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  • 1985-1989
  • 1970-1974
  • 1965-1969  (1,652)
  • 1967  (1,652)
  • Polymer and Materials Science  (1,642)
  • Pancreas  (10)
Material
Years
  • 1985-1989
  • 1970-1974
  • 1965-1969  (1,652)
Year
  • 1
    ISSN: 1432-0428
    Keywords: Spontaneous diabetes ; Chinese hamster ; Cricetulus griseus ; Ultrastructure ; Pancreas ; Beta cells ; Islets ; Alpha cells ; Nerve endings in pancreas ; Glycogen ; Basement membrane ; Capillaries
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé Nous avons examiné au microscope électronique les îlots de Langerhans de 15 hamsters chinois dont 7 étaient diabétiques et 8 étaient non-diabétiques, provenant soit des mêmes nichées, soit sans lien de parenté, mais concordant quant au sexe et à l'âge. Chez les animaux de contrôle, les cellulesβ prédominent et sont riches en granules, formés de vésicules de différentes tailles avec un contenu légèrement granulaire ou homogène. Dans de rares vésicules, on observe un noyau dense ou une barre centrale irrégulière et dense. Les granulations des cellulesα sont uniformément rondes, très denses et limitées par des membranes; elles sont assez clairsemées à l'exception de la périphérie des îlots. Au début du diabète, les cellulesβ sont abondantes mais, soit dégranulées, soit en voie d'infiltration glycogénique. Plus tardivement dans la maladie, les îlots ne contiennent presque que des cellulesα, les cellulesβ ayant graduellement disparu.
    Abstract: Zusammenfassung Die Langerhans'schen Inseln von 15 chinesischen Hamstern (7 diabetischen und 8 entweder verwandten oder nicht verwandten Kontrolltieren gleichen Geschlechts und Alters) wurden elektronenmikroskopisch untersucht. In den Kontrolltieren überwiegen dieβ-Zellen die reich an Granula sind. Die meisten davon sind Bläschen verschiedener Größe mit einem blassen, körnigen oder homogenen Inhalt. Nur einige weisen einen dichten zentralen Kern auf oder einen unregelmäßigen dichten zentralgelegenen Stab. Dieα-Zellen haben einheitlich runde und dichte, durch eine Membrane begrenzte Granula und sind spärlich verteilt, außer an der Peripherie der Inseln. Im frühen Diabetes mellitus sind dieβ-Zellen in großer Zahl vorhanden aber erscheinen entweder degranuliert oder in verschiedenen Phasen der Glykogenablagerung. In späteren Stadien der Krankheit, als Folge des allmählichen Verschwindens derβ-Zellen, bestehen die Inseln fast nur noch ausα-Zellen.
    Notes: Summary Islets of Langerhans of 15 Chinese hamsters (7 diabetic and 8 either related or unrelated controls of the same sex and age) have been examined by electron microscopy. Beta cells of control animals predominate and have abundant granules most of which are vesicles of varying sizes with a pale granular or homogeneous content. Only a few have a dense central core or irregular dense central bar. Alpha cells have uniformly round, dense, membrane-limited granules and are sparse except at the periphery of the islet. Early in diabetes mellitus beta cells are abundant but either agranular or in various stages of glycogen storage. Late in the disease the islets are reduced to almost all alpha cells, the beta cells having gradually disappeared.
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  • 2
    ISSN: 1432-0428
    Keywords: Spontaneous Diabetes ; Chinese hamster ; Cricetulus griseus ; Islet volume ; Beta cell volume ; Pancreas ; Beta cells ; Prediabetes ; Preclinical diabetes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé Nous avons étudié 3 groupes de hamsters chinois de la colonie des laboratoires Upjohn, soit (1) des animaux diabétiques ayant présenté des symptômes pendant 18 mois; (2) des animaux non-diabétiques des mêmes nichées; et (3) des animaux non-diabétiques et non-apparentés mais concordant par l'âge et le sexe. Le diabète spontané de ces animaux est caractérisé par une hyperglycémie, une glucosurie, une diminution du volume des îlots de Langerhans, une diminution du volume total des cellulesβ, une dégranulation des cellulesβ et l'infiltration en glycogène des îlots de Langerhans. Des anomalies de même type, mais moins marquées ont été observées chez les frères et soeurs des animaux diabétiques. A notre connaissance, c'est là la première description de la diminution de la masse des cellulesβ et de leur dégranulation avant l'apparition clinique d'un diabète spontané chez l'homme ou l'animal. Il en ressortirait que cette altération des cellulesβ pourrait bien être un mécanisme étiologique primaire de la pathogénèse du diabète spontané du hamster chinois.
    Abstract: Zusammenfassung Drei Gruppen von chinesischen Hamstern aus der Upjohn-Zucht wurden untersucht. Dazu gehörten: diabetische Tiere, die seit 18 Monaten Symptome aufwiesen, nichtdiabetische Tiere aus gleichem Wurf und nichtverwandte nichtdiabetische Tiere, die in Alter und Geschlecht den anderen entsprachen. Der Spontandiabetes zeichnet sich aus durch Hyperglykämie, Glykosurie, Abnahme des Inselvolumens, Verminderung derβ-Zellmasse, Degranulierung derβ-Zellen und Glykogeninfiltration der Inseln. In den nichtdiabetischen Geschwistertieren wurden ähnliche aber weniger markante Veränderungen festgestellt. Unseres Wissens ist dies der erste Bericht einer Verringerung derβ-Zellmasse mit Degranulierung noch ehe sich ein Spontandiabetes bei Mensch oder Tier manifestiert. Dies deutet darauf daß diese Veränderungen derβ-Zellen einen primären etiologischen Faktor bei der Entstehung des Spontandiabetes beim chinesischen Hamster darstellen könnten.
