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  • Polymer and Materials Science  (117)
  • crystallization  (2)
  • 1
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 36 (1959), S. 361-387 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Continuous films and discontinuous aggregates of nylons were prepared and examined with combined electron diffraction and electron microscope techniques. It was found that the electrons destroy the diffracting ability of the crystals without affecting their shape. The consequences of this fact for the electron microscopy of polymers are pointed out. It was found that the molecules and the planes containing the hydrogen bonds tend to lie in the film plane, but deviations from this orientation amounting to a maximum of 25° were also found. An expression is derived for establishing the fiber axis direction from single, tilted electron-diffraction patterns. In some films, a spherulitic morphology was observed which consists of a flat layer structure within the film plane. In general, however, the spherulites develop through a fibrous texture, which appears to arise through the curling up of flat sheets. These sheets themselves possess a fibrous morphology. The spherulitic orientation, as established previously by x-rays, could now be identified within submicroscopic fibrous aggregates. By examination of individual sheaves in the selected area we could identify ribbons and fibrils which can be considered as being the equivalents of single crystals. The molecules were found to be lying at large angles to the length of even the smallest fibrils. The conclusion was reached that this requires a regular, sharply folded configuration of the molecules, which would also account for the uniform width of the microfibrils. The implications of this new concept are discussed, and earlier models are reviewed in the light of the new facts.
    Additional Material: 20 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Colloid & polymer science 262 (1984), S. 22-45 
    ISSN: 1435-1536
    Keywords: Isotactic polystyrene ; gels ; structure ; morphology ; conformation ; X-ray diffraction ; electron microscopy ; DSC ; FTIR ; crystallization
    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 thermoreversible gelation phenomena exhibited by isotactic polystyrene (i-PS) was examined in depth, utilising a variety of experimental techniques. The primary aims were identification, relationship, description and visualisation of the morphologies corresponding to the two types of crystallization as diagnosed by the different crystal structures revealed by X-ray diffraction. While centred on electron microscopy the investigation used X-ray and electron diffraction, differential scanning calorimetry and Fourier transform infra-red spectroscopy in combination. A satisfactory correlation between all these techniques was established, including the important reassurance that the characteristics of the gel state are preserved on drying, a feature necessitated by most structure methods. Thei-PS gel system as a whole displays particularly clearly the distinction between gel forming and chain folded lamellar crystallization and the coexistence, morphological relationship and competition between the two crystallizable species. In addition, and most significantly, the gel crystals possess a crystal structure involving extended chains, close to an all-trans conformation, which are quite different to those obtained from conventionally crystallizedi-PS (31 helix). This former extended conformation in itself has become the starting point for new geometric and stereochemical considerations and in addition offers a convenient diffraction based fingerprint to delineate between the two modes of crystallization. Thus the conversion of the gel crystal structure to the conventional 31 helix structure on heating could be monitored. Further, that in the processes of heat annealing, remnants of these gel fibres initiate the development and dictate the orientation of a shish-kebab type platelet growth with the 31 helix crystal structure. This conversion process has been followed by electron microscopy and supplemented infra-red spectroscopy, low angle X-ray diffraction and differential scanning calorimetry. The different roles of fibres and platelets on stretching have been identified. Conditions for the existence of the gel crystals in their different variants are specified with relevance to ongoing arguments and discussions in the subject. Further, it was established that passing through the gel phase significantly enhanced the crystallization in the conventional crystal form making the normally slowly crystallizingi-PS into a fast crystallizable polyolefin.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Colloid & polymer science 271 (1993), S. 328-342 
