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  • 1965-1969  (1,881)
  • 1920-1924
  • Physics  (1,849)
  • Electron Microscopy  (32)
  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Acta neuropathologica 12 (1969), S. 329-338 
    ISSN: 1432-0533
    Keywords: Hypokalemic Periodic Paralysis ; Electron Microscopy ; Myopathy ; Sarcoplasmic Reticulum ; Glycogen, Muscular
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Licht- und elektronenoptische Untersuchungen wurden an Muskelbiopsien von 4 Fällen hypokaliämischer periodischer Paralyse durchgeführt. Die frühesten Veränderungen betreffen nach Meinung der Verfasser das sarkoplasmatische Reticulum: Vacuolisierung des Längssystems und vermutlich Multiplikation des Quersystems. Es wird vermutet, daß die Vacuolenbildung die Folge einer Fusion der Vesikeln des Quersystems darstellt. Destruktion von Myofibrillen und Vergrößerung der, interfibrillären Räume treten erst in späteren Phasen des Krankheitsprozesses auf. Ausdehnung und Intensität dieser Veränderungen bedingen das typische histologische Bild myogener Läsionen bei Fällen m klinisch fixierten Symptomen der Myopathie.
    Notes: Summary Light and electron-microscopic studies were performed on the muscles taken from 4 cases with hypokalemic periodic paralysis. The authors conclude that the earliest changes concern the sarcoplasmic reticulum: vacuolisation of the longitudinal system and probably, multiplication of the transverse system. It is suggested, that vacuoles are formed as a result of fusion of the vesicles of the transverse system. Destruction of myofibrilles and enlargement of the interfibrillar spaces appear at a later period of the disease process. Extensive and intensive changes of that kind present a typical appearance of myogenic changes in histological study observed in the cases with clinically fixed symptomes of myopathy.
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Acta neuropathologica 13 (1969), S. 1-11 
    ISSN: 1432-0533
    Keywords: Whipple's Disease ; Granulomatous Encephalitis ; Electron Microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Von 21 Fällen von Whipplescher Krankheit in der Sammlung des Armed Forces Institute of Pathology zeigten 4 Fälle neurologische Symptome mit besonders ausgeprägten Hirnläsionen. Lichtmikroskopisch bestanden die Herde aus knötchenförmigen Anhäufungen von Makrophagen, deren Cytoplasma mit Hämatoxylin-Eosin eine charakteristische schwachblaue und nach Durchführung der Perjodsäure-Schiff-Reaktion eine stark rote Färbung zeigte. Elektronenmikroskopisch fanden sich in den Hirnläsionen Bacillen, die morphologisch den im Darm beschriebenen glichen und die auch dieselben Degenerationserscheinungen aufwiesen. Die Perjodsäure-Schiff-Reaktion färbt Kapselmaterial und Zellwände,die auch nach Untergang der Bacillen noch nachweisbar sind. Diese Beobachtungen werden als weiterer Beweis für die infektiöse Ätiologie der Whippleschen Krankheit angeführt.
    Notes: Summary Among the 21 autopsied cases of Whipple's disease on file at the Armed Forces Institute of Pathology, 4 had neurological symptoms and prominent involvement of the central nervous system, By light microscopy the lesions were composed of nodular aggregates of macrophages having cytoplasm that stained a distinctive pale blue with hematoxylin-eosin and bright red with the periodic acid-Schiff technique. By electron microscopy the cerebral lesions revealed bacilli morphologically identical to and undergoing the same sequence of degenerative changes as those observed in the intestine. The periodic acid-Schiff reaction stains the walls and the capsular material that persists even after intact organisms disappear. These observations further support the infectious nature of Whipple's disease.
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Acta neuropathologica 13 (1969), S. 43-55 
    ISSN: 1432-0533
    Keywords: Subacute Dementia ; Jakob-Creutzfeldt Disease ; Brain Biopsy ; Histochemistry ; Electron Microscopy ; Basement Membrane ; Astroglia Dilatation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Die elektronenoptische und histochemische Untersuchung von Biopsiematerial bei zwei Fällen subakuter Demenz ergab Neurone mit reichlich Lipofuscin-Depots sowie erhöhter saurer Phosphatase-Aktivität. Obwohl diese Veränderungen eine Nervenzellerkrankung anzeigen dürften, werden sie wegen ihrer Ähnlichkeit sowie wegen des Vorliegens anderer, spezifischerer Zellveränderungen als Sekundärphänomene gedeutet. Im ersten Fall wird als primäre Läsion eine Verdickung der Basalmembran der Gefäße, im zweiten Fall eine Astrogliaschwellung angenommen. Da diese Strukturen wichtige Transportfunktionen haben dürften, könnten diese Anomalien leicht die neuronale Versorgung stören und dadurch die neuronalen Läsionen verursachen. Die Bedeutung des Glykogens in diesen Strukturen wird diskutiert.
    Notes: Summary The electron microscopic and histochemical findings in biopsies of two cases of subacute dementia have revealed neurons containing numerous lipofuscin bodies and increased acid phosphatase. Although these changes are considered to indicate neuron disease, they are believed to represent a secondary process because of their similarity and because other more distinctive cell alterations are present. In the first case, the primary abnormality is believed to be thickening of the vascular basement membrane, while in the second case, astroglial dilatation is considered a primary change. Since these structures appear to have important transport functions, these abnormalities could easily impair the nutrient supply to neurons and, in this way, produce the neuronal alteration. The significance of glycogen in these tissues is discussed.
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Acta neuropathologica 13 (1969), S. 131-142 
    ISSN: 1432-0533
    Keywords: Neuropathy, Chronical ; Hypertrophic Neuritis ; Schwann-Cell ; Onion Bulb ; Electron Microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Die wesentlichen Veränderungen bei dem mitgeteilten Fall von chronischer frühinfantiler Neuropathie bestehen in einer Modifikation der Schwann-Zellen, die zur Bildung eines konzentrischen Netzwerkes von Lamellen führt. Dieses wird durch eine doppelkonturierte Hülle der Basalmembran um zahlreiche große bemarkte und unbemarkte Fasern gebildet. Die Anomalien der Markscheiden sowie die Häufigkeit von Desmosomen sind bemerkenswert. Diese Besonderheiten unterscheiden diesen Fall von anderen, bisher beschriebenen chronischen Neuropathien. Trotzdem erscheint es derzeit nicht möglich, eine Aussage über die Spezifität der ultrastrukturellen Befunde am untersuchten Nerven zu treffen.
    Notes: Summary The principal lesion in this case of chronic early infantile neuropathy is a modification of the Schwann cell resulting in the formation of a concentric network of lamellae formed by a double-layered sheet of basement membrane around numerous, large myelinated and unmyelinated fibers. The abnormalities in the myelin sheaths and the frequency of desmosomes are noteworthy. These peculiarities distinguish this case from other chronic neuropathies described up to now. Nevertheless, it is impossible to say at present whether the ultrastructural aspect of the nerve studied here is in any way specific.
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  • 5
    ISSN: 1432-0533
    Keywords: Subacute Sclerosing Leucoencephalitis ; Electron Microscopy ; Tubular Inclusions ; Inclusion Bodies (Cristalline Rods, Fibrillar Bundles, Nuclear Bodies, Osmiophilic Particles)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé Les auteurs rapportent 4 observations caractéristiques de LESS: L'analyse ultra-structurale montre: 10 — des inclusions tubulaires intra-nucléaires neuronales ou gliales et intra-axonales de morphologie superposable à celle des nucléocapsides des myxo-virus, de la rougeole en particulier. 20 — des formations non spécifiques: corps nucléaires, faisceaux cristallins et fibrillaires traduisant un trouble métabolique nucléaire, particules osmiophiles liées à une hyperactivité cellulaire. Les inclusions tubulaires virales sont présentes quelque soit la durée de la maladie (3 mois à 5 ans) indiquant l'absence d'autostérilisation virale dans le S.N.C. La LESS apparaît liée au virus rougeoleux mais le mécanisme indirect immunitaire ou métabolique de cette action est inconnu.
    Notes: Summary Four cases of S.S.L.E are reported. The electron microscopy findings show: 1. Tubulary inclusion bodies: They appear in three cases out of four, either in neuronal and glial nucleus or in axis cylinders. Their morphological features are similar to the nucleocapsides of myxoviruses and particularly measles-virus. 2. Other different types of nonspecific inclusions: nuclear bodies, cristalline-like rods and fibrillar bundles which may be considered as the result of a nuclear metabolic disorder, osmiophilic particles which may be seen as the result of a cellular intracytoplasmic hyperactivity. The tubules are found whatever the duration of the disease (3 months up to 5 years) may be. This might indicate that there is no autosterilization of the virus in the C.N.S. during the course of S.S.L.E. According to the most recent papers, such a disease might be interpreted as an infection indirectly induced by measles-virus with an unknown immunologic or metabolic mechanism.
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  • 6
    ISSN: 1432-0533
    Keywords: Marginal Siderosis ; Electron Microscopy ; Myelin-Sheath-Like Structures ; Plaques Fibromyéliniques ; Gliosis, Perivascular, Subpial
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Bei Kaninchen mit einer experimentell erzeugten Randzonensiderose des Zentralnervensystems konnten elektronenmikroskopisch in der Großhirnrinde eigentümliche Spiralstrukturen beobachtet werden. Diese Spiralen fanden sich vornehmlich im Bereich von subpialen und perivasculären Gliosen vor. Sie bestanden aus äußerst dünnen lamellären Astrocytenausläufern, welche um andere astrocytäre Zellfortsätze oder um Dendriten aufgewickelt waren. Die spiralisierten Astrocytenausläufer wiesen in ihrem Inneren feine Filamente mit einer ziemlich regelmäßigen Anordnung auf. In radiärer Richtung ließen die astrocytären Lamellenspiralen eine periodische Schichtung erkennen, welche etwas an die von echten Markscheiden erinnerte. Es wird in Betracht gezogen, daß sie das submikroskopische Äquivalent der sog. Plaques fibromyéliniques darstellen.
    Notes: Summary Peculiar spiral structures could be observed by electron microscopy in the cerebral cortex of rabbits with an experimentally produced marginal siderosis of the central nervous system. These spirals were found predominantly within areas of subpial and perivascular gliosis. They consisted of extremely thin lamellar astrocyte extensions winding around other astroglial processes or dendrites. The spirally coiled astrocyte extensions exhibited within their interior fine filaments having a rather regular arrangement. In the radial direction, the astrocytic lamellae spirals showed a periodic stratification somewhat resembling that of true myelin-sheaths. They were considered to represent the submicroscopic equivalent of the socalled plaques fibromyéliniques.
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  • 7
    Electronic Resource
    Electronic Resource
    Springer
    Acta neuropathologica 12 (1969), S. 173-182 
    ISSN: 1432-0533
    Keywords: Sodium Deposits ; Electron Microscopy ; Perfusion with Hydroxyadipaldehyde-Antimonate ; Extracellular Space
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Eine Modifikation der Methode zur ultrastrukturellen Darstellung von Natrium wird beschrieben, die eine Perfusion mit leicht alkalischer Mischung von Hydroxydipaldehyd, Phosphatpuffer und Kalium-Pyro-Antimonat verwendet. Im normalen Gehirn werden keine Natrium-Deposite angetroffen. Das spricht dafür, daß im Gehirn keine intraoder extracelluläre Konzentration über 150 mM vorliegt. Bei Vorliegen hoher NaCl-Konzentration sieht man ein großes, dichtes Präcipitat, das nach direkter Injektion in den extracellulären Räumen, Neuronen und Astrocyten lokalisiert werden kann. Im Mark der vergifteten Ratten findet sich ähnlich wie nach direkter Natrium-Injektion ein diskretes, gleichfalls als Natrium aufgefaßtes Präcipitat an der Oberfläche von Oligodendrogliazellen, aber nicht innerhalb dieser Zellen. Ein elektronendichtes Deposit unklarer Herkunft findet sich in den Myelinspalten, die nach akuter TET-Vergiftung auftreten. Der Wechsel in Charakter und Lokalisation dieser elektronendichten Partikel mahnt zur Vorsicht in ihrer Interpretation bei histochemischen Untersuchungsmethoden.
    Notes: Summary A modification of the technique for the ultrastructural demonstration of sodium is described which involves a perfusion with a slightly alkaline mixture of hydroxyadipaldehyde, phosphate buffer and potassium pyroantimonate. No sodium deposits are found in normal brain indicating that no intra or extracellular concentration exceeding 150 mM is present in the brain. In the presence of high concentration of NaCl, a large dense precipitate can be seen which after a direct injection can be localized to extracellular spaces, neurons and astrocytes. In the white matter of tin poisoned rats, as well as after the direct injection of sodium, a discrete precipitate, also believed to represent sodium, is noted at the surface of oligodendrocytes but not within these cells. An electron dense deposit of dubious origin is present in the myelin clefts which occur as a result of acute triethyltin intoxication. The variations in the character and localization of these electron dense particles emphasize the caution which is required in their interpretation following histochemical procedures.