    Notes: Summary Three groups of Chinese hamsters bred at the Upjohn Laboratory were studied: these included diabetic animals in which symptoms were present for 18 months, non-diabetic siblings and non-related, non-diabetic animals of the corresponding age and sex. The spontaneous diabetes is characterized by hyperglycemia, glycosuria, decreased islet volume, decreased beta cell mass, beta cell degranulation and glycogen infiltration in the islets. In the non-diabetic siblings, similar but less marked changes were noted. To our knowledge this is the first reported observation of decreased beta cell mass and beta cell degranulation occurring prior to clinical onset of spontaneous diabetes in man or animal. It suggests that the observed alteration of beta cells is a primary etiologic mechanism in the production of spontaneous diabetes in the Chinese hamster.
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  • 3
    ISSN: 1432-0428
    Keywords: Spontaneous diabetes ; Sand rat ; Psammomys obesus ; Insulin in plasma ; Insulin resistance ; Acetohexamide ; Diet and diabetes ; Nutrition and diabetes ; Obesity ; Pancreas ; Infections ; Adipose tissue in vitro
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé Certaines caractéristiques particulières du rat des sables en font un animal d'expérience de grande valeur. L'augmentation des taux plasmatiques d'insuline et de glucose est liée chez lui à une augmentation de la prise de nourriture. Tout comme c'est le cas pour le diabète humain de type adulte, il semble y avoir participation d'un élément de résistance à l'insuline qui peut être mis en évidencein vitro par la sensibilité diminuée du tissu adipeux du rat des sables à l'insuline de porc. Il semblerait qu'un traitement prophylactique par l'acétphexamide exerce un effet protecteur contre l'effet diabétogène d'un régime riche en calories. — Il semble raisonnable de penser que le syndrome diabétique du rat du sable, si facilement provoqué par la modification du régime, pourrait s'avérer être un instrument de grande valeur dans l'étude des mécanismes pathogénétiques possibles du syndrome diabétique.
    Abstract: Zusammenfassung Die Sandratte verfügt über mehrere einmalige Eigenschaften, die aus ihr ein wertvolles Laboratoriumstier machen. Das häufige Auftreten von erhöhtem Plasma-Insulinspiegel und Hyperglykämie steht im Zusammenhang mit einer gesteigerten Nahrungsaufnahme. Wie im menschlichen Reife-Diabetes scheint auch hier eine Insulinresistenz aufzutreten, und diese istin vitro nachweisbar: das inkubierte Fettgewebe der Sandratte spricht auf eine Stimulierung mit steigenden Dosen von Schweineinsulin nur wenig an. Prophylaktische Behandlung mit Acetohexamid deutet auf eine Schutzwirkung gegen die diabetogenen Folgen einer kalorienreichen Diät. — Es ist zu erwarten, daß das diabetische Syndrom in der Sandratte, das so leicht durch Manipulationen der Diät erzeugt werden kann, ein nützliches Modell zur Untersuchung der möglichen Mechanismen der diabetischen Pathogenese darstellen wird.
    Notes: Summary The sand rat has some unique attributes, which make it a valuable experimental animal. The occurrence of increased plasma insulin levels and of hyperglycemia is linked to an increased food intake. As in the human maturity-onset type diabetes, there seems to be an element of insulin resistance, and this can be demonstratedin vitro by the relative unresponsiveness of sand rat adipose tissue to increasing doses of pork insulin. Prophylactic treatment with acetohexamide seems to have some protective effect against the diabetogenic results of a high calory diet. — It is expected that the diabetic syndrome in sand rats, which can be so easily induced by dietary manipulation, will be a valuable tool in helping to clarify some of the possible mechanisms in the syndrome of diabetes mellitus.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Diabetologia 3 (1967), S. 143-166 
    ISSN: 1432-0428
    Keywords: Spontaneous Diabetes ; Sand rat ; Psammomys obesus ; Pancreas ; Ultrastructure ; Beta cells ; Alpha cells ; Protein synthesis ; Insulin in plasma ; Insulin in pancreas ; Obesity ; Nutrition and diabetes ; Diet and diabetes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé Nous avons étudié avec les microscopes optique et électronique les îlots de Langerhans du pancréas de rats des sables normaux et diabétiques. Lorsqu'ils sont maintenus à un régime normal de laboratoire, on observe chez ces animaux une dégranulation des cellulesβ et les signes d'une synthèse protéique augmentée. Dès qu'apparaît le diabète, on voit apparaître une infiltration glycogénique avec déplacement des organelles cellulaires et, plus tard, une dégénérescence cyptoplasmique avec liquéfaction. L'apparition de ces anomalies morphologiques a été mise en corrélation avec les altérations du glucose sanguin et de l'insuline immunoréactive sérique. Ce qui est remarquable chez le rat des sables, c'est qu'il ne semble pas être à même de s'adapter à l'apport calorique plus concentré de la nourriture de laboratoire. Il réagit par une surproduction insulinique, surproduction qui, en général, évite la cétose. Parfois, cette surproduction suffit à ramener le sucre sanguin à la normale. Dans des cas plus rares, la stimulation de la sécrétion insulinique se termine par une dégénérescence et une nécrose des cellulesβ avec céto-acidose mortelle.
