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  • 1
    Digitale Medien
    Digitale Medien
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 36 (1959), S. 361-387 
    ISSN: 0022-3832
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: 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.
    Zusätzliches Material: 20 Ill.
    Materialart: Digitale Medien
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  • 2
    Digitale Medien
    Digitale Medien
    Springer
    Colloid & polymer science 262 (1984), S. 22-45 
    ISSN: 1435-1536
    Schlagwort(e): Isotactic polystyrene ; gels ; structure ; morphology ; conformation ; X-ray diffraction ; electron microscopy ; DSC ; FTIR ; crystallization
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Maschinenbau
    Notizen: 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.
    Materialart: Digitale Medien
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  • 3
    Digitale Medien
    Digitale Medien
    Springer
    Colloid & polymer science 271 (1993), S. 328-342 
    ISSN: 1435-1536
    Schlagwort(e): Polyethylene ; crystallization ; morphology ; single crystal ; spherulite ; axialite
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Maschinenbau
    Notizen: 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.
    Materialart: Digitale Medien
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  • 4
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 176 (1975), S. 1489-1502 
    ISSN: 0025-116X
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Beschreibung / Inhaltsverzeichnis: 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.
    Notizen: 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.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
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  • 5
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Letters Edition 25 (1987), S. 67-72 
    ISSN: 0887-6258
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 6
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Letters Edition 26 (1988), S. 259-262 
    ISSN: 0887-6258
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 7
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 17 (1975), S. 997-1018 
    ISSN: 0006-3592
    Schlagwort(e): Chemistry ; Biochemistry and Biotechnology
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Biologie , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: A mathematical model was developed to simulate, on a digital computer, the continuous fermentation of whey lactose to lactic acid with neutralization by ammonia. The simulation predicted the retention times for experimental test and the use of two stages for greatest efficiency. In the experimental tests, Lactobacillus bulgaricus was inoculated into whey in a 14-liter continuous fermentor at 44°C and with automatic pH control. A series of steady-state conditions was managed nonaseptically for 42 days without evident contamination and with an actual increase in the efficiency of conversion. Lactic acid was produced predominately' throughout the period, with less than 0.2% of other compounds. The product contained approximately 8 times as much crude protein (N × 6.25) as the original whey. In a single-stage fermentation at pH 5.5, a retention time of 15 hr resulted in a residual lactose concentration of 0.7%; and little improvement was realized by increasing the retention time. Increasing the pH to 5.8 resulted in a significant improvement, but further increasing the pH to 6.0 resulted in only a small additional gain. By the employment of two fermentors in series at pH 5.5 with a total retention time of 31 hr, the residual lactose was reduced to less than 0.1%. Lactic acid was produced as a function mainly of maintenance rather than growth metabolism.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
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  • 8
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 151 (1972), S. 169-187 
    ISSN: 0025-116X
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Beschreibung / Inhaltsverzeichnis: Im Zuge von Untersuchungen über die Faltungsstruktur bei Kristallen ungesättigter polymerer Kohlenwasserstoffe und über die Beziehungen zwischen Kristallmorphologie und Abbauprozessen wurden Einkristalle von Polydodecenamer und Polydecenamer dem oxydativen Angriff durch Ozon und durch Salpetersäure ausgesetzt. Aus der zeitlichen Änderung des Gehaltes an Doppelbindungen (IR) und der Molekulargewichtsverteilung (GPC) folgt, daß auch Doppelbindungen tief im Inneren der Kristalle in einem solchen Ausmaß angegriffen werden, daß eine Unterscheidung zu dem an der Kristalloberfläche stattfindenden Abbau nicht mehr klar möglich ist. (Dieser Befund steht im Gegensatz zu analogen Untersuchungen über die Spaltung von Einfachbindungen beim Polyäthylen.) Der Angriff erfolgt jedoch auch nicht rein statistisch. Es entsteht vielmehr ein kristallines Dimeres, das trotz vorhandener Doppelbindungen sehr resistent gegenüber dem vollständigen Abbau ist. Die Gründe für dieses unerwartete Verhalten werden diskutiert, wobei auch die Möglichkeit von besonders ideal-kristallinen Untereinheiten, die viel kleiner sind als die gewöhnlich betrachteten Modelle von Kristallen aus gefalteten Ketten, in Betracht gezogen wird. Im Gegensatz zu den leicht zugänglichen Doppelbindungen in den Kristallen der Polyalkylenamere wird für die gelegentlich in den Polyäthylenketten vorkommenden Doppelbindungen bestatigt, daß sie gegenüber dem Angriff durch Ozon dann weitestgehend abgeschirmt sind, wenn sie im Kristallgitter eingeschlossen sind, und das, obwohl die Kristallstruktur derjenigen der Polyalkylenameren sehr ähnlich ist. In Verbindung mit ähnlichen Ergebnissen für Guttapemha7 scheint es so, daß die leichtc Zugänglichkeit gegenüber Ozon eine Eigentümlichkeit der Kristalle solcher Polymeren ist, bei denen das Ungesättigtsein eine wirklich charakteristischc Eigenschaft der Moleküle ist.