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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    Acta neuropathologica 12 (1969), S. 307-313 
    ISSN: 1432-0533
    Keywords: Swayback of Lambs ; Electron Microscopy ; Corpus Callosum ; Myelogenesis ; Axonal Changes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Elektronenmikroskopische Untersuchung des Corpus callosum normaler Lämmer und von solchen mit „Swayback” (enzootische Ataxia) ergab den morphologischen Nachweis normaler Myelinentwicklung in beiden Tiergruppen. Von zwei Zellfortsätzen umgebene Axone wurden häufig beobachtet. Reaktive Veränderungen wurden in Axonen der „Swayback”-Lämmer gefunden. Die Bedeutung dieser Befunde wird besprochen.
    Notes: Summary An electron microscopic study of the corpus callosum of normal and swayback lambs has revealed morphological evidence of normal myelinogenesis in both groups of animals. Axons wrapped by two cell processes were frequently encountered. Reactive changes were found in axons in the swayback lambs. The significance of these findings is discussed.
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  • 9
    Electronic Resource
    Electronic Resource
    Springer
    Acta neuropathologica 12 (1969), S. 103-115 
    ISSN: 1432-0533
    Keywords: Spongy Degeneration of the CNS ; Van Bogaert-Bertrand-Disease ; Electron Microscopy ; Astrocytic Mitochondria ; Abnormal Cerebral Edema
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Es wird über licht- und elektronenoptische Untersuchungen an Muskel-und Hirnbiopsien eines Falles von spongiöser Degeneration des ZNS berichtet. Die in der grauen und weißen Hirnsubstanz enthaltenen Vacuolen entsprechen a) Spalten in den Markscheiden infolge Aufsplitterung an der intraperiodischen Linie und b) geschwollenen Astrocytenperikaryen und-fortsätzen. Ungewöhnliche Mitochondrien mit Gehalt an kristallinem Material fanden sich nur in Astrocyten. Die ultrastrukturellen Befunde entsprechen denen des Hirnödems. Es wird angenommen, daß die Astroglia eine primäre Rolle in der Flüssigkeitsansammlung spielt, während die Markscheidenschwellung als eine Sekundärläsion aufgefaßt wird. Die mögliche Bedeutung abnormer Astrocyten-Mitochondrien wird diskutiert.
    Notes: Summary Light and electron microscopy study of skeletal muscle and cerebral biopsies from a case of spongy degeneration of central nervous system is reported. The multiple vacuoles present in cerebral gray and white matter correspond to (a) clefts within myelin sheaths resulting from splitting at the intraperiod line and (b) swollen astrocytic perikarya and processes. Unusual mitochondria containing crystalline-like material were observed only in astrocytes. The ultrastructural findings are consistent with cerebral edema. It is suggested that the astrocytes play a primary role in the fluid accumulation while the myelin swelling is a secondary lesion. The possible role of the abnormal astrocytic mitochondria is discussed.
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  • 10
    Electronic Resource
    Electronic Resource
    Springer
    Acta neuropathologica 12 (1969), S. 183-188 
    ISSN: 1432-0533
    Keywords: Dystrophia myotonica ; Electron Microscopy ; Sarcolemmal Nuclei ; Myofibrillar Material
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung In fünf Fällen von Dystrophia myotonica zeigte die elektronenoptische Untersuchung von bioptisch entnommenem Material zentrale und subsarkolemmale Kerne, die komplexe vacuoläre Areale um myofibrilläres Material enthalten. Diese bisher nicht beobachtete Veränderung könnte durch Verlagerung von myofibrillärem Material in den Kern während seiner Wanderung in das Faserzentrum durch Invagination, aber nicht Durchbrechung der Kernmembran bedingt sein.
    Notes: Summary In five cases of dystrophia myotonica electron microscope preparations of muscle taken at biopsy showed both centrally placed and subsarcolemmal nuclei containing complex vacuolar areas enclosing myofibrillar material. It is suggested that this appearence, which has not been seen in any other condition, may be due to the forcing of myofibrillar material into the nucleus during its migration to the centre of the fibre invaginating but not breaching its membrane.
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  • 11
    Electronic Resource
    Electronic Resource
    Springer
    Acta neuropathologica 12 (1969), S. 276-299 
    ISSN: 1432-0533
    Keywords: Herpes simplex Virus ; CNS Tissue Culture ; Multiplication in vitro ; Cytopathic Alterations ; Electron Microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Die häufig diskutierte, (Mit)beteiligung von Herpes simplex-Virus (HSV) bei bestimmten Alterationen im ZNS sowie der hohe Neutropismus des HSV führte zur Frage, inwieweit sich HSV auch in in vitro gezüchteten, spezifischen Zellen vom Nerven-system vermehren und züchten läßt, und ob sich hierbei licht-und elektronenmikroskopisch charakteristische Alterationen nachweisen lassen. Es zeigte sich, daß sich das HSV in allen verschiedenen angezüchteten spezifischen Zellen (von Plexus chorioideus des Rhesusaffen, Kaninchenspinalganglien, menschlichen Oligodendrogliomen, Meningeomen sowie fibrillären und protoplasmatischen Astrocytomen) kultivieren und vermehren läßt. Hierbei kommt es in den spezifischen Zellen nicht nur lichtmikroskopisch zu charakteristischen cytopathischen Veränderungen, sondern auch biologisch zu einer signifikanten Vermehrung des Virus in diesen Zellen. Auch elektronenmikroskopisch lassen sich viele der charakteristischen Bildungs-, Reifungs- und Ausschleusungsstadien des Virus in den Kernen und im Cytoplasma der Zellen beobachten. Die Besonderheiten der elektronenmikroskopisch erhobenen ultrastrukturellen Befunde werden ausführlich beschrieben, und die sich daraus abzuleitenden Möglichkeiten werden im Hinblick auf die biologischen Eigenheiten des HSV bei in vivo-Infektionen, aber auch im Hinblick auf die Deutung lichtmikroskopisch histochemischer und immunhistologischer Befunde nach in vivo-Infektionen mit diesem Virus ausführlich diskutiert.
    Notes: Summary The participation of herpes simplex virus (HSV) in certain alterations of the CNS has been partially questioned and frequently discussed. Therefore, the question arose whether HSV can also be cultivated and multiplied in vitro in CNS specific cells, and if so, whether characteristic alterations and structures can be observed by means of light and electron-microscopic examinations. Our data demonstrate that HSV multiplies in all different specific cells originating from plexus chorioideus of rhesus monkeys, from spinal ganglia of rabbit, from human oligodendroglioma, meningeoma as well as from fibrillar and protoplasmatic astrocytoma. Characteristic cytopathic alterations of these specific cells and significant multiplication of the virus in these cells are to be found. Many of the characteristic forms of formation, maturation and release of HSV can be seen by electronmicroscopic examinations. The particular ultrastructural data observed by electron microscopy are described in detail and the resulting possibilities are broadly discussed not only with regard to the biologic particularity of HSV in in vivo infection but also in view of the interpretations, deriving from histochemical and immunohistological data obtained by light microscopy after in vivo infection.
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  • 12
    Electronic Resource
    Electronic Resource
    Springer
    Acta neuropathologica 13 (1969), S. 157-168 
    ISSN: 1432-0533
    Keywords: Gangliosides ; Tay-Sachs Disease ; Brain Subcellular Localization ; Hale Stain ; Electron Microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Die Reaktion von kolloidalem Eisen mit Sialomucinen (Hale stain) wurde zur elektronenmikroskopischen Darstellung der neuraminsäurehaltigen Ganglioside in den subcellulären Fraktionen des Gehirns angewandt. Zunächst wurde mit Hilfe tritiummarkierter Ganglioside überprüft, ob bei der Gewinnung subzellulärer Fraktionen Ganglioside nicht unspezifisch subcellulär adsorbiert werden. Eine nennenswerte Adsorption konnte ausgeschlossen werden. Das Verfahren wurde zuerst auf die aus Meerschweinchengehirnen isolierten Fraktionen angewandt. Da Nervenendigungen, Mitochondrien und Synapsenbläschen Hale-positiv reagierten, dienten Enzyminkubationen mit Neuraminidase und Hyaluronidase zur Differenzierung von anderen Hale-positiven sauren Substanzen. Schließlich wurde die Methode auf die cytoplasmatischen multilamellären Körperchen (MCB) übertragen, die aus Gehirnen an Tay-Sachs'scher Krankheit Verstorbener isoliert wurden. Aus den Versuchen konnte abgeleitet werden, a) daß die Hale-Färbung auch Ganglioside anfärbt, b) daß Ganglioside auf der Oberfläche der Membran von den multilamellären Körperchen und mit hoher Wahrscheinlichkeit auch auf der Membran der Nervenendigungen lokalisiert sind, c) daß die Synapsenbläschen eine positive Reaktion ergeben, die jedoch nicht mit Sicherheit auf vorhandene Ganglioside zurückgeführt werden kann, d) daß die äußere Mitochondrienmembran Hale-positive Substanzen enthält, deren Natur unbekannt ist.
    Notes: Summary The reaction of colloidal ferric oxide with sialomucins (Hale stain) was applied to sialic acid-containing gangliosides in subcellular fractions of the brain, in order to investigate their localization by electron microscopy. Prior to all experiments, a check was made, by means of tritium-labeled ganglioside, to confirm that the ganglioside content in the subcellular particles was not the result of an unspecific adsorption during the isolating procedure. No considerable unspecific adsorption could be registered. Hale stain was first applied to subcellular fractions obtained from guinea-pig brains. Since nerve-endings, mitochondria and synaptic vesicles gave a positive staining reaction, incubations with neuraminidase and hyaluronidase were carried out in order to achieve a differentiation. Finally, the method was applied to the membranous cytoplasmic bodies (MCB) which were isolated from the brain of a patient with Tay-Sachs disease. It was concluded that: a) Hale stain stains gangliosides also, b) gangliosides are localized in the membrane of membranous cytoplasmic bodies and also very probably in the membrane of nerve-endings, c) synaptic vesicles give a Hale-positive reaction which cannot with certainty be attributed to gangliosides, d) the outer membrane of mitochondria contains Hale-positive substances, the nature of which is not known.
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  • 13
    Electronic Resource
    Electronic Resource
    Springer
    Acta neuropathologica 13 (1969), S. 197-216 
    ISSN: 1432-0533
    Keywords: Peripheral Nerves ; Axons ; Myelin Sheaths ; Schwann Cells ; Electron Microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Eine kombinierte licht- und elektronenmikroskopische Untersuchung am normalen N. suralis von 7 Menschen im Alter von 15–59 Jahren wurde vorgenommen. Qualitative und quantitative Beobachtungen an Schwann-Zellen und Fibroblasten, markhaltigen und marklosen Fasern wurden an isolierten Faszikeln durchgeführt. Schwannzellen überwiegen gegenüber Fibroblasten im Verhältnis von etwa 9:1. Die meisten Schwannzellen (etwa 80%) liegen an marklosen Fasern. Die Faktoren, welche die Dichte dieser Zellen pro Querschnittsareal beeinflußen, werden diskutiert. Einige ultrastrukturelle Befunde an bemarkten Fasern werden beschrieben und ihre Zahl pro mm2 sowie die Häufigkeitsverteilung ihrer Dicke wird angegeben. Eine indirekte Methode zur Bestimmung der mittleren Internodienlänge für jede der Markfasergrößenpopulationen an Querschnitten von Faszikeln normaler Nerven durch Bestimmung des Verhältnisses der markhaltigen Fasersegmente zu ihrer Kernzahl wird vorgeschlagen. Die Ultrastruktur der marklosen Nervenfaern wird beschrieben und die Identifizierung dieser Axone mit extremen Durchmessern diskutiert. Ihre Dichte und Größenfrequenzhistogramme sind die ersten, die am Menschen durch systematische elektronenoptische Untersuchungen veröffentlicht werden. Das mittlere Verhältnis von marklosen zu bemarkten Fasern ist etwa 3,7:1 und schwankt in den Faszikeln der Einzelindividuen.
    Notes: Summary A combined light and electron microscope study of the normal sural nerve in 7 people aged 15–59 years is reported. Qualitative and quantitative studies of the Schwann cells and fibroblasts, myelinated and unmyelinated fibres are made in isolated fascicles. Schwann cells predominate over fibroblasts in the ratio of about 9-1. Most Schwann cells, almost 80%, are attached to unmyelinated fibres. Factors influencing the densities of these cells per cross sectional area are discussed. Some ultrastructural features of the myelinated fibres are described and their numbers per sq.mm and frequency distribution of their sizes are produced. An indirect method is proposed for assessing the mean internodal length for earch of the myelinated fibre size populations in cross sections of fascicles of normal nerves by estimating the proportion of myelinated segments cut through their nucleus. The ultrastructure of unmyelinated fibres is described and the identification of axons of extreme diameter is discussed. Their densities and size frequency histograms are the first to be reported in man by systematic electron microscope studies. The average ratio of unmyelinated to myelinated fibre density is about 3.7:1 though it varies in the fascicles of the different individuals. The implications of axonal diameter in the presence of myelin are commented on.
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  • 14
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    Springer
    Acta neuropathologica 13 (1969), S. 289-293 
    ISSN: 1432-0533
    Keywords: Oligodendroglioma ; Nuclear Inclusions ; Electron Microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Es wird die Ultrastruktur von intranucleären stabförmigen Gebilden bei einem Oligodendrogliom beschrieben.
    Notes: Summary Ultrastructure of intranuclear rodlets in an oligodendroglioma is described.