    ISSN: 1435-1536
    Keywords: Polyethylene ; crystallization ; morphology ; single crystal ; spherulite ; axialite
    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 Three-dimensional shape of polyethylene single crystals grown from the melt has been studied. Two distinct types of lateral habit have been obtained: lenticular shape (type A) and truncated lozenge (type B) in the range of regime I and II. Electron microscopy has revealed chair-like shape of type B crystal and reconfirmed the planar shape of type A crystal. In the type B crystal, spiral growth has occurred frequently in the {110} sectors and the sense of the handedness of spiral terraces has been maintained. It has been, suggested that the frequens occurrence of spiral growth is responsible for a morphological change (axialite-spherulite) accompanying the regime I–II transition. The origin of the chair-like crystals has been discussed and, a possible mechanism has been suggested for the formation of spiral terraces; the mechanism is based on a distortion caused by the three-dimensional shape of chair-like crystals. It has been found that the chair-like crystals are curved in the opposite way to S-shaped lamellae observed by Bassett and Hodge in banded spherulites. In fact, the present work has led to the recognition of further classes of crystal with curving cross-sections and of distinctions between them. In final analysis, a unifying thread has been identified between lateral habits, growth kinetics and three-dimensional shape of lamellae, in turn, leading to some rationalization of multilayer developments including twisting in banded spherulites, the latter based on existing suggestions in the literature.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 176 (1975), S. 1489-1502 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Der Einfluß einer regelmäßigen Folge chemischer Gruppen entlang einer Polymerkette auf die Struktur und Eigenschaften von Einkristallen mit gefalteten Ketten wurde an linearen Polyestern mit verschiedenen Längen der Bausteine untersucht. Einkristalle von Poly(oxytetramethylenoxysebacoyl) (Polyester 4,10), Poly(oxyhexamethylenoxysebacoyl) (Polyester 6,10), und Poly(oxydecamethylenoxysebacoyl) (Polyester 10,10) wurden aus Lösungen hergestellt und ihre Strukturen sowie ihr Temperverhalten untersucht. Zwei verschiedene Strukturen von Lamellen rnit gefalteten Ketten wurden, abhlngig vonder Zusammensetzung des Polyesters, erhalten. Obwohl in beiden Strukturen die Ketten senkrecht zur Lamellenoberflache stehen, sind die Estergruppenebenen “OOl” im Falledes Polyesters 4.10 parallel zu der Lamellenoberflache. im Gegensatz zum Polyester 10.10 bei welchem die Estergruppenebenen geneigt sind.Trotz der Tatsache, daß die Lamellen nur etwa 100Å dick sind und nur wenige Identitiitsperioden enthalten können. wöchst die Lamellendicke aller drei Polyester mit der Kristallisationstemperatur kontinuierlich an. Es wird ein Modell mit Faltungslamellen verschiedener Faltenstammllngen, die sich um diskrete Werte unterscheiden, vorgeschlagen. Diese Faltenstammlangen konnen dann in verschiedenen Verhaltnissen gemischt werden. was den kontinuierlichen Anstieg der Lamellendicke erklären könnte.Beim Tempern wachst die Lamellendicke von Polyester 4,lO und 6,lO in diskreten Schritten an, was auf eine Umordnung von Falten zu einer einheitlicheren Mischung von Faltungslangen hinweist. Im Gegensatz dazu wachst im Polyester 10,10 die Lamellen-dicke beim Tempern kontinuierlich an, was auf die Neigung der Estergruppenebenen beziiglich der Lamellenoberfliche, wodurch die Falten nicht aquivalent werden. zuriickzu-fuhren ist. Einige Verallgemeinerungen beziiglich der Faltenlangenanderungen werden vorgesc hlagen.