    Abstract: Zusammenfassung Es wird über elektronen- und lichtmikroskopische Untersuchungen an Pankreas-Inseln normaler und diabetischer Sandratten berichtet. Nach Verabreichung einer synthetischen Keks-Diät wurden eine Degranulation derβ-Zellen und Zeichen einer vermehrten Proteinsynthese beobachtet. Gleichzeitig mit dem Auftreten von Diabetes erfolgte Glykogeninfiltration, begleitet von einer Verdrängung der Zellorganellen und gelegentlicher Degeneration und Verflüssigung des Cytoplasmas. Diese Veränderungen wurden mit Blutzucker-und immunreaktivem Serum-Insulinspiegel in Zusammenhang gebracht. — Sandratten sind einzigartig in der Hinsicht, daß sie nicht in der Lage sind, das vermehrte Kalorienangebot der synthetischen Diät auf normale Art zu bewältigen. Sie reagieren mit Mehrproduktion von Insulin. Die gesteigerte Insulmausschüttung hält das Tier gewöhnlich frei von Ketose, bringt den Blutzucker gelegentlich auf normale Werte zurück, endet aber in seltenen Fällen mit einer Degeneration und Nekrose derβ-Zellen mit anschließender fataler Ketoacidose.
    Notes: Summary Ultrastuctural and light microscopic studies of pancreatic islets in normal and diabetic sand rats are reported. Following the institution of a synthetic chow diet, beta cell degranulation and enhanced protein synthesis were observed. With the appearance of diabetes, glycogen infiltration occurred, with displacement of cellular organelles and eventual cytoplasmic degeneration and liquefaction. These alterations were correlated with blood glucose and serum immunoreactive insulin levels. — The sand rats are unique in that they are not able to cope with the increased caloric load of synthetic chow. They respond by marked insulin production; an increase that usually maintains the animal free of ketosis, occasionally returns them to a euglycemic state, and may rarely be terminated by beta cell degeneration and necrosis with fatal ketoacidosis.
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    Diabetologia 3 (1967), S. 212-221 
    ISSN: 1432-0428
    Keywords: Spontaneous Diabetes ; KK mice ; Japanese mice ; Obesity ; Growth hormone ; Pituitary ; Islets of Langerhans ; Pancreas ; Ultrastructure ; Beta cells ; Insulin in pancreas ; Sex and diabetes ; Adrenal cortex ; Zinc
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé 1. Un état diabétique est démontré chez des souris d'une souche japonaise, la souche KK, mis en évidence par une élévation du sucre sanguin et par une diminution de la tolérance au glucose. 2. Le poids corporel des souris KK dépasse la normale; il s'agit d'une obésité modérée. 3. L'activité insulinique du pancréas et le contenu en hormone de croissance de l'hypophyse de souris KK dépassent ceux observés chez des souris C57BL. 4. Histologiquement, on trouve chez les souris KK une hypertrophie et une hyperplasie des îlots de Langerhans, une hypertrophie et une dégranulation des cellules B, une abondance de ribosomes et de réticulum endoplasmique des cellules B, un développement marqué de la région de Golgi des mêmes cellules, et une diminution du contenu en zinc des cellules insulaires. D'autres anomalies ont également été observées dans d'autres organes des souris KK, plus particulièrement pour l'hypophyse, le foie, les surrénales et la parathyroïde.
    Abstract: Zusammenfassung 1. Bei Mäusen des KK-Stammes (japanische Zucht) ist mit Bestimmung von Glucosetoleranz und Blutzuckerwerten ein diabetischer Zustand nachweisbar. 2. Das Körpergewicht von KK-Mäusen liegt über der Norm, und es besteht eine leichte Fettsucht. 3. Die Insulinaktivität des Pankreas und der Gehalt der Hypophyse an Wachstumshormon sind bei KK-Mäusen höher als bei C57BL-Mäusen. 4. Das Pankreas der KK-Mäuse zeigt auffallende Veränderungen, wie Hypertrophie und Degranulierung derβ-Zellen, reichlich Ribosomen und endoplasmatisches Reticulum in denβ-Zellen, sowie starke Ausbildung des Golgiapparates und Verminderung des Zinkgehaltes der Inselzellen. 5. Auch andere Organe (z.B. Adenohypophyse, Leber, Nebenniere und Nebenschilddrüse) der KK-Mäuse weisen Veränderungen auf.
    Notes: Summary This review demonstrates the following points:1. By glucose tolerance test and the determination of non-fasting blood sugar values, mice of KK strain (a Japanese strain) have been shown to be in a diabetic state. 2. KK mice have greater than normal body weights, and moderate obesity. 3. Pancreatic insulin activity and adenohypophyseal growth hormone content of KK mice are greater than those of C75BL mice. 4. The pancreas of KK mice presents many striking changes, such as the hypertrophy and hyperplasia of the islets, the hypertrophy and degranulation of B cells, the abundance of B cell ribosomes and endoplasmic reticulum, the enlargement of the Golgi areas of B cells, and the diminution of the zinc content of insular cells. 5. In other organs (eg. adenohypophysis, liver, adrenal and parathyroid) of KK mice, many changes are also observed. The above features of KK mice are discussed in relation to the presumed metabolic disorder in the mice.