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  • 15
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    Acta neuropathologica 14 (1969), S. 118-125 
    ISSN: 1432-0533
    Keywords: Carbon Monoxide Poisoning ; Electron Microscopy ; Myelin Disintegration ; Cerebral Anoxia
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Nach experimenteller CO-Vergiftung fanden sich schwerere und ausgedehntere Läsionen in der weißen als in der grauen Hirnsubstanz. Zwischen akuter und chronischer CO-Vergiftung ergaben sich keine wesentlichen qualitativen Unterschiede der Hirnveränderungen. Die Läsionen nach chronischer Intoxikation waren jedoch schwerer als nach akuter Vergiftung. Die Nervenzellen zeigten leicht dilatiertes oder fragmentiertes EPR und Golgi-Komplexe, doch boten die Mitochondrien meist keine pathologischen Veränderungen. Bei chronischen Fällen fand sich gelegentlich eine deutliche Schwellung des EPR von Oligodendrogliazellen. Die Capillaren blieben intakt und die perivasalen Astrogliaendfüßchen waren nicht geschwollen. Im Mark kam es zu teilweisem Ausfall der normalen Markscheidenbestandteile. Die Marklamellen zeigten mäßige Exfoliation sowie eine Umwandlung in homogene oder strukturlose Substanz. Bemarkte Axone waren teilweise kontrahiert und zeigten auf Querschnitten unregelmäßige Form. Gelegentlich fand sich eine Vergrößerung der axonalen Mitochondrien und Zerstörung ihrer inneren Parallelstrukturen. Als Hauptfaktoren in der Pathogenese der Hirnveränderungen nach experimenteller CO_Vergiftung werden zerebrale Anoxie infolge CO-Hämoglobinbildung, cytotoxische Wirkung von CO auf das Hirngewebe und eine Störung der Blutzirkulation angenommen.
    Notes: Summary In experimental carbon monoxide poisoning, more marked and widespread pathological changes in the brain were seen in the white matter as compared with the gray matter. No essential difference, in the appearance of cerebral alterations, was detected between acute and chronic carbon monoxide poisoning. It was confirmed that the changes resulting from chronic poisoning showed a higher degree of severity as compared with those resulting from acute poisoning. Nerve cells with slightly dilated or fragmented endoplasmic reticulum and Golgi complex in the gray matter were found infrequently. However, most mitochondria did not show any kind of abnormality in such cells. A remarkable dilatation of the endoplasmic reticulum of oligodendrocytes was sometimes seen in chronic cases. Capillaries remained intact and astrocytic perivascular foot-plates were not swollen. In the white matter, the normal constituents of the myelin sheath were partially lost and the myelin lamellae showed moderate exfoliation, or a change into homogenous or structureless substance. Myelinated axons were partially contracted and showed an irregularity in shape in transverse sections. Enlargement of occasional axonal mitochondria and the destruction of their internal parallel structures were observed. Cerebral anoxia caused by carboxyhaemoglobin, together with the cytotoxic action of carbon monoxide on the brain tissue and the disturbance of blood circulation in the brain are suggested as the chief factors in the pathogenesis of the cerebral alterations induced by experimental carbon monoxide poisoning.
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  • 16
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    Acta neuropathologica 14 (1969), S. 185-193 
    ISSN: 1432-0533
    Keywords: Hypoxia ; Sodium Azide ; Electron Microscopy ; Ferritin ; Capillary Permeability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Experimentelle histotoxische Hypoxämie wurde in Ratten durch Natriumacid-Vergiftung erzeugt. Die mikroskopische Untersuchung der Hirne ergab keine Veränderung, aber bei der elektronenmikroskopischen Untersuchung fanden sich als Frühveränderungen in der Hirnrinde und im Subcortex eine Erweiterung der intercellulären Räume und eine Anschwellung der pericapillären Astrocytenfortsätze. Ferritinalbumin-Mischung, die als Indicator des Eiweißtransportes benutzt wurde, zeigte keine Vermehrung der Capillarpermeabilität. Es wird vermutet, daß Natriumacid den Wasserstoffwechsel beeinträchtigt, wobei es eine osmotische Ausgleichstörung im Gehirn erzeugt.
    Notes: Summary Histotoxic hypoxia was experimentally produced in the rat brain by sodium azide intoxication. In spite of the absence of light microscopic alterations, electron micrographs showed the early changes in the cerebral cortex and subcortex which consisted of widening of the intercellular space and swelling of the pericapillary astrocytic end-feet. However, ferritin-albumin mixture, used for the tracer of protein transport, did not show any increase in the capillary permeability. Sodium azide was considered to disturb the water metabolism, producing osmotic unbalance in the brain.
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  • 17
    ISSN: 1432-0533
    Keywords: Methamphetamine Poisoning (Artificial Psychosis) ; Synapses ; Nerve Conduction and Transmission ; Electron Microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Amphetaminchlorid in Mengen von 1 mg pro kg pro Tag wurde 8 männlichen Meerschweinchen ungefähr 1 Jahr lang täglich injiziert, um eine chronische Amphetaminvergiftung zu erzeugen. Bei jedem vergifteten Tier wurde die Feinstruktur des Gehirns elektronenmikroskopisch untersucht. Die Befunde waren folgende: 1. Verschmelzung der Membranen zwischen Axonen in den Nervenendigungen sowie zwischen Axonen und Dendriten wurden in der Großhirnrinde, im limbischen System, im Thalamus und Hypothalmus beobachtet; ferner wurde eine sich vom Cytoplasma bis zur Nervenendigung erstreckende Membranstruktur in diesen Hirnbereichen festgestellt. 2. Im Frontal-, Parietal-, Temporal- und Occipitalhirn sowie im limbischen System fanden sich vermehrt membranbegrenzte Vesikel im Cytoplasma der Nervenzellen und verdicktes und vermehrtes ER in den Nervenfasern. In Anbetracht klinischer Symptome der Patienten mit Amphetaminvergiftung wurde angenommen, daß die Verschmelzung von Membranen zwischen Nervenfortsätzen und das Auftreten der Membranstrukturen in allen Teilen des Nervenzellcytoplasmas vom Perikaryon bis zur Nervenendigung die wichtigsten Befunde sind, die darauf hindeuten, daß die Vergiftungsvorgänge einen wesentlichen Einfluß auf das Leitungssystem der Nerven ausüben können.
    Notes: Summary In 8 male albino strain guinea pigs, 1 mg/kg of methamphetamine HCl was injected daily for 7 months to 1 year to produce chronic methamphetamine intoxication and to study the fine structure of the brain electron microscopically. The following results were obtained: 1. Coalescence of membranes, between axons at the nerve endings and between axons and dendrites, was found in the cortex of the cerebrum and limbic system, in the thalamus and hypothalamus. Membranous structures were found in all portions of the cytoplasm of the nerve cells. 2. Within the cytoplasm of the nerve cell, coated vesicles were increased in number with hypertrophy and increase of endoplasmic reticulum within nerve fibres in the frontal, parietal, temporal and occipital regions, and in the limbic system. In view of these findings, as well as the clinical neurological symptoms in patients with methamphetamine poisoning, the coalescence of membranes between nerve processes and the appearance of membranous structures in all portions of nerve cell cytoplasm from body to nerve endings appear to represent the most important findings, they probably produce a profound disturbance in the system of nerve conduction and transmission.
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  • 18
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    Acta neuropathologica 14 (1969), S. 237-249 
    ISSN: 1432-0533
    Keywords: Electron Microscopy ; Wallerian Degeneration ; Nodal Changes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Es wird über ultrastrukturelle Veränderungen in den Ranvierschen Knoten des N.suralis der Ratte im Laufe der Wallerschen Degeneration berichtet. Die Untersuchungen erfolgten 12 und 120 Std nach einer örtlichen Quetschungsverletzung. Die ersten bemerkbaren Veränderungen finden sich im Axon. Nodale und paranodale Anhäufungen von Mitochondrien, multivesikulären und lamellären Körpern, wie auch kleinen blasen- und röhrenartigen Bildungen sind teilweise in den Knoten sichtbar und am deutlichsten nach 24–36 Std erkennbar. Gleichzeitig erfolgt eine Aufsplitterung der Neurofilamente und Neurotubuli, die ihre Liniengestaltung verlieren und sich zusammenballen. Die Zone der erhöhten Dichte gerade unterhalb des nodalen Axolemmas bleibt erhalten. Veränderungen im Myelin beginnen etwas später und bestehen in einem vesikulären Verfall der Endomyelinlamellen und einer Trennung der Endomyelinschlaufen vom Axolemma durch Schwannzellenfortsätze. Dieser Vorgang schien mit einem Zurückziehen des Myelins vom Knoten im Zusammenhang zu stehen. Schwannzellenfortsätze erstrecken sich auch so weit, daß sie das nodale Axon bedecken, wobei sie die nodalen Schwannzellenfortsätze vom Axolemma trennen. Das Endstadium ist die Unterbrechung des nodalen Axons und die Verschmelzung der Myelinenden als Teil der Ovoidbildung.
    Notes: Summary Observations are reported on the ultrastructural alterations at the nodes of Ranvier in the rat sural nerve during the course of Wallerian degeneration. These were examined between 12 and 120 hours after a localized crush injury. The earliest detectable changes are in the axon. Nodal and paranodal accumulations of mitochondria, multivesicular bodies, lamellar bodies and small vesicular and tubular profiles are seen at a proportion of the nodes and are most evident at 24–36 hours. Concomitantly with this, the neurofilaments and neurotubulus fragment, lose their alignment and clump together. The zone of increased density just beneath the nodal axolemma is preserved. Changes in the myelin begin slightly later and consist of vesicular breakdown of the terminal myelin lamellae, and separation of the terminal myelin loops from the axolemma by Schwann cell processes. The latter event appeared to be associated with retraction of the myelin from the node. Schwann cell processes also extend to cover the nodal axon, separating the Schwann cell nodal processes from the axolemma. The final stage is the interruption of the nodal axon and the fusion of the ends of the myelin as part of ovoid formation.
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  • 19
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    Acta neuropathologica 13 (1969), S. 149-156 
    ISSN: 1432-0533
    Keywords: Electron Microscopy ; Leucodystrophy, Metachromatic ; Enzyme Histochemistry, Electronmicroscopical ; Lysosomes ; Neurochemistry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé Dans la leucodystrophie métachromatique, les lipides anormaux s'accumulent dans les lysosomes des cellules gliales et des phagocytes. Les inclusions lipidiques les moins organisées sont les plus riches en phosphatases acides. Celles dont l'ultrastructure est prismatique ont une activité enzymatique très faible et semblent plus proches de corps résiduels que de lysosomes actifs. Il semble que l'absence d'arylsulfatase lysosomiale induise la persistance des sulfatides accumulés dans les lysosomes alors que les autres lipides provenant de la dégénérescence myélinique, seraient normalement catabolisés. Un remaniement progressif de l'ultrastructure du contenu des lysosomes en est la conséquence.
    Notes: Summary In metachromatic leucodystrophy abnormal lipids are stored within the lysosomes of the glial cells and phagocytes. The lipid inclusions which are the less structured are the richest in acid phosphatases. Those of which the ultrastructure is prismatic show a very low enzymatic activity and are more similar to residual bodies than to active lysosomes. It appears that the lack in lysosomal arylsulfatase leads to an accumulation of the sulfatide moiety of the stored lipids while the other lipids originating from the myelin breakdown, would be normally catabolized. This leads to a progressive transformation of the ultrastructure of the lysosome contents.
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  • 20
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    Acta neuropathologica 13 (1969), S. 169-181 
    ISSN: 1432-0533
    Keywords: Japanese Encephalitis ; Experimental ; Electron Microscopy ; Virus Particles in Neurons
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Groß- und Kleinhirnrinde, Plexus chorioideus und Rückenmark von Mäusen wurden nach intracerebraler Inoculation einer Hirnemulsion mit Virus der Encephalitis japonica (JEV) elektronenoptisch untersucht, um den Ort der JEV-Replikation zu bostimmen. 72 Std nach der Inoculation bei Beginn der encephalitischen Symptome enthielten 70 bis 80% aller Rindenneurone und Vorderhornzellen viele sphärische Partikel, die meist im zarten endoplasmatischen Reticulum (EPR) und vereinzelt im granulären EPR lokalisiert waren. Die Einzelpartikel zeigten eine gleichförmige Substruktur aus einem elektronendichten zentralen Hof von 25–30 mμ Durchmesser, einer äußeren, weniger elektronendichten Zone und einer äußersten Grenzmembran von 40 mμ Durchmesser. 96 Std nach der Inoculation zeigte das Cytoplasma der Rinden- und Vorderhornneurone sehr viele Vacuolen und Vesiceln. Partikel wurden weit verstreut in den Vacuolen und Vesiceln sowie erstmals im ERP der Sternzellen und Purkinjezellen angetroffen, allerdings in geringerer Zahl. Keine derartigen Partikel wurden in Kontrolltieren und normalen Mäusegruppen angetroffen. Sogenannte eosinophile intranucleäre Einschlüsse in Epithelzellen des Plexus chorioideus zeigten keine derartigen Partikel im Kern oder in den cytoplasmatischen Bläschen. Nachdem keine als JEV identifizierbaren Partikel in Glia- und Endothelzellen nachzuweisen waren, wird angenommen, daß das JEV echt neurotrop ist und sich im EPR der Nervenzellen repliziert.