    Notizen: As part of an enquiry on the fold structure of crystals from unsaturated chains and on the relation between crystal morphology and degradation, single crystals of two polyalkenamers were subjected to oxidative attack by ozone, and to a lesser extent by nitric acid, and the resulting changes in the concentration of double bonds and the distribution of molecular lengths were followed. It was found that double bonds were attacked deep within the crystal without a clear distinction between the fold surface and the crystal interior in contrast to the analogous studies involving the severance of single bonds in polyethylene. Nevertheless, the attack does not follow a random pattern but leads to a crystalline dimeric residue which remains highly resistant in spite of containing double bonds. The implications of this unexpected finding, which include the possibility of a highly perfect crystalline subunit much smaller than involved in the much argued models of chain folded crystals, are discussed. It is reconfirmed that the occasional intrachain double bonds in polyethylene are largely shielded from ozone while in the lattice in contrast to the high accessibility of these bonds in the present polyalkenamers of closely similar crystal structure. In view of similar results on guttapercha7 it appears that the latter property may be a feature common to polymer crystals where the unsaturation is intrinsic to the molecule.
    Zusätzliches Material: 12 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 9
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 151 (1972), S. 189-206 
    ISSN: 0025-116X
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Beschreibung / Inhaltsverzeichnis: Aus verdünnter Lösung erhaltene Kristalle von Guttapercha (trans-1.4-Polyisopren) wurden untersucht. Es wurden zwei Arten von Einkristallen beobachtet, die sich im Habitus beträchtlich unterscheiden und die mit Hilfe der Elektronenbeugung den beiden schon lange bekannten Modifikationen zugeordnet werden konnten. Das Verhalten beim Schmelzen und beim Tempern wurde zu den beiden Formen in Beziehung gebracht, und es wurde ein Übergang zwischen ihnen beobachtet bei Temperaturen, bei denen beide Phasen offenbar auch nebeneinander stabil sind. Außerdem wurde die Faltungslänge und ihre Abhängigkeit von den Versuchsbedingungen untersucht.Die Einkristalle wurden dem oxydativen Abbau durch Ozon unterworfen, wobei besonders die Änderungen im IR-Spektrum und in der Molekulargewichtsverteilung interessierten. Wie erwartet, wurden die Doppelbindungen zerstört, jedoch nur bis zu einem gewissen Umsate; ein erheblicher Anteil bleibt auch bei langen Reaktionszeiten erhalten. Der Kettenabbau erfolgt dernrt, daß am Ende der Reaktion eine groß Menge cines trimeren bis tetrameren trans-1.4-Polyisoprens mit Carboxyl- und Carbonyl-Endgruppen vorliegt, das dem weiteren Angriff des Ozons widersteht. Im Gcgcnsatz zu analogen Versuchen mit Polyäthylen wurde keine selektive Spaltung der Bindungen an der Kristalloberfläche (Faltungsstellen) gegenüber dem Kristallinneren beobachtet. Vieles deutet darnuf hin, daß eine gute Zugänglichkeit der Doppelbindungen im Kristallinneren, bei gleichzeitiger Resistenz von Kettenabschnitten „oligomerer Länge“, für Kristalle aus gefalteten Ketten hochgradig ungesättigter Polymerer charakteristisch zu sein scheint.
    Notizen: Guttapercha (trans-1.4-polyisoprene) was crystallized from solution and its single crystal habit and chain folding characteristics were examined. The two polymorphic forms, known from previous studies, could now be assigned to two different single crystal habits by means of electron diffraction patterns, and conditions of their formation could be circumscribed. Similarly, the melting and annealing behaviour could be associated with the two forms and a transition between them observed at temperatures where the two phases can still coexist by present evidence. The fold length and its variations were also defined.Single crystals were exposed to the degrading effect of ozone, and changes in IR-spectra and molecular weight distribution were followed. It was observed that, as expected, double bonds were severed; nevertheless a sizeable portion of them remained intact. At the same time the chain was broken down into a sharply defined fragment length which was identified as a trimer or tetramer of trans-1.4-polyisoprene with carboxylic and carbonylic termination. No appreciable selectivity as regards fold traverses analogous to the degradation products in polyethylene was observed. It is pointed out that appreciable accessibility of double bonds within the crystals, coupled with oxidation resistance of small oligomeric lengths, seems to be characteristic of chain folded crystals of unsaturated compounds with possible implications for studies on the crystal structure and on degradation behaviour in general.
    Zusätzliches Material: 12 Ill.
    Materialart: Digitale Medien
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  • 10
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Zeitschrift für die chemische Industrie 80 (1968), S. 410-410 
    ISSN: 0044-8249
    Schlagwort(e): Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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