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  • 6
    Electronic Resource
    Electronic Resource
    Springer
    Diabetologia 3 (1967), S. 249-265 
    ISSN: 1432-0428
    Keywords: Spontaneous Diabetes ; Dog ; Cat ; Diabetes in dogs and cats ; Pancreas ; Islets of Langerhans ; B cells ; Insulitis ; Hyalin ; Capillaries ; Kidney ; Retina ; Microaneurysms ; Pituitary
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé Les auteurs présentent une étude histopathologique de 30 chiens et de 5 chats spontanément diabétiques. — Les îlots de Langerhans et les cellules B étaient fortement diminués en nombre chez la grande majorité des chiens. Les cellules B étaient souvent dégranulées et hydropiques. Chez les chiens dont le diabète avait évolué pendant longtemps, les îlots étaient très rares et les cellules B absentes. — Chez les 5 chats spontanément diabétiques par contre, les îlots et les cellules B étaient nombreuses. Les cellules B étaient dégranulées et hydropiques chez 4 chats. Chez 1 des chats, les cellules B paraissaient normales. De nombreux îlots présentaient des dépôts de substance hyaline dans le stroma. Chez un chat, il existait une infiltration lymphocytaire très dense dans un îlot. — Ni chez les chiens, ni chez les chats, il n'a été vu de lésions glomérulaires identiques à celles de glomérulosclérose diabétique humaine. Les lésions les plus fréquentes consistaient en un épaississement des axes membraneux des touffes glomérulaires et une hypertrophie de la paroi des artérioles afférentes.— Dans les rétines des chiens diabétiques il existait une acellularité focale ou généralisée de la paroi des capillaires. Un petit nombre de microanévrysmes ont été trouvés chez 3 chiens diabétiques. L'incidence plus faible des lésions de rétinopathie vasculaire, comparativement aux diabétiques humains, s'explique probablement par la durée de vie plus courte du chien et du chat. Il est possible aussi que les capillaires rétiniens de ces animaux soient moins susceptibles de développer des lésions dégénératives. — Un degré marqué de stéatose hépatique a été observé chez beaucoup de chiens et de chats. Les surrénales étaient souvent hypertrophiées et contenaient des adénomes, mais ces lésions ne paraissent pas différentes de celles que l'on peut trouver chez des chiens et des chats non diabétiques de même âge. L'hypophyse a été prélevée chez 7 chiens. Dans 2 cas, elle contenait un adénome. Une étude cytologique plus complète des hypophyses sera publiée ultérieurement.
    Abstract: Zusammenfassung Die Autoren berichten über die Ergebnisse von Untersuchungen an 30 spontan-diabetischen Hunden und 5 spontan-diabetischen Katzen. Bei der großen Mehrzahl der diabetischen Hunde war die Zahl der Langerhansschen Inseln und der B-Zellen stark herabgesetzt. Die B-Zellen waren oft degranuliert und hydropisch. Bei Hunden mit schon lang anhaltender Krankheit waren die Inseln nur noch vereinzelt und B-Zellen überhaupt nicht mehr nachweisbar. — Im Gegensatz zu diesen Ergebnissen fanden sich bei allen 5 Katzen zahlreiche Inseln und B-Zellen. Bei 4 dieser Katzen jedoch waren die B-Zellen, wie bei den Hunden, degranuliert und hydropisch entartet. Bei einer Katze war das Aussehen der B-Zellen normal. Im Stroma der Inseln von 2 Katzen konnten starke Hyalinablagerungen nachgewiesen werden. In einem Falle zeigten die Inseln eine starke lymphocytäre Infiltration. — Weder bei den Hunden noch bei den Katzen waren typische Läsionen der Glomeruli, wie sie bei der Glomerulosklerose des menschlichen Diabetes auftreten, nachweisbar. Die häufigsten Veränderungen bestanden aus einer mehr oder weniger ausgeprägten Verdickung des mesangialen Teils der Kapillaren der Glomeruli und aus einer Hypertrophie der Wand der zuführenden Arteriolen. Bei einigen Hunden und Katzen bestanden auf chronische Pyelonephritis zurückführende Narben. — In der Retina der diabetischen Hunde waren zellenlose und funktionslose Kapillaren vorhanden, und degenerierte Pericyten (“ghostcells”) waren häufiger als bei normalen Hunden. In drei Hunden wurden einige Mikroaneurismen beobachtet. Daß diese für die Retinopathie des Diabetes typischen Läsionen beim Hund verhältnismäßig selten auftreten könnte mit der kürzeren Lebensdauer der Krankheit bei diesen Tieren zusammenhängen. Es ist jedoch nicht ausgeschlossen, daß die Retina von Hunden und Katzen weniger zu degenerativen Veränderungen neigt. — In der Leber vieler Hunde und Katzen wurde eine schwere Steatose beobachtet. In vier Hunden zeigte sich beginnende Lebercirrhose. In diabetischen Hunden und Katzen waren die Nebennieren oft hypertrophisch und enthielten Adenome, die allerdings auch bei nichtdiabetischen alternden Hunden beobachtet wurden. In 2 von 7 Hypophysen diabetischer Hunde fanden sich Adenome, über deren cytologische Untersuchung in einer späteren Veröffentlichung berichtet wird.