    Notes: Summary Cerebral and cerebellar cortices, choroid plexus and spinal cord of mice, inoculated intracerebrally with a brain emulsion containing Japanese encephalitis virus (JEV), were studied electronmicroscopically to determine the cell type and the site of JEV replication. 72 hours after inoculation, when the mice began to show encephalitic symptoms, 70 to 80% of all cortical neurons and anterior horn cells contained many spherical particles mostly located in the smooth endoplasmic reticulum and a few in the granular endoplasmic reticulum. The individual particles demonstrated an uniform substructure consisting of an electron dense central core of 25–30 mμ diameter, an outer less electron dense zone and an outermost limiting membrane of 40 mμ diameter. 96 hours after inoculation, the cytoplasm of cortical neurons and anterior horn cells was observed to contain very many vacuoles and vesicles. Particles were found widely scattered throughout the vacuoles and vesicles, and were observed for the first time in the endoplasmic reticulum of the stellate neurons and in Purkinje cells, though fewer. No such particles were observed in control and normal mouse groups. So-called eosinophic intranuclear inclusions of epithelial cells of choroid plexus failed to show any particles in their nuclei or cytoplasmic vesicles. Considering that no particulate matter, identifiable as JEV, was identified within any of the glial cells or endothelium in this examination, it was concluded that JEV was really neurotropic and replicates in the endoplasmic reticulum of the neurons.
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  • 21
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    Acta neuropathologica 13 (1969), S. 250-266 
    ISSN: 1432-0533
    Keywords: Electron Microscopy ; Congenital Myopathy ; Nemaline Myopathy ; Z-band Structure ; Sarcoplasmic Masses
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé L'étude ultrastructurale d'une observation de «Nemaline-Myopathy» a été centrée sur les rapports structurels entre bâtonnets et stries Z normales dans différentes conditions de fixation. L'aspect des stries Z, en section transversale, varie en effet avec la fixation: réseau de ponts «obliques» (par rapport à l'alignement quadratique régulier des terminaisons des filaments fins) après fixation osmiée, réseau de ponts «transversaux», isolé ou superposé au premier réseau, après fixation aldéhydique initiale. L'aspect des bâtonnets en section transversale varie également avec la fixation; la disposition quadratique des filaments constitutifs des bâtonnets est visible après l'une et l'autre fixation, mais un réseau quadratique régulier, de 75 Å de côté, n'est clairement apparent qu'après fixation aldéhydique. Le point important est que ce dernier aspect diffère complètement du réseau «oblique» des stries Z normales, et peut être rapproché au contraire du réseau «transversal» de la strie Z obtenu après fixation aldéhydique; l'hypothèse est ainsi soulevée de la constitution des ponts dans les bâtonnets aux dépens d'un seul des deux constituants morphologiques de la strie Z. La topographie des bâtonnets a été également étudiée: tantôt périphérique, au sein de masses sarcoplasmiques latérales, tantôt centrale, au sein de petits foyers de désintégration myofibrillaire. La structure des plaques motrices visibles dans les préparations était normale. La spécificité de la lésion élémentaire et l'autonomie de ce type de myopathie sont ensuite discutées.
    Notes: Summary Ultrastructural study of an observation of “Nemaline Myopathy” has been focused on structural relationships between rods and normal Z-bands in different conditions of fixation. The Z-band structure studied in transversal section, varies with the fixation: network of “oblique” (relative to the regular quadratic pattern of the thin filament endings) bridges after osmic fixation; network of “transversal” bridges, alone or associated to the first network, after aldehydic fixation. The rod structure, in transversal section, is also varying with the fixation: a quadratic disposal of the filamentary content is visible after both fixations, but a regular quadratic network, 75–85 Å side, is clearly appearent only after aldehydic fixation. This last network differs from the “oblique” network of the normal Z-band; it can be compared to the “transversal” one obtained in the Z-band after aldehydic fixation. The hypothesis that bridges in the rods are formed only by one of the two normal morphological components of the Z-band, is raised. Topography of the rods in muscle fibers has been studied: either in peripheral sarcoplasmic masses, or in small central-located foci of myofibrillar disintegration. The end-plates structure was normal. Specificity of the elementary lesion, and autonomy of that type of myopathy is discussed.
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  • 22
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    Acta neuropathologica 13 (1969), S. 301-323 
    ISSN: 1432-0533
    Keywords: Meningiomas ; Electron Microscopy ; Endotheliomatous, Fibromatous Type ; Light Cells ; Dark Cells ; Histogenesis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung 17 chirurgisch entfernte Meningiome vom endotheliomatösen und 5 vom fibromatösen Typ wurden elektronenmikroskopisch untersucht. Unterschiede im Entwicklungsgrad der cytoplasmatischen Fortsätze und der Beziehungen zwischen den Plasmamembranen der Tumorzellen wurden in den endotheliomatösen Meningeomen beobachtet. In 4 fibromatösen Tumoren sind die zelligen Areale von bindegewebigen Räumen umgeben. Auch wenn die meisten Tumorzellen helle Zellen sind und sich nicht wesentlich von den Tumorzellen der endotheliomatösen Meningiome unterscheiden, ist die histologische Anordnung der fibromatösen klar von derjenigen der endotheliomatösen Meningeome zu trennen. Ausschlaggebend dafür ist die starke Entwicklung des Bindegewebes. Die Dunkelzellen lassen sich in zwei Typen gliedern: Typ I wird in vier Tumoren mit stark ausgebildetem Bindegewebe angetroffen. Die Analyse der inneren Zellstruktur sowie das Vorliegen von Übergängen zwischen hellen und dunklen Zellen machen es wahrscheinlich, daß diese nur verschiedene Typen einer einzigen Ursprungszelle darstellen. Die Bedeutung dieser verschiedenen Erscheinungsformen der Meningiomzellen wird diskutiert. Die Ultrastruktur der Tumorzellen ähnelt derjenigen der normalen arachnoidalen Zellen. Rückschlüsse auf die blastodermale Herkunft der normalen und tumoralen meninigalen Zellen auf Grund ihrer ultrastrukturellen Merkmale erscheinen verfrüht.
    Notes: Summary Seventeen surgically removed meningiomas of the endotheliomatous and five of the fibromatous type were investigated with an electron microscope. Differences of the development of cytoplasmic processes and the relations between plasma membranes of blastomatous cells were observed in endotheliomatous meningiomas. In four of the fibromatous tumors the cell groups were surrounded by spaces of connective tissue. Although most of the tumor cells were light cells and are not essentially different from the tumor cells of the endotheliomatous meningiomas, the histological structure of fibromatous meningiomas is clearly distinguished from the endotheliomatous type, because of the greater amount of connective tissue. The dark cells may be divided into two types: the first was found in those four tumors, where the connective tissue is well developed, while the second one only occurred in one of the tumors. The analysis of the inner cell structure as well as the presence of interstages between dark and light cells makes it probable that dark and light cells are different types of one original cell. The cause of this different appearance of the menigioma cells is discussed. The fine structure of the tumor cells showed a great similarity with that of normal arachnoidal cells. Conclusions on the blastodermic origin of normal and blastomatous meningial cells on the basis of ultrastructural characteristics, however, seem to be premature.
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  • 23
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    Acta neuropathologica 14 (1969), S. 201-214 
    ISSN: 1432-0533
    Keywords: Electron Microscopy ; Epilepsy, Experimental ; Focus ; Cobalt Gelatine ; Plasmatic Infiltration ; Brain Edema
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Bei 25 erwachsenen Ratten wurde ein epileptogener Kobaltgelatineherd in einer Standardregion der Hirnrinde erzeugt. Die Tiere wurden am 1., 3., 5., 8., 14. 21. und 28. Tag nach der Operation getötet. Das Gebiet des epileptogenen Herdes wurde elektronenmikroskopisch untersucht. Die frühesten Veränderungen bestanden in ödem. Später traten Veränderungen der Astrocytenfortsätze auf, die sich an die Basalmembranen der Capillaren anlegten; die Intercellularräume erweiterten sich, füllten sich mit elektronenoptisch dichten Massen und entwickelten ein “plasmatisches Infiltrat”. Allmählich breitete sich dieses Exsudat weiter um die Capillaren aus; es trat an Orten auf, wo die Astrocytenfortsätze und die Dendriten schwer geschädigt waren und erfüllte die weiteren Intercellularräume des Neuropils. Die Nervenzellen zeigten eine auffallende Widerstandsfähigkeit gegenüber diesem pathologischen Prozeß. Manchmal waren sie umschlossen von Exsudatmassen und zum Teil oder ganz der zarten neuralen und Astrocytenfortsätze beraubt, von denen sie normalerweise umgeben sind. Unsere Befunde werden als das ultrastrukturelle Korrelat der Schols'schen “plasmatischen Infiltration” interpretiert.
    Notes: Summary In 25 adult rats an epileptogenic cobalt-gelatine focus was produced in a standard region of the cerebral cortex. The animals were killed successively on the 1st, 3rd, 5th, 8th, 14th, 21st and 28th day after operation and the region of the epileptogenic focus was examined electron microscopically. The earliest changes were those of oedema. Later there occurred disturbances of the astrocytic processes which cling to the basement membranes of the capillaries; the intercellular spaces widened and filled with rather E. M. dense masses and a “plasmatic infiltrate” developed. Gradually this exudative substance spread even further from the capillaries. It appeared in places where the astrocytic processes were severely demaged and the dendrites were partly dissipated and it filled out the wide intercellular spaces of the neuropil. The nerve cells showed a striking resistance toward this pathological process. Sometimes they floated in the exudative masses but were partly or totally deprived of the fine neural and astrocytic processes which normally surround them. Our findings are interpreted as the ultrastructural correlate of Scholz's “plasmatic infiltration”.
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  • 24
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    Calcified tissue international 3 (1969), S. 151-162 
    ISSN: 1432-0827
    Keywords: Calcification ; Physiologic ; Phosphonic Acids ; Phosphates ; Crystallization ; Electron Microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé On a étudié la formation de l'hydroxyapatite de calcium cristallin à partir de solutions d'ions de calcium et de phosphate et l'inhibition de la croissance de cristaux de l'hydroxyapatite de calcium au moyen de polyphosphonates et de polyphosphates. Les polyphosphonates, éthane hydroxy-1-diphosphonate-1,1 de disodium et dichlorométhanediphosphonate de disodium, sont inhibiteurs efficaces contre la croissance de cristaux de l'hydroxyapatite de calcium. Les polyphosphates sont aussi inhibiteurs efficaces contre la croissance de cristaux de l'hydroxyapatite de calcium tant que le niveau exigé de polyphosphate intact est présent dans le système. Cependant, à cause de leur instabilité hydrolytique, qui est soulignée par une température élevée, valeur de pH basse, et certaines enzymes, la concentration du polyphosphate diminue avec le tempsin vitro, et son activité comme inhibiteur est perdue. Au contraire aux polyphosphates, les polyphosphonates sont hydrolytiquement stables. Les polyphosphonates sont chimiosorbés sur la surface des microcristallites de l'hydroxyapatite de calcium, ainsi empêchant l'occurrence d'autre croissance de cristaux semblable à l'action d'autres poisons connus de croissance de cristaux. On propose l'extension de cette action sur la formation de l'apatite et cette stabilité des polyphosphonates aux applications médicales et dentaires concernant le metabolisme pathologique de calcium et de phosphate.
    Abstract: Zusammenfassung Die Bildung des kristallinen Calciumhydroxyapatit aus Lösungen, welche Calcium- und Phosphationen enthalten, und die Hemmung der Bildung von kristallinen Calciumhydroxyapatit durch Polyphosphonate und Polyphosphate wurden untersucht. Polyphosphonate, Dinatriumäthan-1-hydroxyl-1,1-diphosphonat und Dinatriumdichloromethandiphosphonate verhindern das Kristallwachstum des Calciumhydroxyapatits. Die Polyphosphate verhindern ebenfalls das Kristallwachstum des Calciumhydroxyapatits, solange die notwendige Konzentration des nicht hydrolysierten Polyphosphats vorhanden ist. Wegen ihrer hydrolytischen Unbeständigkeit, die durch hohe Temperatur, niedrige pH und bestimmte Enzyme erhöht wird, vermindert sich jedoch die Konzentration des Polyphosphats allmählichin vitro, und ihre Hemmungsaktivität geht verloren. Im Gegensatz zu den Polyphosphaten sind die Polyphosphonate hydrolytisch beständig. Die Polyphosphonate werden an der Oberfläche der Mikrokristallite des Calciumhydroxyapatits chemisorbiert und verhindern, wie andere bekannte Kristallwachstumsgifte, auf diese Weise weiteres Kristallwachstum. Die Beständigkeit der Polyphosphonate und ihre Chemisorption an dem Apatit empfehlen ihren Gebrauch in der ärztlichen und zahnärztlichen Praxis, soweit sie den pathologischen Calcium- und Phosphatstoffwechsel betreffen.
