen mit verschiedenen Faltungszahlen zugeschrieben werden. Messungen der Schmelzwärme, Dichten und NMR-Linienweiten zeigen einen nichtkristallographischen Anteil, vergleichbar mit dem von gewöhnlichen Polyäthylenkristallen, wohingegen die Schmelzpunkte wegen des niedrigen Molekulargewichts reduziert sind. Als Folgerung daraus wird der nichtkristalline Anteil allein den rauhen Oberflächen zugeschrieben. Das allgemeine Problem des “amorphen” Anteils an Einkristallen wird in diesem Zusammenhang diskutiert.
    Notes: Summary A variety of techniques, comprising degradation, low angle X-ray diffraction, and measures of crystallinity, have been applied to polyethylene crystals showing crystallographic contact between constituent layers. The results are analysed in the light of the model proposed in the preceding communication, and defined more concretely in the present paper. This model requires that the short molecules-one to three times the layer thickness in length-which largely constitute these crystals should have their ends at the lamellar surfaces. As a consequence, in the presence of the finite molecular weight spread, these surfaces will have to the rough owing to uneven lengths of the lamellar traverses. This roughness enables intermeshing of layers, which constitutes the observed crystallographic contact. Infra red experiments verify that the ends are at the surfaces; G. P. C. analysis of nitric acid degraded material measures the surface roughness as detected by fluctuations in the depths of the folds. The continuous variation of the layer thickness with crystallization temperature observed by X-rays can be attributed to changes in the proportion of molecules with different numbers of folds. Measurements of heats of fusion, densities, and NMR line widths, reveal a non-crystallographic component comparable with the usual crystals of polyethylene, while the melting points are reduced because of the low molecular weights. As the crystallographic information has to be transmitted from one layer to the next there can be no true amorphous barrier between them. In consequence, the crystallinity deficiency is attributed to the rough surfaces only. Implications for the general problem of “amorphous” content in single crystals are discussed.
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    Colloid & polymer science 239 (1970), S. 641-654 
    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 In dieser Arbeit wird der Ursprung von Grenzflächennetzwerken an Polyäthylenkristallen betrachtet, so wie sie den kristallographischen Kontakt zwischen einander überlappenden Kristallen deuten. Bisher wurden derartige Fehlstellen nur unter besonders ungewöhnlichen und undefinierten Umständen beobachtet. Auf der Suche nach einer Erklärung wurde ein weiter Bereich an Polyäthylenfraktionen untersucht. Es ließ sich zeigen, daß die Fähigkeit, Fehlstellen in Zwischenflächen zu bilden, von der Anwesenheit von Molekülen abhängt, deren Länge nur das zwei- oder dreifache der Dicke der Lamellen beträgt. Detaillierte Korrelation wurde zwischen dem Grad des Kontaktes der Lamellen und dem Molekulargewicht hergestellt. Kristallographischer Kontakt wird durch die Zahl der Molekülenden hervorgerufen, bleibt jedoch aus, wenn viel Material mit Molekulargewichten wesentlich größer als 15000 anwesend ist. Neue elektronenmikroskopische Beobachtungen zeigen, daß Grenzflächenfehlstellen auftreten können, wenn sich gefaltete Bändchen von übereinander gelagerten Schichten kreuzen. Betrachtet im Hinblick auf die Größe derBurgers-Vektoren der Fehlstellen, zeigt sich, daß die Wechselwirkungen zwischen Falten auf der Schichtoberfläche nicht ausreichen, um den kristallographischen Kontakt zu erklären. Eine alternative Art des Kontaktes wird vermutet: die Molekülenden können aus der Schicht austreten und in gewissem Grad das Gitter der darüberliegenden Schicht durchdringen. Zwei Bedingungen für die Gültigkeit dieses Modells sind erforderlich, eine Tendenz, daß die Enden sich in den Kristalloberflächen befinden, und ferner, daß die Kristalloberflächen rauh genug sind, um freie Stellen für das Eindringen der Enden zu besitzen. Messungen zur Testung dieser Bedingungen werden in der folgenden Veröffentlichung mitgeteilt.