    Notes: Summary A histological study of 30 spontaneously diabetic dogs and 5 spontaneously diabetic cats is presented. — The islets of Langerhans and the B cells were strongly reduced in number in a large majority of the diabetic dogs. The B cells were often degranulated and hydropic. In cases of longer duration, the islets were scarce and B cells could no longer be found. — In contrast to the findings in diabetic dogs, all five cats showed numerous islets and B cells. However in 4 cats, the B cells showed complete degranulation and hydropic changes, as in the dogs. In one cat, the B cells had a normal appearance. Extensive hyalin deposits were found in the stroma of the islets in 2 cats. In one cat, an islet showed a dense lymphocytic infiltration. — No lesions identical to human diabetic glomerulosclerosis were found in any of the dogs or cats. The changes most frequently observed were a variable degree of thickening of the mesangial stalk of the glomerular capillaries, and an hypertrophy of the wall of the afferent arteriole. Scars resulting from chronic pyelonephritis, were found in a few dogs and cats. — Acellular, non-functional capillaries, with degeneration of pericytes (“ghost-cells”) were found in larger numbers in the retinas of the diabetic dogs than in non-diabetic control dogs. A very few microaneurysms could be found in 3 dogs. The lower incidence of the most typical lesions of diabetic retinopathy in dogs, as compared with the human diabetic, is probably related to the shorter duration of the disease in these animals. However, a lower susceptibility of the retina of dogs and cats to develop degenerative changes cannot be excluded. — A severe steatosis was observed in the liver of many dogs and cats. In 4 dogs, the liver showed early cirrhosis. In diabetic dogs and cats, the adrenal cortex often showed hypertrophy and contained adenomas; however, these changes have also been reported in non-diabetic aging dogs. An adenoma was found in 2 of the 7 pituitaries obtained from diabetic dogs; the cytological aspect of these adenomas and of the pituitaries will be reported in a later publication.
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  • 7
    Electronic Resource
    Electronic Resource
    Springer
    Diabetologia 3 (1967), S. 47-49 
    ISSN: 1432-0428
    Keywords: Calcium ; Magnesium ; Insulin ; Secretion Rabbit ; Pancreas ; Foetus
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé Le glucose, le glucagon, le tolbutamide et la L-leucine stimulent la libération d'insuline par le pancréas de lapin étudié in vitro. Cette stimulation n'a pas lieu lorsque le milieu d'incubation est préparé sans calcium. L'absence de magnésium n'a pas d'effet sur la sécrétion insulinique stimulée par le glucose, alors que le magnésium à la concentration de 10mM exerce un effet inhibiteur. La concentration optimale du calcium extracellulaire pour la sécrétion insulinique est de 2.64 mM. La stimulation de la sécrétion insulinique par le glucose est également supprimée par l'absence de calcium pour le pancréas de foetus de lapin âgé de 27 jours.
    Abstract: Zusammenfassung Die Freisetzung von Insulin aus Kaninchen-Pankreas in vitro wird durch Glucose, Glucagon, Tolbutamid oder L-Leucin stimuliert. In allen diesen Fällen bleibt die Stimulation in Abwesenheit von Calcium in Inkubationsmedium aus. In Abwesenheit von Magnesium stimulierte Glucose die Insulinsekretion weiter, währenddem eine Erhöhung der Magnesiumkonzentration auf 10 mM deutlich hemmend wirkte. Die optimale Sekretion von Insulin erfolgte bei einer Calciumkonzentration von 2.64 mM. In Abwesenheit von Calcium wurde die Freisetzung von Insulin auch aus dem Pankreas von 27 Tage alten Foeten gehemmt.
    Notes: Summary Glucose, glucagon, tolbutamide and L-leucine stimulated insulin secretion from rabbit pancreas studiedin vitro. In each case stimulation was inhibited by omitting calcium from the incubation medium. The omission of magnesium had no effect on glucose stimulated insulin secretion but 10 mM magnesium inhibited secretion. Optimal secretion of insulin occurred at an extracellular calcium concentration of 2.64 mM. The omission of calcium inhibited glucose-stimulated insulin secretion from pancreas of 27 day rabbit foetuses.
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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    Diabetologia 3 (1967), S. 74-84 
    ISSN: 1432-0428
    Keywords: Spontaneous diabetes ; Chinese Hamster ; Cricetulus griseus ; Insulin in Plasma ; Insulin in pancreas ; Pancreas ; Free fatty acids ; Detection of diabetes ; Muscle metabolism ; Adipose tissue metabolism ; Liver glycogen
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé Nous avons dépisté le diabète chez le hamster chinois par des dosages qualitatifs de la glucosurie. Nous avons ensuite caractérisé chaque cas par la mesure quantitative du glucose urinaire, par des surcharges au glucose et par le dosage de la glycémie à jeun et non à jeun, des corps cétoniques, des acides gras libres (AGL) plasmatiques, de l'insuline plasmatique et pancréatique, et des taux hépatiques de glycogène. En outre, nous avons mesuré l'utilisation du glucose par le diaphragme et le tissu adipeux épididymaire, avec et sans stimulation par l'insuline. Les animaux nécessitant l'administration d'insuline ont reçu leur dernière injection au moins 24 heures avant chaque étude. Les taux de glucose dans l'urine ont varié entre 51 et 1600 mg par 24 heures. Le test de surcharge au glucose s'est révélé nettement anormal chez les animaux diabétiques, la surcharge étant de 250 mg de glucose par kg de poids. Chez les diabétiques, la glycémie après surcharge est fortement variable, contrairement à l'uniformité de la réponse observée chez les non-diabétiques. Le glycogène hépatique à jeun est de 3, 1±1,0% pour les diabétiques, et de 0,4±0,7% de poids frais d'organes pour les non-diabétiques. Les taux plasmatiques des AGL et des corps cétoniques sont manifestement élevés chez les hamsters chinois diabétiques et cétosiques alors que le contenu en insuline du plasma et du pancréas est abaissé de façon marquée. Ceci n'a pas été observé chez les diabétiques moins sévères qui se rapprochent des non-diabétiques. Les AGL plasmatiques sont élevés chez tous les hamsters chinois (moyenne pour les non-diabétiques 1800μE/l, pour les diabétiques sévères 2800μE/l) Les taux d'AGL sont les mêmes à jeun et non à jeun chez les animaux non-diabétiques ou souffrant d'un diabète léger. L'utilisation du glucose par le muscle et le tissu adipeux du hamster diabétique ne diffère pas significativement de celle des tissus non-diabétiques et leur stimulation par l'insuline est semblable. L'insuline immunoréactive des hamsters traités à l'insuline reste élevée dans le plasma pendant plus de 26 jours après la dernière injection. — Ces observations semblent indiquer que le pancréas des hamsters chinois diabétiques sécrète plus difficilement de l'insuline en réponse à une stimulation par le glucose. Les taux normaux d'insuline plasmatique chez les hamsters avec un diabète léger, mais présentant pourtant une nette glucosurie, une hyperglycémie et une réponse anormale à la surcharge en glucose, suggèrent l'existence d'une interférence avec l'action normale de l'insuline et peut-être une augmentation de la production de glucose par le foie.