    Notes: Abstract The formation of crystalline calcium hydroxyapatite from solutions of calcium and phosphate ions and the inhibition of calcium hydroxyapatite crystal growth by polyphosphonates and polyphosphates have been studied. The polyphosphonates, disodium ethane-1-hydroxy-1,1-diphosphonate and disodium dichloromethane diphosphonate, are effective inhibitors of calcium hydroxyapatite crystal growth. The polyphosphates are also effective inhibitors of calcium hydroxyapatite crystal growth as long as the required level of intact polyphosphate is present in the system. However, because of their hydrolytic instability, which is enhanced by high temperature, low pH, and certain enzymes, the concentration of the polyphosphate decreases with timein vitro, and its activity as an inhibitor is lost. In contrast to the polyphosphates, the polyphosphonates are hydrolytically stable. The polyphosphonates are chemisorbed on the surface of the microcrystallites of calcium hydroxyapatite and, in the manner of other known crystal growth poisons, thus prevent further crystal growth. The stability of the polyphosphonates and their chemisorption on apatite suggest their use in medical and dental applications involving pathological calcium and phosphate metabolism.
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  • 25
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    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 219-229 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The compressibility of polyisobutylene and polystyrene above their glass transition temperature is treated as the sum of two parts; a free-volume compressibility and, as originally suggested by Bridgman, a compressibility of the molecules themselves. Two different models are used to treat the free-volume compressibility, and as a result values for the molecular compressibility are estimated. These are in reasonable agreement with other values in the literature. The magnitude of this “molecular compressibility” is then considered in relation to some existing treatments of intermolecular forces. These suggest that intermolecular contacts are more compressible than covalent bonds, and on this basis the observed levels of molecular compressibility can be explained.
    Additional Material: 6 Ill.
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  • 26
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 429-429 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 27
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 433-462 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The intrachain and interchain vibrations below 900 cm-1 of polydimethylsiloxane (PDMS) have been studied by slow neutron inelastic scattering. A composite motion observed at +25°C for the methyl groups corresponds to nearly free rotation about the threefold axis of symmetry together with a large-amplitude rotation of the entire methyl group. At -123°C, rotation about the threefold axis evolves to a torsional oscillation. The large-amplitude rotation evolves to the skeletal vibrations of a helical conformation. Vestiges of the cooperative skeletal vibrations of the conformation at -123°C persist into the 25°C spectrum. The results indicate the presence of interrupted helical conformations at 25°C, which result from thermal disordering of the low temperature helices. The effects of crosslinking, low molecular-weight oils, and silica filler on the freedom of the methyl group motions and on skeletal vibrations have been determined. The effects of different crosslinking agents and different relative amounts of filler and oil on both the macroscopic physical properties and the observed molecular motions of PDMS can also be interpreted in terms of an interrupted helix.
    Additional Material: 16 Ill.
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  • 28
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 463-473 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polymers of poly(N-acyl and N-aroyl aziridines) were studied by x-ray diffraction. All the crystalline polymers studied have a triclinic unit cell with two monomer units per unit cell. The a and c (fiber direction) parameters (4.9 and 6.5 A, respectively) are essentially the same for all the cells. The b parameter for the N-acyl polymers, however, increases steadily by a factor of 2 A per methylene group added to the lateral chains. The densities calculated for the unit cells are in agreement with the experimental values obtained. The most probable structure is one in which the molecules assume a planar configuration with the main chain not fully extended. The lateral groups are tilted from the c axis by an angle of 54° in a parallel configuration and alternate on each side of the main chain. This permits these lateral groups to assume packing similar to that of polyethylene. A brief description of the techniques used in this interpretation is included.
    Additional Material: 8 Ill.
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  • 29
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 475-481 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Experiments in which an oscillatory shear flow is superimposed on a steady state shear flow were performed on polyethylene melts by the use of a cone and plate type rheogoniometer. The phase difference between oscillatory shear stress and shear strain increases in all cases and for all frequencies with the increase of the superimposed shear rate. Between ω0, the frequency at which the phase difference is π/2 and the steady shear rate \documentclass{article}\pagestyle{empty}\begin{document}$ \dot \gamma $\end{document}, as found by Booij for polymer solution, the relation ω0 = 1/2 \documentclass{article}\pagestyle{empty}\begin{document}$ \dot \gamma$\end{document}. holds also for polyethylene melts. The significance of this relation is discussed briefly from the viewpoint that the entanglement density decreases with the increase of the imposed shear rate.
    Additional Material: 9 Ill.
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  • 30
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 483-495 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The peak separation in gel-permeation chromatography (GPC) is attributed to the contributions of the steric exclusion and the lateral diffusion processes. The advantage of using the distribution coefficient KGPC of the solute molecule in interpreting the GPC separation mechanism is assessed. The physical significance of KGPC and its relation to measurable GPC parameters are examined in detail. A simple mixing experiment for determining the exclusion effect is described. The results of this experiment, as well as those of the flow rate study, show that the exclusion effect plays the primary role in GPC peak separation. For a column packed with Bio-Rad porous glass of 200 Å designation, the diffusion effect does not contribute significantly to peak separation. However, for the case of a Waters Associates column packed with polystyrene gel of 104 Å designation, both the exclusion and the diffusion effects are shown to be important. A diffusion theory which includes the concept of a restricted diffusion coefficient is proposed to interpret the diffusion effect observed in the polystyrene gel column. The results of the theoretical calculation are found to agree with the observed flow rate dependence of the calibration curve.
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  • 31
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 497-513 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Triplet → singlet energy transfer in nylon 66 film (donor) dyed with proflavine (acceptor) is demonstrated by a decrease of the nylon phosphoresence lifetime and an increase in the proflavine delayed fluorescence/nylon phosphoresence ratio with increasing proflavine concentration. Although the observed donor phosphorescence decay is apparently exponential, the transfer is probably via a long-range dipole-dipole (Förster) interaction, rather than by triplet exciton migration. Arguments are advanced to support this view. Proflavine delayed fluorescence produced by a direct excitation process is also observed. The decay time for this process is roughly an order of magnitude less than that for the sensitized process. All emission intensities are shown to vary linearly with exciting light intensity. Finally, temperature dependence of proflavine delayed fluorescence under different excitation conditions is shown. The efficiency of direct excitation process increases markedly near -50°C as the temperature is increased; the sensitized delayed fluorescence intensity follows that of the nylon phosphorescence with increasing temperature, as expected.
    Additional Material: 7 Ill.
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  • 32
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 515-524 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An x-ray study of poly(N-butyl isocyanate) (PBIC) was undertaken with the aim of providing the structural information required for the calculation of its ultraviolet absorption spectrum. Well defined diffraction patterns are obtained from powder samples and oriented films of the polymer cast from cyclohexane solution. All the reflections can be satisfactorily indexed in terms of a pseudo-hexagonal unit cell with a = 13.3 Å and c = 15.4 Å. This indexing and the intensity distribution lead to the conclusion that PBIC has a helical structure with a translation of 1.94 Å and a rotation of 135° per monomeric unit (i.e., the c axis corresponds to 8 units in 3 helical turns). In the absence of single-crystal data on closely similar model compounds, a range of possible bond lengths and angles was assumed. The atomic coordinates of the chromophoric group of PBIC were then computed using the restrictions imposed by the helical parameters. From an investigation of all the assumed range of bond lengths and angles, a few closely similar structures having no unacceptably short van der Waals contacts were found. A comparison of calculated and measured densities indicates that there are two molecules per unit cell. Construction of space-filling models of PBIC supports this conclusion.
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  • 33
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 113-122 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Differences in structural parameters, shrinkage, and retractive forces have been compared for nylon 66 tire yarns annealed at several temperatures in silicone oil and in air. It is found that significantly different structural changes occur for oil-annealing and air-annealing. Retractive forces measured in hot oil are characterized by a high initial force, followed by a rapid decay and a second, more gradual, increase which is also followed by a decay at sufficiently high temperatures. In heated air, the first, short-term, retractive force is absent. It is postulated that these differences are due to the different rates of heat transfer at gas-solid and at liquid-solid interfaces, and that rapid heat transfer (as in the case of oil-annealing) promotes two mechanisms of molecular change which are characterized by different degrees of structural parameter change, and by different amounts of shrinkage.
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  • 34
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 143-151 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A theoretical discussion is presented on the mechanisms by which an isolated pulsating air bubble in a viscoelastic solid dissipates its energy. The analysis is limited to the situation where the amplitude of motion is assumed to be sufficiently small that the stress strain relations may be described by linear equations with convected differentiation replaced by ∂/∂t. The theoretical thermal, radiation, and viscous damping constants are calculated for resonant air bubbles in unvulcanized natural rubber; however, the results are typical of elastomers in general.
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  • 35
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 163-170 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A resolution index for gel-permeation chromatograph (GPC) columns is defined by the relation log (RI) = αW, where RI is the resolution index, α is the slope of the calibration curve of logarithm of molecular weight against peak position for narrow polymer fractions, and W is the width of the GPC curves for narrow fractions. This resolution index is calculated approximately for several GPC columns individually and in series combinations by using data obtained on narrow fractions of polystyrene. The index increases with number of columns and with flow rate over a limited range of flow rate, does not vary much with solvent, and does not correlate well with plate count obtained with low molecular weight molecules. It is believed that the resolution index provides an improved indication of the performance of GPC columns.
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  • 36
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 183-200 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Equipment and methods have been developed which allow photomicrographic determination of the stress-strain properties of the individual craze. Serial cyclic tensile tests on polycarbonate crazes are described. Under stress the typical dry polycarbonate craze thickens solely by straining; no adjacent polymer of normal density is converted to craze material. The craze exhibits a yield stress followed by a recoverable flow to roughly 40-50% strain at 6000-8000 psi. On return to zero stress the craze exhibits creep recovery at a decelerating rate. The yield stress and loss factor of each cycle decrease with increasing initial strain and cycles initiating at 50% strain or more show completely Hookean behavior. Creep recovery results in recovery of yield stress and loss factor also. Craze tensile behavior is suggested to be essentially an extension of the craze formation process. Decrease in elastic modulus and yield stress with increasing strain are rationalized in terms of strain-produced decrease in density and resultant increase in stress concentration factor on the microscopic polymer elements of the craze. Polymer surface tension and the large internal specific surface area of the craze are suggested to be important factors in the large creep recovery rates of the craze.
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  • 37
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 231-240 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The birefringence of several biaxially oriented polypropylene films swollen with a number of fluids has been measured and found to exhibit a minimum when plotted against the fluid refractive index, as predicted by the theory of Wiener. However, a discrepancy in the form birefringence behavior is observed when samples of different degrees of crystallinity but the same total birefringence are compared. These results are interpreted in terms of Bullough's theory and suggest that this discrepancy arises because of different morphologies. A refractometric technique was employed that makes possible the simultaneous determination of birefringence and the volume fraction of fluid.
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  • 38
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 249-252 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: NO ABSTRACT.
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  • 39
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 253-254 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 40
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 2029-2041 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Drawing of single-crystal mats of linear polyethylene has been investigated. Drawing is possible at temperatures higher than about 90°C. The drawing is accompanied by distinct necking, with a large decrease in the thickness of the mat and a very high maximum draw ratio, sometimes over 30. The maximum draw ratio is approximately proportional to the thickness of the lamellae. This behavior strongly suggests the unfolding of chains during drawing. A change of orientation of crystal axes occurs before necking without change of lamellar orientation. The a axis orients in the drawing direction; the b axis orients perpendicular to the direction of drawing; and the chain axis tilts away from the thickness direction of the mat. The structure of films drawn from mats is characterized by a distinct double orientation of crystals. This biaxial orientation in the drawn films has a high degree of correlation with the orientation of crystal axes observed before necking, and suggests that necking takes place in such a way that the chain tilts gradually about the b axis and ultimately unfolds. The postulate of formation of transitory two-dimensional crystals in necking seems useful in explaining the double orientation in the drawn film. The orientation behavior of crystal axes observed before necking is not always similar to that observed in the deformation of a single crystal. The difference is thought to be due to the effect of forces induced by drawing that act in the direction normal to the lamellae within a mat.
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  • 41
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 2043-2050 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: This is the first paper of a series of reports concerning extended-chain crystals of flexible, linear high polymers. The general conditions for crystal growth are discussed. Polymer crystallization is described as a two-step process: nucleation of each crystallizing molecule to a folded-chain conformation, followed by an increase in fold length in a solid-state reorganization step. This reorganization step is enhanced in the case of polyethylene by crystallization at high temperature under elevated pressure. Mechanical deformation during crystallization is also able to produce extended-chain crystals. The most promising method, however, is crystallization during polymerization. Previous work on crystallization of polyethylene under elevated pressure is critically reviewed.
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  • 42
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 2051-2059 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A report on crystallization of polyethylene at elevated pressures to an extended-chain morphology is presented. The crystals have been characterized by electron microscopy and density determination. Pressure, supercooling (temperature), and crystallization time have been varied to find the best conditions for production of perfect crystals. At 10-30°C supercooling completely crystallized polyethylene was obtained between 4.5 and 7 kb crystallization pressure in 1-8 hr. Analysis of fracture surfaces of samples crystallized for different lengths of time shows an increase in size and number of crystal lamellae and an improvement of extended chain crystals in the early stages of crystallization. A further improvement of the less well crystallized material between the lamellae occurs after 15 min of crystallization time.