    Notes: The influence of chemical groups regularly spaced along a polymer chain on structure and behaviour of chain folded single crystals was studied on linear aliphatic polyesters with different lengths of repeating unit. Poly(oxytetramethyleneoxysebacoyl) (or polyester 4,10), poly(oxyhexamethyleneoxysebacoyl) (or polyester 6,10), and poly(oxydecamethyleneoxysebacoyl) (or polyester 10,10) single crystals were grown from solution and their structure and annealing behaviour were examined. Chain folded lamellae with two different structures were formed depending on the chemical composition of polyester. Although in both structures the chains are perpendicular to the lamella surface, the ester group planes {00l} are parallel to the lamella surface in polyester 4,10 as opposed to the polyester 10,10 where the ester group planes are inclined.In spite of the fact that the chain folded lamellae are of about 100Å thick and can accommodate only few crystallographic repeats along, the lamella thickness of all three polyesters increases continuously with crystallization temperature. A picture of chain folded lamellae containing folds of different but quantized lengths mixed in different proportions is proposed in order to explain the continuous increase of lamella thickness.On annealing, the lamella thickness of polyester 4,10 and 6,10 increases in discrete steps suggesting that a rearrangement of folds leading to a more uniform fold length mixture takes place. In contrast, in polyester 10,10 the lamella thickness increases continuously on annealing which is attributable to the inclination of the ester group planes to the lamellar surface and to the ensuing non-equivalence of the folds which distinguishes it from the other two polyesters. Some generalizations about fold length changes are being made.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 19-34 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It is demonstrated that dicarboxylic acids of uniform lengths, obtained by degrading chain-folded polyethylene single crystals, can be converted to paraffins via the intermediate diiodide by means of the procedure of Barton et al. Thus we are now in the position of obtaining uniform paraffins of chain lengths longer than hitherto available for the study of the crystallization of oligomeric chains. Measurements of melting points and heats of fusion revealed major differences between the paraffins and the corresponding parent dicarboxylic acids. It follows that such measurements on the unmodified products of the nitric acid degradation cannot be used directly for the assessment of the chain traverse length and the degree of crystallinity. It was found further, that the intermediate diiodide is a sufficiently close approximation to the paraffin for the purposes just quoted.
    Additional Material: 9 Ill.
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  • 6
    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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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 707-712 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It is reported that mats formed by the sedimentation of single crystals of methyl- and ethyl-branched polyethylene exhibit strength and ductility comparable with that of melt-crystallized films. In fact, in the case of methyl-branched polymers, extensions of up to 50× were obtained on cold drawing. Observations on separate crystals suggest that this extension is due to the pulling out of individual lamellae. In view of the magnitude of the extension, this implies unfolding of the molecules. That considerable coherence can be obtained without original molecular ties between crystals is of significance as regards the molecular interpretation of the strength and ductility of crystalline polymers.
    Additional Material: 3 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 751-751 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1467-1490 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It was established that polyethylene and polyoxymethylene crystallize epitaxially on NaCl cleavage faces over a temperature range in which the usual polymer single crystals dissolve but a crystallization memory remains due to very small quantities of self-seeding nuclei persisting in the solution. By performing this epitaxial crystallization in the presence of self-seeding nuclei, it could be established that epitaxial crystallization at these elevated temperatures involves only the very largest molecules in the distribution. Further, the self-seeding nuclei themselves could be isolated for observation, and these results were found consistent with previous predictions. By utilizing both the adhesion of these nuclei to NaCl and the selective nature of the epitaxial crystallization, the largest molecules could be extracted and reintroduced again to the same or different solutions. This opens up the possibility of a novel kind of chromatography for the separation and characterization of the highest molecular weight end of a distribution to a sensitivity which cannot be approached by other methods. The epitaxy phenomenon itself, under the circumstances involved, provides a new decoration method for the study of the surface topography of alkali halides. The origin of such as epitaxy occurring at low supercoolings and terminating at a limiting thickness raises important questions regarding long-range forces and some unsettled features in the theory of chain-folded crystal growth in polymers.
    Additional Material: 14 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 991-1012 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Single-crystal preparations of polyethylene were treated with the selective oxidizing agent, fuming nitric acid. The degraded products were examined as regards layer thickness (by low-angle x-ray studies), chemical and weight changes, recrystallization and annealing treatments, and by broadline NMR, as part of a systematic investigation aimed at clarifying the nature of disordered material in single crystals. It emerges that there is a disordered-mobile region along the fold surface of the crystals in agreement with other parallel works along similar lines. In a more detailed analysis we can now decompose the nitric acid attack into components affecting the basal and side surfaces, respectively. Taking into account the recrystallization-annealing observations, we infer that the fold surface is heterogeneous with folds of more than one kind. These results were combined with a preliminary molecular weight distribution study by gel permeation chromatography. Taking into account all the available evidence, we are led to suggest a composite structure where surface looseness, coresponding to long loops and hairs, is superimposed on the more regular folded surface. This model is in the process of being tested. The problems concerning the assignment of a value to the amount of surface looseness are being discussed. In addition, a discontinuity in the thermal behavior of the crystals between 75 and 80°C. has been detected.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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