    Abstract: Zusammenfassung Beim chinesischen Hamster wurde der Diabetes durch qualitative Urinuntersuchungen auf Glucose aufgespürt. Es wurde dann jeder Fall näher charakterisiert durch quantitative Uringlucosebestimmungen, Glucosebelastungsproben und Messungen von Nüchtern- und Nichtnüchternwerten für Blutzucker, Blutketonkörper, freie Fettsäuren (FFS) und Insulin im Plasma, von Insulin im Pankreas, und von Nüchternwerten für Leberglykogen. Außerdem wurde der Glucoseverbrauch des Zwerchfells und des epididymalen Fettgewebes sowie mit, als auch ohne Insulin gemessen. Diejenigen Tiere, die Insulin erforderten, erhielten ihre letzte Injektion 24 Stunden vor dem Versuch. Glucosurie schwankte zwischen 51 und 1600 mg/24 Std. Bei einer Belastung von 250 mg/kg wiesen die diabetischen Tiere eine wesentlich verminderte Glucosetoleranz auf. Sie sprachen sehr unterschiedlich auf die Glucosebelastung an, während die nichtdiabetischen Tiere in ihrer Reaktion einheitlich waren. — Im Vergleich zu den nichtdiabetischen Hamstern, wo die Mittelwerte für Nüchternleberglykogen bei 0.4±0.7 Prozent des Frischlebergewichtes lagen, hatten die diabetischen Tiere einen Glykogengehalt der Leber von 3.1±1.0 Prozent. — Chinesische Hamster mit schwerem Diabetes haben deutlich erhöhte FFS-Werte und Ketonkörper, sowie einen wesentlich niedrigeren Plasma- und Pankreasinsulinspiegel. Bei Tieren mit leichter Diabetes hingegen sind diese Untersuchungen, im Vergleich zu den Kontrolltieren, unverändert. Alle chinesischen Hamster haben hohe Plasma-FFS-Werte (nichtdiabetische 1800μE/L, schwer diabetische 2800μE/L). Nüchtern- und Nichtnüchternwerte für FSS sind beim leicht diabetischen oder gesunden Tier etwa gleich hoch. Der Glucoseabbau durch Muskel- und Fettgewebe des diabetischen und nichtdiabetischen Hamsters unterscheidet sich nicht sehr, und beide Gruppen sprechen ungefähr gleich stark auf Insulinstimulierung an. Das im Plasma der insulinbehandelten Tiere vorkommende immunreaktive Insulin ist noch 26 Tage nach der letzten Injektion nachweisbar. — Diese Ergebnisse lassen vermuten, daß der Pankreas des diabetischen Hamsters nur schwerlich in der Lage ist, nach einer Glucosestimulierung Insulin auszuschütten. Die Beobachtung, daß der Plasma-Insulinspiegel im leichten Diabetes normal ist, diese Tiere jedoch Glucosurie, Hyperglykämie und abnormale Glucosetoleranz aufweisen, führt zu der Annahme, daß ein leichter Diabetes beim chinesischen Hamster eine Beeinträchtigung der Insulinwirkung mit sich bringen, und Ursache einer vermehrten Glucoseproduktion durch die Leber sein kann.
    Notes: Summary Diabetes in Chinese hamster was initially detected by qualitative tests for urine glucose. The disease was characterized by quantitating urine glucose, glucose tolerance tests and measurement of fasting and nonfasting blood sugar, blood ketones, plasma free fatty acids (FFA), plasma insulin, pancreatic insulin and fasting levels of liver glycogen. In addition, basal levels of glucose utilization by diaphragms and epididymal adipose tissue and the response of these tissues to insulin was measured. Those animals requiring insulin received their last injection 24 hours prior to study. Glucosuria varied from 51 to 1600 mg/24 hours. Diabetics had significantly decreased tolerance to a 250 mg/kg glucose load. The response varied considerably in diabetics but was uniform in the nondiabetics. Diabetics had mean fasting liver glycogen levels of 3.1±1.0 compared with 0.4± 0.7 percent of fresh liver weight for nondiabetics. Severely ketotic, diabetic Chinese hamsters had significantly elevated FFA and ketone levels and significantly lower plasma and pancreatic insulin levels but mild diabetics did not differ from controls with respect to these parameters. All Chinese hamsters had high plasma FFA levels (nondiabetics 1800μE/l, severe diabetics 2800μE/l. Fasting and nonfasting FFA levels did not differ in mild diabetic and nondiabetic animals. Muscle and adipose tissues from diabetic hamsters had basal rates similar to nondiabetics and had similar responses to insulin. Hamsters maintained on insulin had greatly elevated immunoreactive insulin levels in their plasma, which persisted for 26 days. — The data suggest that severely diabetic hamsters may have a decreased ability of the pancreas to secrete insulin in response to a glucose stimulus. The observations that plasma insulin levels are normal in mild diabetics but that these animals have glucosuria, hyperglycemia and abnormal glucose tolerance suggest that mild diabetes in the Chinese hamster may involve interference with insulin action and/or increased hepatic glucose output.