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  • 43
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1451-1459 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The adiabatic compressibility for two samples (F-1 with DP-3748 and F-2 with DP-2114) of poly(4-vinyl-N-n-butylpyridinium bromide) in aqueous solution has been determined from ultrasonic velocity and density data. The sample (F-1) with the higher degree of polymerization shows comparatively higher velocity and density in solution. However, the evidence for the difference in compressibility is not very decisive. The apparent molal volume ΦV2 and apparent molal compressibility ΦK2 for F-1 are found to be slightly higher than for F-2. In aqueous solution, the decrement of adiabatic compressibility per unit concentration, (β1 - β)/c, is found to be almost constant throughout the entire concentration range, whereas in the presence of excess added electrolyte (1.0M KBr solution), the compressibility decrement shows a decrease with dilution. The latter values are lower than those found in water, since the molecules, in the presence of excess electrolyte, are coiled up more and are less compressible. The ΦV2 and ΦK2 values in water are constant throughout the entire concentration range, as the free counterions formed on dissociation in the dilute region are not solvated and hence contribute little to the compressibility. On the other hand, in the presence of excess KBr (1.0M), the ΦV2 and ΦK2 values show a sharp decrease with increase of polyelectrolyte concentration and finally attain a constant value. This is explained by the fact that because of the formation of a charge-transfer complex between the bromide ion and the polycation, more than the equivalent number of bromide ions is bound, leaving free an equal amount of K+ ions which are solvated and cause the lowering of apparent volumes and compressibilities. Condensation of charges begins at a certain polyelectrolyte concentration, and no further increase of K+ ions is observed. A special situation arises in 0.1M KBr solution. The ΦV2 and ΦK2 values at first increase sharply with increase of polyelectrolyte concentration, but then level off to attain a constant value, at comparatively high concentration. In 2.0% poly(4-vinyl-N-n-butylpyridinium bromide) solution, the concentration of polymer repeat unit (0.08M) is almost equal to the concentration of the added electrolyte (0.1M KBr) used to suppress dissociation. As the polyelectrolyte concentration in 0.1M KBr solution is progressively decreased, more bromide ions are made available for forming the charge-transfer complex with the polycation, leaving the K+ ions free to contribute to the compressibility.
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  • 44
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1483-1487 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Expansion of a small spherical hole in a highly elastic solid is treated theoretically. Both elastic and surface energy terms are considered; the corresponding surface forces are assumed to be additive. The surface energy of the elastomer is assumed to be similar to that of simple liquids. Pressures or triaxial tensions required to inflate pre-existing holes to an indefinitely large size are calculated. Small holes require extremely large pressures, of the order of 1000 atm for holes of 10 Å radius. These results suggest a means of determining the distribution of hole sizes in elastomers and account in principle for experimental observations of cavitation processes. Detachment of the elastomer from a small rigid inclusion is treated in a similar way. The general absence of dilation or cavitation on stretching carbon black-filled elastomers is thus accounted for solely in terms of the small size of these filler particles.
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  • 45
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1033-1057 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The phenomenon of double melting, as manifested by two characteristic endotherms in the melting region on a differential thermal analysis (DTA) scan, has been studied in nylon 66 and polystyrene as a function of sample treatment by annealing or drawing. A variety of techniques were used in these studies including DTA, x-ray diffraction, electron microscopy, and mechanical testing. It is shown that the two endotherms are not caused by a bimodal crystal size distribution, by recrystallization, by orientation changes, or by phase changes. It is proposed that one endotherm is caused by the melting of foldedchain crystals, while the other is due to the melting of less perfect bundle crystals. This view is well supported by the results, especially by the DTA measurements made at different heating rates. Published data on the thermal behavior of annealed and drawn poly(ethylene terephthalate) and on polyethylene crystallized at various pressures may also be explained on this basis if it is allowed that in polyethylene the chains may be more extended.
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  • 46
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1059-1073 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Nylon 66 films exhibiting form I melting behavior show the γ mechanical relaxation at -140°C. Samples which have form II melting behavior do not show this relaxation. The γ relaxation disappears when material having form I behavior is converted to material having form II behavior by annealing or by cold drawing. The form I and form II types of melting behavior are also found in poly(ethylene terephthalate); the interconversions and thermal behavior of the forms are analogous to the nylon 66 case. In poly(ethylene terephthalate), the β relaxation at -40 to -60°C is present only when form I melting behavior is found. Conversion to form II melting behavior by annealing or drawing (80°C) again causes the relaxation to disappear. No β relaxation was found in amorphous polymer. The γ dispersion in nylon 66 and the β dispersion in poly(ethylene terephthalate) can therefore be associated with the crystalline structure responsible for form I melting behavior. Form I melting behavior has been associated with foldedchain crystals based on previous work. It is therefore postulated that the γ dispersion in nylon 66 and the β dispersion in poly(ethylene terephthalate) are associated with motions in the chain folds. This assignment is not inconsistent with the change in the γ dispersion of nylon 66 with the number of backbone CH2 units, since these will affect the fold structure.
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  • 47
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1075-1084 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Raman spectra have been obtained for a typical poly(vinyl chloride) (PVC) of low crystallinity and for a highly crystalline sample of syndiotactic PVC obtained by irradiation of a urea-canal complex. Raman measurements have been made on the three different ordered chain structures possible for ordinary PVC. Extended and folded conformations for the syndiotactic structure and a helical structure for the isotactic molecule obey different selection rules and have different dichroic properties in the infrared and Raman spectra. The observed Raman spectrum is consistent with the model of the extended syndiotactic conformation for crystalline PVC. With the new Raman data some additional assignments can be made in the vibrational spectra of PVC.
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  • 48
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1085-1099 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Measurements of infrared absorbance as a function of temperature down to 77°K have been made on poly(ethylene terephthalate). Transitions observed by other techniques such as torsion pendulum measurements are reflected in the infrared measurements by an abrupt change in the slope of the absorbance versus temperature. The infrared measurements are made on bands of known structural origin so the structures contributing to each transition can be determined. The β transition is shown by infrared to be a composite of two peaks with the lower-temperature portion arising from the amorphous regions and the higher-temperature portion from the crystalline regions.
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  • 49
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1681-1694 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Creep compliance data, J(t), at 35°C for poly(β-hydroxyethyl monomethacrylate), crosslinked by ethylene glycol dimethacrylate in a range of concentration C from 0.0855 to 2.053 × 10-4 mole/cm3 and swollen to various degrees in diluents, were examined for time-concentration superposition. From the dependence of time scale shift factors on v2, the volume fraction of polymer, free volume parameters were calculated for two samples with C = 0.0855 × 10-4 and 0.136 × 10-4 mole/cm3, swollen in the range of v2 from 0.134 to 0.591. Special attention was given to the magnitude of the shift factor on the log J(t) axis and its dependence on concentration, which was found to depend substantially on the crosslinking and the swelling degrees of the samples. This shift was approximately log v2 for lightly crosslinked samples, swollen to a small degree, measured in the neighborhood of the main transition. For higher degrees of crosslinking and/or swelling, the shift was much less and for the most highly crosslinked networks swollen to equilibrium it was even negative. The correction appears to be very sensitive to the strain of the effective chains and to the location on the time scale with respect to the transition and rubberlike zones of viscoelasic behavior. It was found that the parameters of the WLF equation calculated in our previous study from the time-temperature superposition of the creep curves in the rubber-glass transition are valid also for the rubberlike region.
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  • 50
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1303-1314 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Column chromatographic fractionation of polystyrene was carried out with the methyl-ethyl ketone-methanol system, and effects of various experimental conditions on the fractionation efficiency were studied. For samples with molecular weights below about 6 × 105, neither the temperature gradient (0.7°C/cm), nor the flow rate of solvent (30-270 ml/hr) seriously influences the fractionation efficiency. The effect of temperature gradient becomes apparent only in the high molecular weight region and only if the gradient of the solvent composition is too steep. High flow rates (ca. 125 ml/hr) clearly affect the fractionation efficiency for a high molecular weight sample (Mw = 5.46 × 105). Precipitation chromatography for the fractionation system was calculated from the phase equilibrium data according to the mass transport equation proposed by Schulz et al. The theoretical analysis gives support to the observed dependence of the temperature effect on molecular weight. Comparison of the observed and theoretical relations between elution volume and molecular weight of the fraction, on the other hand, indicates that the process of fractionation is simply elution of polymer off the support without reprecipitation. Certain conditions of polymer deposition on the support are required for optimal results.
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  • 51
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 587-592 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 3 Ill.
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  • 52
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 593-600 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A model is proposed to account for the regular twisting of radial ribbons in certain polymer spherulites. The model assumes that the ribbons have crystallographically regular fold surfaces and that growth of the ribbons is nucleation-controlled. The model leads directly to a possible mechanism of spherulitic growth in some polymers.
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  • 53
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A general description is given for relations among the optical quantities obtained from fluorescence polarization measurements on bulk polymer stained by fluorescent groups: the moments of distribution of orientations of the fluorescent groups, and those of the structural units of the polymer (chain segments) on which the groups are adsorbed. Two assumptions as to the biaxial symmetry of the bulk polymer and the cylindrical symmetry of the optical anisotropy of the fluorescent element, both for the absorption and emission processes, reduce the intensities of the polarized fluorescence to a 3 × 3 matrix L which is asymmetric (Lij ≠ Lji), as has frequently been observed in experiments. The components of the L matrix are related to those of the J matrix which is so defined as to describe the fourth moments of the distribution of orientations of the structural units on the basis of a random distribution of the rotational angle of the unit about the segment axis. It is found that the use of the method of fluorescence polarization combined with absorption dichroism and/or emission gives the values of the optical anisotropy ratios of the fluorescent unit, and that the effects of the thermal agitation of the structural unit can be separated from the moments of the orientation distribution for the simplest case.
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  • 54
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 743-745 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 2 Ill.
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  • 55
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 747-747 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 56
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 735-742 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It is shown that, at the yield stress, glassy polymers exhibit viscous flow which is in agreement with the generalized theory of Eyring. The study of the yield stress over a wide range of temperatures and strain rates provides evidence on the secondary transitions found by other methods. From our measurements we conclude that every secondary transition corresponds to the liberation of one of the degrees of freedom of a segment of the main chain.
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  • 57
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 747-748 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 58
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 749-749 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 59
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 753-762 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Eight epoxy-diamine networks have been formed, diamines with 2 to 12 methylene groups being used as curing agents. Dynamic mechanical tests revealed four transition regions in the dynamic loss modulus/temperature relationship. Two possible explanations for the relaxation of the glycidyl portion of the structure are proposed. One of the relaxations could be due to the breakdown of hydrogen bonds through the hydroxyl and ether groups. The second could be ascribed to the relaxation of the unbonded glycidyl groups or a second relaxation of the glycidyl groups after the breakdown of the hydrogen bonds.
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  • 60
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 763-773 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Triad tacticity data obtained by NMR analysis have previously been interpreted in terms of two basic statistical models in order to elucidate the stereospecific polymerization mechanism. In this paper the characteristics of these two basic models for stereospecific polymerization, the enantiomorphic-sites (EMS) model, and the polymer-end control (PEC) model, are examined and compared. The tacticity values accessible to the two-parameter EMS model, which includes the influence of the chain end unit, are shown to be highly restricted. Only about 20% of the isotacticity versus syndiotacticity plot is accessible to this model. To this extent the consistency of a set of triad tacticity data with the model can be tested. No such tacticity limits are exhibited by the two-parameter PEC model, which includes the influence of the penultimate unit. Any set of tacticity values which can be interpreted in terms of the two-parameter EMS model can also be interpreted in terms of the two-parameter PEC model.
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  • 61
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 783-794 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Previous theoretical calculations of elastic constants for cellulose based on force constants for bond stretching and bending of valence angles have yielded axial stiffness values admittedly too low. The present analysis accounts for a hitherto unexamined geometrical effect associated with deformation of interchain hydrogen bonds. To do this, most primary bond deformations are neglected so the resulting calculation gives an upper bound for the axial stiffness. By using two different sets of hydrogen bond force constants, values of 24.6 and 31.9 × 1011 dyne/cm2 were obtained for Young's modulus in the chain direction. These values are very much larger than earlier calculations and experimental determinations from cellulosic fibers, indicating both the importance of the effect considered here and the likelihood of an exact analysis yielding an acceptable result.
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  • 62
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 809-819 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A novel gas-flow method of measuring the diffusion, solubility, and permeability of gases and vapors in polymer films is described. The specific advantages of this system over the time-lag technique are discussed. Transport data, including activation energies and enthalpies of solutions, for hydrogen and deuterium in poly(vinyl fluoride) are presented, and the effects of the glass transition and of orientation on the observed transport rates are discussed.
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  • 63
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 795-807 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dynamic mechanical properties determined with a torsion pendulum were used to ascertain the glass transition temperature Tg of poly-ε-caprolactone. By measurements on compatible blends of poly-ε-caprolactone and poly(vinyl chloride), the Tg of amorphous poly-ε-caprolactone was shown to be 202°K at about 1 cps. This is 16°K lower than the Tg of annealed, crystalline polymer. The blend transition data were well fitted by both the Fox and the Gordon-Taylor expressions. The Fox expression was also used to describe the decrease from 233°K of the secondary low-temperature relaxation due to poly(vinyl chloride) by assuming the low temperature relaxation of poly-ε-caprolactone, 138°K, was responsible for the decrease in the blends. The 138°K relaxation due to poly-ε-caprolactone was decreased when more than 50% poly(vinyl chloride) was present.