    Notes: Summary The investigation is concerned with the origin of interfacial dislocation networks in polyethylene crystals, such as are indicative of crystallographic contact between overlying lamellae. Previously such dislocations were only observed under exceptional and undefinable circumstances. In search for an explanation, a wide range of polyethylene fractions have been investigated. It has been established that the ability to form interfacial dislocations depends on the presence of molecules whose length is only two or three times the thickness of the lamellae. Detailed correlations have been made between the degree of lamellar contact and molecular weight. Crystallographic contact is promoted by the number of molecular ends, but is suppressed if much material above about 15000 in molecular weight is present. New electron microscope observations reveal that interfacial dislocations can occur when the folded ribbons of the superposed layers cross. Considered in relation to the magnitude of theBurgers vectors of the dislocations, this shows that interactions between folds on the layer surfaces are not sufficient to explain the crystallographic contact between the layers. An alternative mode of contact is suggested: molecular ends can protrude from one layer and penetrate in some degree the lattice of an overlying layer. Two conditions are necessary for this model to be valid, a tendency for ends to be at the crystal surfaces, and crystal surfaces ‘rough’ enough to provide sites where ends can interpenetrate. Measurements made to check these conditions are reported in the following publication.
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 309-317 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 5 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 1485-1500 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The present paper is a study of the annealing, melting, and recrystallization behavior of solution grown isotactic polystyrene crystals in order to elucidate changes both in total lamellar thickness and in the thickness of the crystalline “core” as a function of temperature. The lamellar thickness was obtained from x-ray long spacings and the core thickness from the broadening of appropriate reflections, both assessed by a high sensitivity x-ray detector system able to produce records within a few minutes during time dependent processes. The x-ray results were correlated with differential scanning calorimetry (DSC) measurements. On heating, first the usual annealing effects with little net melting were observed, but on increasing the temperature large changes in long spacing, which were reversible with temperature, were seen accompanied by only small changes in crystal core thickness. The second effect was found to be associated with a substantial degree of melting. Even after heating above the temperature where complete melting was indicated by DSC, the recrystallization rate was found to decrease as the melt temperature was increased and to be much faster than on cooling from the usual melts. Strikingly, this recrystallization was accompanied by a decrease in long period with time even under isothermal conditions. It is inferred that the memory of the preceding crystalline stack is preserved throughout the melting range and even beyond this, far into the molten state. This “seeding” effect is intrinsic to the polymer even if its nature cannot be specified. The principal effects in question can then be explained by envisaging that randomly placed lamellas gradually disappear within the stack on melting and successively reappear on crystallization during cooling. These ideas agree well with previous work on reversible long spacing changes in polyethylene (see ref. 9) and are likely to be of wider generality for melting and recrystallization phenomena in systems having stacked lamellar morphologies.
    Additional Material: 12 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 779-799 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Extensive gel-permeation chromatography (GPC) results are presented which reveal in much more detail than hitherto the effects of fractionation during the crystallization of polyethylene from solution. It is suggested how these results may be used to assess the affects of fractionation on the production of single crystals. In addition the results are compared with the fractionation which would be expected assuming the crystals to be in equilibrium with the solution. It was found that the results can be explained very well on this basis. A discussion of this rather unexpected result is included.
    Additional Material: 9 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 863-875 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Folded-chain crystals of certain polyamides present some novel diffraction effects due to the small number of repeat units within the lamellar thickness. X-ray diffraction evidence is available in the complete range from low to wide angles. This information is interpreted in terms of the structure factor of an individual lamella together with the lattice factor appropriate for the stacking of lamellae. When due account is taken of the lattice factor, whose effect can be detected even at large angles, three features of the lamellar structure can be deduced. First, the evidence is in favor of the straight-chain stems traversing almost the total thickness of each lamella, implying sharp folds at the lamellar surfaces. Some consequences of this result on the interpretation of data obtained from annealed mats are mentioned. Second, the detailed determination of the stem structure demands that the majority of the folds in nylon 66 lie in the acid group. Third, there are regions of depleted electron density at the lamellar surfaces, though features of the crystal structure are still retained. This indicates the presence of some folds deeper in the crystal than the majority.
    Additional Material: 7 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1457-1465 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effect upon seeding behavior of adding well characterized fractions has been studied, so as to assess the technique as a measure of small amounts of high molecular weight. The material available to us restricted the study to fractions with comparatively low average molecular weights. Self-seeding is shown to be an extremely sensitive measure of high molecular weight tails. Knowledge of the molecular weights concerned enabled estimates to be made of the weight of molecules involved in seeding. Instability of seeds has been observed, and is explained in terms of a particular amorphous crystalline “equilibrium” within the seeds.
    Additional Material: 4 Ill.
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