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  • 9
    ISSN: 1432-0428
    Keywords: Spontaneous Diabetes ; Spiny mice ; Acomys cahirinus ; Obesity ; Pancreas ; Ultrastructure ; Beta cells ; Insulin in pancreas ; Glycogen ; Islets of Langerhans ; Endo-exocrine cells
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé L'Acomys Cahirinus ou souris à piquants est un rongeur vivant dans les régions semi-désertiques de l'est de la Méditerranée. La découverte d'un diabète spontané chez certains de ces animaux a fait entreprendre l'élevage d'une colonie dans laquelle ce syndrome s'est maintenu jusqu'à maintenant. Il atteint environ 15% des animaux, qu'ils soient obèses ou non. Il apparaît sur un terrain insulaire très particulier puisque le pancréas endocrine montre une hyperplasie très importante jusqu'à constituer 15% du pancréas total. Cette hyperplasie existe chez tous les animaux, hyperglycémiques ou non. — L'étude au microscope électronique est encore trop incomplète pour une analyse corrélative détaillée entre les données métaboliques et morphologiques. Elle permet toutefois de décrire les différentes structures cellulaires de l'Acomys ainsi que leurs modifications dans les conditions pathologiques. Les changements du complexe de Golgi et des mitochondries et certains aspects plus pathologiques,comme l'accumulation de glycogène, sont décrits ainsi que des images plus particulières à l'Acomys, telles les confluences de vésicules et les cellules hypergranulées. — L'extrême hyperplasie du pancréas endocrine de la souris à piquants s'accompagne à son niveau d'un grand polymorphisme cellulaire. Les différentes cellules ainsi observées sont interprétées comme des aspects de différents moments physiologiques et non comme des types cellulaires particuliers. Ces données font conclure à la non-existence d'autres entités cellulaires que les cellules A, B et éventuellement D. Un aspect particulièrement intéressant de la souris à piquants est celui dela présence de cellules mixtes. Cette image est discutée dans le cadre très particulier du syndrome diabétique observé chez l'Acomys.
    Abstract: Zusammenfassung Acomys cahirinus, die Stachelmaus, ist ein kleines Nagetier, das in den an die Wüste grenzenden Gegenden des östlichen Mittelmeerraumes lebt. Da in dieser Tierart Spontandiabetes auftritt, zumindest in Laboratoriumszucht, halten wir dieses Tier am Institut de Biochimie Clinique seit etwas mehr als drei Jahren. Diabetes mellitus tritt bei ungefähr 15% der Tiere die ein Jahr alt werden ein; einige davon sind fettsüchtig, nicht aber alle. Diabetes erscheint trotz einer sehr stark entwickelten Hyperplasie der Langerhans'schen Inseln, die bis zu 15% des erwachsenen Organs ausmachen können! Diese Hyperplasie ist bei allen Tieren zu sehen, unabhängig davon ob eine diabetische Stoffwechselstörung vorliegt oder nicht. Mit dem Elektronenmikroskop haben wir die Langerhans'schen Inseln von 22 Stachelmäusen untersucht und berichten hier über die verschiedenen beobachteten Zelltypen, zu verschiedenen Zeitpunkten der Entwicklung der diabetischen Stoffwechselstörungen. Befunde an den B-Zellen dieser Tierart betreffen die hochgradige Entwicklung des Golgi Apparates, die große Unterschiedlichkeit und manchmal extreme Glycogen-Ablagerung in diabetischen Tieren, die häufige Verschmelzung der Membranen der Granula, und das Auftreten von ganz übermäßig hypergranulierten Zellen. — Die Hyperplasie der Langerhans'schen Inseln in Stachelmäusen geht mit einem betrachtenswerten zellulären Polymorphismus einher. Die Autoren sind jedoch nicht der Meinung, daß diese Befunde auf das Vorhandensein von vielen verschiedenen Zelltypen in diesen Inseln deutet. Es scheint ihnen viel wahrscheinlicher, daß es sich um verschiedene funktionelle Zustände einer kleinen Anzahl von Zelltypen handelt, wobei nur A, B, und vielleicht D Zellen mit Sicherheit als identifiziert gelten können. Ein besonders frappanter Aspekt dieses zellulären Polymorphysmus istdie häufige Beobachtung von gemischten oder Intermediärzellen (exokrin-endokrin sowie auch endokrin A-B). Diese Beobachtung wirft die Frage auf ob die Stimulation, die zu der Hyperplasie des endokrinen Systems in dieser Tierart führt, vielleicht mit einer Verminderung der nuklearen Hemmung, die bei voll differenzierten Zellen die Regel ist, einhergehen könnte.