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  • 64
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 821-827 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A specimen of linear polyethylene was subjected to isothermal secondary crystallization at a series of temperatures below the primary isothermal crystallization temperature, the melting and primary crystallization stages being held constant throughout the investigation. Dilatometric measurements exhibit an S-character at low values of undercooling Tp - Ts, where Tp and Ts are, respectively, the primary and secondary crystallization temperatures, whereas at larger undercooling, an initial very rapid crystallization is followed by a very slow stage. When corrected for thermal contraction of the polymer, the net degree of secondary transformation is seen to peak at a temperature about 5°C below Tp. The S-character of the isotherms and the peaked temperature variation of degree of transformation lead to the conclusion that a large portion of the secondary crystallization consists of the nucleation and growth of the new crystallites. Johnson-Mehl-Avrami analysis leads to a model of heterogeneous nucleation within the remaining amorphous zones, followed by one-dimensional, diffusion-controlled growth.
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  • 65
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 845-853 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The conformational energy contribution (ΔUconf) to the heat of solution in polymer-solvent systems is presented and discussed in connection with chain conformational properties. In particular, ΔUconf has been discussed in terms of various possible mechanisms of coil deformation.
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  • 66
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 829-844 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(vinyl chloride) sheet was oriented by hot drawing. The yield behavior of the oriented sheet was then investigated under uniaxial tension at room temperature as a function of the angle between the tensile axis and the molecular alignment direction. The onset of yield was localized in deformation bands. The variation of yield stress with direction and the direction in which the deformation bands formed were found to be satisfactorily accounted for in terms of a yield criterion based on that of von Mises, provided that a term representing internal compressive stress in the molecular alignment direction was included. The internal stress was found to increase from zero with increasing draw ratio of the prior hot drawing. It is pointed out that other workers have found polymers to obey the yield criterion of Coulomb rather than that of von Mises.
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  • 67
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 867-877 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: SynopsisThe diffusion of six solvents in three crosslinked, glassy epoxy polymers is studied. Case II swelling and Fickian sorption are observed as two simple limiting cases. The mechanism of diffusion changes from one limit to another as the nature of the solvent or the crosslink density of the polymer is altered. With mixed solvents, properly chosen, a superposition of Fickian diffusion and case II swelling is observed.
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  • 68
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 879-887 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The Fickian diffusion coefficient of methylene chloride in a glassy epoxy polymer is calculated with the use of Crank's model of discontinuous change of D with concentration C. The diffusion constant is obtained as 1.93 × 10-6 cm2/sec. The swollen layer behind the advancing solvent front is essentially in the rubbery state of the same polymer. The case II swelling by benzene is discussed in terms of a convective transport arising from the partial stress (internal) tensor of the penetrant. The superposition of Fickian and case II diffusion found with mixtures of methylene chloride and benzene is also discussed briefly.
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  • 69
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 983-992 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Interferometric studies have been made on cotton fibers as well as on twisted nylon filaments. The results so obtained provide strong evidence that the fibrils in the cotton fiber become less inclined to the fiber axis as one proceeds from the surface to the core. Also, studies on twisted nylon filaments by the fiber refractometer and Becke line techniques indicate that the latter, as practiced in this laboratory, does give values of refractive index which are heavily weighted towards the fiber periphery.
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  • 70
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 947-962 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Diffusion coefficients and solubilities of methane in polyisobutylene have been measured at four temperatures between 102 and 188°C. in the pressure range 23-341 atm. Diffusion coefficients extrapolated to atmospheric pressure range from 1.72 × 10-6 cm.2/sec. at 102°C. to 1.5 × 10-5 cm.2/sec. at 188°C. corresponding to an activation energy for diffusion of 8.7 ± 0.4 kcal./mole. Solubilities are small, about one molecule of methane for every forty carbon atoms in the polyisobutylene at 300 atm. partial pressure of methane. Solubilities vary little with temperature, but show an apparent minimum between 127 and 188°C. With improved methods of data analysis, diffusion coefficients and solubilities have been recalculated from previously reported studies on nitrogen in branched polyethylene and methane in branched polyethylene, linear polyethylene, and polystyrene. Recalculated diffusion coefficients are essentially the same as those reported previously, but the recalculated solubilities are decreased from 2 to 30%. The solubilities of all five systems show strong deviations from Henry's law, i.e., increases in partial pressure of methane and nitrogen with respect to solubility exceed linearity. The partial pressure (or fugacity) - solubility data may be interpreted in terms of a sorption model in which sorbed molecules are accommodated in widely dispersed, unoccupied volumes or sites in the polymer. An almost equivalent, solution model in which the first sorbed molecules to enter the polymer are accommodated to a large extent in existing volumes in the polymer, with successively sorbed molecules swelling the polymer to a greater extent (i.e., partial molal volume of sorbed molecules, V1, increasing with concentration) can also account for these data.
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  • 71
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 963-981 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The structural and steric isomerism of propylene polymers has been estimated on the basis of solution properties as well as infrared and high-resolution nuclear magnetic resonance spectra. Three general types of polypropylenes were prepared: polymers prepared with the cationic catalytic system AlCl3-C2H5Cl, stereoblock polymers obtained by successive extraction from a commercial product and isotactic polymers of low molecular weight obtained by thermal degradation of a highly isotactic polymer followed by hydrogenation with Adam's catalyst in dioxane at 40°C. The characterization of all samples was accomplished by equilibrium ultracentrifugation, vapor-pressure osmometry, viscometry, and gel-permeation chromatography. It is found that the molecular chain of cationically prepared polymer is somewhat branched owing to structural isomerism during polymerization. Isoamyl acetate is found to be a theta solvent for stereo-block as well as for atactic and syndiotactic polymers; the theta temperature is determined as the temperature at which the light-scattering second virial coefficient A2 vanishes. A close correlation is found between the theta temperature and stereoisomerism. The absorbances of the 1154 and 974 cm-1 bands in the infrared spectra decrease with decreasing molecular weight; in addition to the mere existence of alternating CH2 and CH(CH3) groups in the polymer chain, rather long sequences of this type are required for the appearance of these bands. Changes in the absorption band at 997 cm-1 show that chains consisting of over ten isotactically connected monomer units can assume a helical conformation. From the high-resolution NMR spectra of different polypropylenes, including isotactic polymers of low molecular weight, it is found that in estimating the microstructure, account must be taken of the effects of stereoisomerism within tetrads of monomer units on the apparent widths of the methylene proton resonances. If substantial concentrations of several of the possible types of tetrads are present (i.e., if the tactic sequence lengths are quite short), then it is difficult to determine the relative amounts of tactic dyads accurately from the 100 Mcps methylene proton resonances.
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  • 72
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 27-36 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Silica flocculated with a high molecular weight poly(DMVPMS) contains aggregates that are stable enough to permit size measurement with a Coulter counter. The average size of these aggregates increases up to a critical level of added polymer; the primary particles reappear at higher levels of added polymer. The aggregate size is reduced by continued mixing and the particle size distribution before flocculation is approached. Subsidence rates, equilibrium sediment volumes, and refiltration rates give somewhat different estimates of the degree of flocculation. Additional aggregation beyond that measured by the Coulter counter must be considered in the interpretation of these data. The decrease in floc strength during continued agitation is attributed to a disaggregation of the bridging polymer, to a decrease in the interparticle bonding of the bridging polymer, and to an increase in the surface coverage with polymer.
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  • 73
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Results from characterization of melt-polymerized nylon 66 by various solution property measurements are reported and employed in analysis of typical molecular weight and compositional distributions for these systems. Critical attention is paid to application of standard procedures including light scattering, viscosity, membrane osmometry and other colligative property measurements in arriving at satisfactory specification of polymer molecular weight averages. Particular consideration is given to polymers extending appreciably beyond the lower and higher limits in molecular weight normally encountered. The conclusions drawn are: (1) in the range of number-average molecular weights less than about 25 000, nylon 66 as ordinarily prepared by melt condensation consists principally of linear species approximating the “most probable” distribution; (2) small amounts of cyclic oligomers are present in all samples: (3) increase in the extent of the melt polycondensation to progressively higher stages is accompanied by secondary reactions and the formation of branched components terminating ultimately in crosslinked, insoluble gels. Intrinsic viscosity-molecular weight relationships in seven solvents, applicable to nylon polymers meeting the requirements of (1) above, are derived.
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  • 74
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 37-45 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The well known procedure of determining the degree of crystallinity by means of measuring the density presupposes the knowledge of both the densities ρc and ρa of the crystalline and of the noncrystalline regions. By combination of small-angle and wide-angle x-ray scattering and of density measurements it can be shown that this method is not justified in the case of drawn polyethylene if the values of ρc and ρa known from isotropic material are used. Both ρc and ρa depend considerably on annealing and drawing conditions. In addition the effective density ρc* of the more densely packed phase in a two-phase structure is much lower than the value ρc calculated from the positions of the x-ray reflections due to a large number of lattice defects. This conclusion is based on the results of three independent sets of experiments: determination of the mean-square fluctuation of density 〈η2〉 by means of x-ray small-angle scattering; x-ray wide-angle measurements of the positions of the crystal reflections and of the halo arising from the noncrystalline regions; and comparison of densities and long periods of samples treated at various annealing temperatures.
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  • 75
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 57-76 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: For an infinitely repeated regular polymer chain structure the only vibrations which are optically active are those in which the phase of the motion is the same in each unit (the factor-group modes). Frequencies for which the phase difference is nonzero are optically inactive but can become activated by the presence of defects in the chain. Such defects would normally be chemical impurities or conformational irregularities in the chain. A simple theory is developed which shows that for a dilute system of defects the major characteristics determining possible activation of the nonfactor-group modes are: (1) the strength of the coupling between the defect vibration and the vibrations of the neighboring chain, and (2) whether or not the natural frequency of the defect vibration lies inside a lattice band of the regular chain. An analysis of the low- and high-frequency regions of the spectrum of low-density polyethylene, based on the above considerations, indicates that several features of the spectrum can be associated with defect-induced absorption. A similar explanation can account for certain intensity changes in the C—Cl stretching region of syndiotactic poly(vinyl chloroide) when this polymer is submitted to mechanical treatment.
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  • 76
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 105-111 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Heterogeneous nucleation and crystallization of FEP Teflon and nylon 6 melts against high energy surfaces (i.e., gold) produce an interfacial region, in these polymers, of high mechanical strength. Dissolution of the metal substrate rather than removal by mechanical means results in a polymer surface which is amenable to conventional structural adhesive bonding. Nucleation and crystallization of the polymer melts in contact with phases of low surface energy (e.g., vapor) result in the generation of weak boundary layers.
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  • 77
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 123-142 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Isothermal and nonisothermal spherulitic crystallization in even-odd and poly(ω-aminocarboxylic acids) has been studied for a range of fusion conditions and solidification temperatures. The variety of spherulites so formed are classified mainly by optical microscopy. It is found that polyamides with similar types of repeat units generally exhibit similar morphological features under corresponding crystallization conditions. The basic patterns are illustrated in the text. Changes in spherulitic birefringence with temperature are also discussed. In some cases, at temperatures not far below the polymer melting point, platelet-like crystalline aggregates are formed in thin film preparations. These platelets exhibit properties characteristic of single crystals.
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  • 78
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 153-161 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The morphology of polyethylenes formed upon polymerization by γ-radiation below the melting point in various reaction media was investigated by using electron microscopy and scanning electron microscopy. When the polymerization was carried out in bulk at 30°C and in methanol, the polymer was fibrillar, and a small-angle x-ray scattering curve of the polymer did not indicate the existence of a long period. This suggests that the chains in the crystals have an extended conformation. When the polymerization was carried out in the presence of xylene at 30°C, platelet crystals having a folded structure were obtained. It was thus shown that the morphology of the growing polymer crystals is very much affected by the solubility of the polymer in the reaction medium. The effect of stirring during polymerization on the crystalline morphology was also studied.
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  • 79
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 171-182 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: To clarify the deformation mechanism in polyblends of polypropylene with ethylene-propylene rubber having different compositions, simultaneous measurements of the infrared dichroism with stress and strain under a constant rate of strain of 1.64%/min have been carried out. The orientation function of the crystallographic c axis of polypropylene in the blends has been obtained as a function of strain ranging from 0 to 20% and of polypropylene content ranging from 0.3 to 1.0. These results have been compared with the temperature dependences of the dynamic Young's modulus and of the loss modulus, as well as of stress-strain curves for the same blends. The modulus data analyzed by Kerner's equation reveal the occurrence of phase inversion at polypropylene contents higher than about 0.5, and this is supported by the infrared dichroism data. The strong effect of quenching on crystalline structure and mechanical properties of pure polypropylene has also been elucidated.
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  • 80
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 209-217 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The intrinsic viscosity of a polymer in a solvent mixture is related to the excess free energy of the solvents. Intrinsic viscosities at different temperatures are obtained for poly-2-vinylpyridine-chloroform-ethyl alcohol, poly(methyl methacrylate)-chloroform-ethyl alcohol, polystyrene-cyclohexane-benzene, polystyrene-dioxane-chloroform, and polystyrene-cyclohexane-ethanol. Qualitative, but not quantitative, agreement is found between theory and experiment.
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  • 81
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 201-208 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polymer crystals are characterized by strong anisotropy of binding forces among units, i.e., the intrachain force constant f is much larger than the interchain force constant g. The anisotropic lattice is reduced to an isotropic one, in which each lattice point represents N* units (segment) along the chain axis of the anisotropic lattice [N = 2(f/g)1/2]. Vibrational modes of the reduced lattice correspond to interchain modes of the original lattice, i.e., modes whose frequencies are governed by interchain potential. Anharmonicity of crystalline force field is assumed to be related predominantly with interchain force alone. Thermodynamic and transport equations for a simple lattice are applied to the reduced, isotropic lattice, and numerical results are obtained for high-density polyethylene. The Grüneisen constant γ was obtained from the pressure dependence of sound velocity. The heat capacity of the reduced lattice, Cinter (interchain specific heat), was calculated from Grüneisen's equation, α = γβCinter (where α = thermal expansion coefficient, β = compressibility), and the mass of a segment m* was estimated from Dulong-Petit's equation, Cinter = 3ρk/m* (where ρ = density, k = Boltzmann constant). The value of m* is consistent with N* from force constants, m* = N*m (where m = mass of a unit in the original lattice). m*θ3 (where θ denotes the Debye temperature of the reduced lattice) is calculated from low temperature specific heat. The value of m* calculated from m*θ3 and θ from other sources agrees with that from the estimate by Dulong-Petit's equation. The high-temperature thermal conductivity K was calculated through Leibfried-Schloemann's equation by employing γ and m*θ3 as estimated as described above; satisfactory agreement was obtained with experiment. Poly(methyl methacrylate) and polystyrene were also studied by similar methods.
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  • 82
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The mechanical anisotropy of regenerated cellulose films is investigated, first, on the basis of the theory of infinitesimal elasticity. Fairly good agreement of calculated with observed results is obtained on the basis of orthogonal anisotropy with respect to the machine direction and the transverse and thickness directions of the films. The shear modulus G23 along the film plane and the Poisson ratio v32 are 1.5 times; 102 kg/mm2 and about 0.4, respectively, in the standard dry state. Second, the mechanical anisotropy in three different dry states is analyzed in terms of the degree of biaxial orientation of two kinds of structural units, cellulose II crystallites and noncrystalline chain segments, and their mechanical anisotropy. The calculation for averaging the mechanical anisotropies of these structural units on the basis of the homogeneous strain hypothesis gives results much higher than the experimental data, whereas the calculation on the basis on the homogeneous stress hypothesis gives results rather lower than experiment. As a modification of the two extreme calculations, a different averaging gives considerably better agreement between the calculated and observed results. The mechanical anisotropy in the wet state is further analyzed primarily in terms of the degree of biaxial orientation of noncrystalline chains by a modification of Krigbaum treatment, based on application of the kinetic theory of entropy elasticity for semicrystalline polymers, to anisotropic systems. The calculation gives results, however, much lower than those obtained experimentally, unless the ratio of the end-to-end distance of the noncrystalline chain to its fully stretched length is taken as unusually large. This may be due to underestimation of the contribution of the crystalline phase to terms of the same type as appear in the Krigbaum treatment.
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  • 83
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1755-1760 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Rates of crystallization of polyethylene fractions have been studied at high undercoolings by differential calorimetry to demonstrate the utility of this technique for fast crystallization analysis. It has been shown that there is continuity in the crystallization kinetics from low to high undercoolings. On the other hand, the influence of molecular weight on the crystallization rates, as the undercooling increases, is very moderate, as would be expected.
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  • 84
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1405-1414 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Molecular motions in poly(vinylidene fluoride) were studied by the dielectric technique. Three distinct absorption peaks (αc, αa, and β) were observed in the frequency range from 0.1 cps to 300 kcps and in the temperature range from -66 to 100°C. The molecular mechanisms for these absorptions and their temperature dependence are discussed, and results are compared with x-ray diffraction and the NMR measurements. It is concluded that the αc absorption located at 97°C (1 kcps) is related to molecular motion in the crystalline region. The αa absorption located at -27°C (1 kcps) can be interpreted as due to the micro-Brownian motion of the amorphous main chains. The β absorption located at -47°C (1 kcps) is attributed to local oscillation of the frozen main chains.
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  • 85
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1435-1438 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 2 Ill.
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  • 86
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A new light-scattering experiment which allows a direct determination of the conformation of macromolecules deformed in flow is described. Light-scattering relationships based on the interference function are developed, and results of an experimental study are detailed. The deformed conformation of high molecular weight polyisobutylene was determined in a Couette-type shear field. Decalin was the solvent. Variables investigated were the shear rate (0 to 600 sec-1), the polymer molecular weight (1.0 × 107 to 1.6 × 107), and the polymer concentration (2.0 × 10-4 to 8.0 × 10-4 g/cc). Conformation variables determined were the orientation of the molecule in the shear field and its maximum and minimum extension ratios in the plane defined by the direction of flow and the direction of the shear rate. The deformation of the macromolecule was found to be markedly discrepant when compared to the dynamic macromolecular models which assume complete coil flexibility, and more closely in agreement with the recent theories of Cerf, developed for nonfree-draining coils which exhibit a finite internal viscosity.
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  • 87
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1439-1443 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 4 Ill.
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  • 88
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1444-1449 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 3 Ill.
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  • 89
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1461-1472 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Thermal analysis has been carried out on drawn nylon 6 filaments annealed at various temperatures between 150 and 210°C and then methoxymethylated to various degrees. It is shown that the melting point inherent to the morphology of drawn nylon 6 can be obtained from samples in which the reorganization of defect crystallites in the course of thermal analysis is prevented by a proper degree of methoxymethylation of amorphous regions. The melting point thus obtained is in linear relation with the reciprocal crystallite size in the direction of fiber axis which has been obtained from small-angle x-ray data and crystallinity. The extrapolation and the slope of this linear relation give the equilibrium melting point of nylon 6 as 245°C and an end-surface free energy of 42 erg/cm2. The results seem to provide strong support for the presence of chain-fold surfaces in the drawn and annealed polymers.
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  • 90
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 2061-2072 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Extended-chain crystals of high molecular weight polymethylene, a polyethylene with a broad molecular weight distribution, and three fractions of polyethylene were grown from the melt under elevated pressure. Comparison of the crystal size distribution in the molecular chain direction (measured on fracture surfaces by electron microscopy) with the molecular weight distribution (measured by gel-permeation chromatography) gave the following results. Up to molecular weight 10,000 all samples showed eutectic separation into fully extended chain crystals of narrow molecular weight distribution. Above molecular weight 10,000 mixed crystals were formed. Under the chosen crystallization conditions larger chain extension was achieved with higher molecular weights. However, an increase in molecular weight by a factor of 1000 led only to a tenfold increase in chain extension. These facts are discussed in the light of a proposed mechanism of crystal growth.
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  • 91
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1111-1115 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 2 Ill.
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  • 92
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1119-1121 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 1 Tab.
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  • 93
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1116-1118 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 94
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1123-1150 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Stress, strain, and birefringence measurements have been carried out on swollen and unswollen networks of ′cis-1,4-polybutadiene polymers. Neither stress-strain nor birefringence-strain relations of unswollen specimens obey the Gaussian network theory, but both can be fitted by the Mooney-Rivlin equation. On the contrary, data on specimens swollen in tetralin, decalin, benzene, and carbon tetrachloride strictly obey the Gaussian network theory. Existing methods for evaluating the temperature coefficient of the unperturbed dimensions, d In 〈r2〉/dT, from the stress-temperature relation are applied to the present data and discussed in some detail. It is concluded that reliable values of d In 〈r2〉/dT are not obtainable from data on unswollen samples because of the pronounced non-Gaussian effect. The value 7.5 Å3 for the optical anisotropy Å3 (an alternative to the stress-optical coefficient) for unswollen specimens is markedly larger than values (5.8 Å3 on the average) for swollen specimens. This is interpreted as due to the shortrange orientational order among polymer segments. The quantities 〈r2〉, ΔΓ, and their temperature coefficients are calculated for both cis-1,4-polybutadiene and cis-1,4-polyisoprene chains, on the basis of the rotational isomeric state approximation for bond rotations. Values of ΔΓ for cis-1,4-polybutadiene calculated using Clément and Bothorel's set of anisotropic bond polarizabilities are in good agreement with observed values for swollen specimens. Those for cis-1,4-polyisoprene obtained using the same set of anisotropic bond polarizabilities are somewhat smaller than observed values for unswollen specimens. This departure is in the direction expected from the behavior of ΔΓ upon swelling (i.e., a decrease in ΔΓ upon swelling).
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  • 95
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1151-1163 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The strength-limiting process in the fracture of semicrystalline fibers and highly oriented films is the rupture of tie molecules connecting the folded chain lamellae in the machine direction. This view is supported by the data on stress and temperature dependence of lifetime of fibers under load and on radical formation during the fracture experiment. The observed tensile strength, however, is about 10 times smaller and the number of fractured chains between 100 and 1000 times larger than expected on the basis of the known number of tie molecules in the fracture plane. This discrepancy is a consequence of the inhomogeneity of the micromorphology of fiber structure, which causes a much larger stress concentration on the most unfavorably located tie molecules than the average value one would expect in the case of perfectly uniform stress distribution on identical tie molecules. The fluctuation of amorphous layer thickness, of number and length of tie molecules, produces such a high stress concentration on some tie molecules throughout the sample that they rupture long before the average stress concentration is sufficient for chain fracture. By accumulation of damage caused by gradual chain rupture the weakening of the sample locally proceeds so far that at the maximum damage concentration, microcracks start to form, and the fiber breaks.
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  • 96
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1165-1186 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The proton spin-lattice relaxation times (T1) of linear polyethylenes (PE) of varying morphology were measured as a function of temperature. The T1 of oriented bulkcrystallized and solution-crystallized material was isotropic, in disagreement with calculations based on a sample dipole pair model. Motion in the non-crystalline regions of the samples is shown to be responsible for the T1 minimum occurring around -20°C. The dependence of T1 at the minimum on the long period reinforces the model of an amorphous fraction composed of disordered lamellar surface layers. The temperature of the T1 minimum and the dependence of T1 on the long period imply that the mobility of these amorphous regions is reduced in cold-drawn and solution-crystallized samples. This mobility irreversibly increases with annealing. In highly relaxed samples the motion of a small portion of the disordered regions is almost liquidlike, as indicated by the presence of a second shorter T1.
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  • 97
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1187-1195 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Extensive studies of the kinetics of spherulitic crystallization have been made on fractionated samples of TMPS. An analysis of these results reveals that a two-dimensional growth rate mechanism is a more likely mode of growth than a three-dimensional one. This conclusion is substantiated by experimental evidence from optical microscopy and light scattering from within spherulites. The crystallite end surface energy is found to increase as the molecular weight is raised.
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  • 98
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1627-1638 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A new type of long-range interaction between chain segments and solvent molecules in a polymer molecule is introduced. It can be depicted as an “interfacial” free energy, due to the more or less diffuse interface between the interior of a polymer coil and the surrounding solvent. Flory's calculation of the coil expansion α is extended for this effect, by using theoretical approaches developed by van der Waals, Cahn and Hilliard, and Debye for inhomogeneous systems (interfaces). It is found that Flory's equation for α is replaced by: \documentclass{article}\pagestyle{empty}\begin{document}$ \alpha ^5 - \alpha ^3 = 2C_M \psi _1 M^{1/2} \left[ {1 - \left( {\theta /T} \right) + \left( {15/2\alpha ^2 } \right)\left( {\theta /T} \right)\left( {l^2 /\overline {r_0^2 } } \right)} \right] $\end{document} where the last term is due to the “interfacial” free-energy correction. The Debye molecular interaction length l is also found in theories on light scattering of binary mixtures near the critical solution temperature. An important result of this equation is that at T = θ, α is not equal to unity, as before, but somewhat larger, depending on the molar mass of the polymer and the solvent type. A calculation shows that the “interfacial” free energy correction may contribute substantially to the “solvent” effects on the expansion of a polymer molecule at the θ temperature, as has recently been reported in the literature.
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  • 99
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1651-1667 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The plastic deformation of poly-4-methylpentene-1 (P4MP1) crystals on a unidirectionally drawn substrate has been investigated by electron microscopy. In addition to cracks spanned by fibrils and buckling perpendicular to the stretch direction, both features found in deformation studies of other polymers, a unique slip mechanism leading to sectorization of P4MP1 crystals is observed; deformation was also found to occur by means of localized lamellar thinning. The exact type of plastic deformation occurring in P4MP1 crystals is found to depend on the orientation of the lamellae with respect to the tensile axis. Some evidence for a periodicity on the fibrils studied is given.
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  • 100
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1669-1679 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A method for evaluating the relaxation time as a function of both temperature and volume from volume contraction experiments, as proposed by Kovacs, was experimentally examined by using monodisperse poly-α-methylstyrene samples of various molecular weights and blends. It was concluded that his theory can be successfully applied to the present experimental data, though his two different approximations give somewhat different values of the shift factor for the time-temperature superposition of volume contraction data. A difference was observed between the temperature dependence of the shift factor of monodisperse polymers and that of blends.
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