    Notes: Summary Acomys Cahirinus, the spiny mouse, is a small rodent living in the semi-desertic areas of the Eastern Mediterranean. The observation that diabetes may occur spontaneously in this species, at least under laboratory conditions, has led to its breeding at the Institut de Biochimie Clinique, where a colony has been maintained over the last 3 years. Diabetes occurs in approximately 15% of the animals reaching one year of age; some of these are obese, but not all. Diabetes occurs in the presence of, and despite a striking hyperplasia of the endocrine pancreas, which may make up as much as 15% of the total organ in adult mice. This hyperplasia is present in all animals, whether hyperglycemic or not. — The islets of Langerhans of 22 spiny mice have been examined with the electron microscope and form the basis for an analysis of the different cell types observed, at different times relative to the onset of diabetes. Findings in the B cells of this species have included the generally high degree of development of the Golgi complex, the great variability of glycogen accumulation in diabetic animals, the frequent fusion of the granular sacs, and the occurrence of grossly hyper-granulated cells. — The hyperplasia of the islets of Langerhans in spiny mice is associated with a remarkable cellular polymorphism. However, the authors do not feel that this is the result of the presence in these islets of many distinct cell types. It would seem much more likely, that they represent different functional states of a small number of distinct types of cells, among which only A, B and perhaps D cells have been securely identified. Another feature of this cellular polymorphism is thefrequent presence of mixed or intermediate cells (exocrine-endocrine, or endocrine A-B), which suggests that the stimulation leading to hyperplasia of the endocrine cells in this species might result in the removal of some part of the nuclear inhibition usually associated with fully differentiated cells.
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  • 10
    Electronic Resource
    Electronic Resource
    Springer
    Diabetologia 3 (1967), S. 238-248 
    ISSN: 1432-0428
    Keywords: Spontaneous Diabetes ; Genotype: C57BL/K5-db ; Diabetes in mice ; Mutation: diabetes ; Obesity ; Prediabetes ; Insulin in plasma ; Insulin in pancreas ; Islets of Langerhans ; Pancreas ; Insulin resistance ; Glucose utilization ; Gluconeogenesis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé La mutation, diabète (db), a été observée dans la souche de souris C57BL/Ks. C'est un gène autosomal récessif avec pénétrance complète, et qui mène chez les homozygotes à un trouble métabolique ressemblant au diabète sucré chez l'homme. Une accumulation excessive de graisses se produit à l'âge de 3–4 semaines et est bientôt suivie par l'apparition d'hyperglycémie, de polyurie et de glucosurie. L'évolution clinique suit ensuite deux étapes. Durant la première, les taux d'insuline plasmatique sont élevés et la lipogénèse, la gluconéogénèse, ainsi que l'oxydation du glucose sont accélérées; il y a diminution de la granulation des cellulesβ et d'autres altérations suggérant l'existence d'une compensation d'un état nécessitant une utilisation insulinique accrue. La deuxième étape, par contre, est caractérisée par des taux normaux d'insuline plasmatique, avec diminution marquée de l'utilisation du glucose malgré la persistance d'une gluconéogénèse nettement exagérée. Ces observations nous semblent indiquer l'existence d'une utilisation défectueuse de l'insuline à la périphérie, plutôt qu'une anomalie primaire de la synthèse ou de la libération de l'hormone au niveau du pancréas.
    Abstract: Zusammenfassung Die Mutation Diabetes (db), die in dem Mäusestamm C57BL/Ks auftritt, ist ein autosomales rezessives Gen mit voller Penetranz und verursacht bei homzygoten Mäusen eine dem im Menschen auftretenden Diabetes mellitus ähnliche Stoffwechselstörung: übermäßige Ablagerung von Fett im Alter von 3–4 Wochen, mit anschließender Hyperglykämie, Polyurie und Glucosurie. Der klinische Verlauf erfolgt dann in zwei Phasen. In der ersten Phase ist ein wesentlicher Anstieg der Plasmainsulinwerte im Vordergrund, mit Beschleunigung von Lipogenese, Gluconeogenese und Glucoseoxydation. Das Abnehmen der Granula in denβ-Zellen der Langerhansschen Inseln und andere Veränderungen deuten auf eine Anpassung an einen steigenden Insulinbedarf. In der zweiten Phase, dagegen, sind die Insulinspiegel eher normal, und der Glucoseverbrauch nimmt ab, bei Weiterbestehen der beschleunigten Gluconeogenese. Diese Ergebnisse deuten eher auf eine mangelhafte periphere Insulinwirkung als auf eine ungenügende Synthese der Ausschüttung des Hormones durch das Pankreas.
    Notes: Summary The mutation, diabetes (db), that occurred in the C57BL/Ks strain of mice is a unit autosomal recessive gene with full penetrance, and causes metabolic disturbances in homozygous mice resembling diabetes mellitus in man. Abnormal deposition of fat at 3 to 4 weeks of age is followed by hyperglycemia, polyuria and glycosuria. The diabetic condition appears to develop in two stages. In the early stage, there are marked increases in the levels of plasma insulin, the rates of lipogenesis, gluconeogenesis, and glucose oxidation, and there is a reduction ofβ-cell granules in the islet of Langerhans with other changes suggestive of a compensating adaptation to increased insulin demand. On the other hand, the late stage is characterized by a near normal level of circulating insulin, a marked decrease in glucose utilization but with a continued high rate of gluconeogenesis. These findings suggest a defect in the peripheral utilization of insulin rather than in the synthesis and release of the hormone from the pancreas.
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  • 11
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 11 (1967), S. 73-84 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Complexes of aluminum alkyls with Lewis bases catalyze the polymerization of vinyl chloride. Triethylaluminum is most effective, but other compounds of type R3Al, R2AlCl, R2AlH, and LiAIR4 are operable. Dialkylmagnesiums are active, but Grignard reagents, as well as a number of other metal alkyls are inactive. Among Lewis bases, tetrahydrofuran (THF) and tetrahydropyran give the best yields of poly(vinyl chloride). Oxygen bases, such as ethers and esters, are more effective than nitrogen bases, e.g., tertiary amines. Cyclic compounds are better than acyclic ones. The polymerization occurs in a variety of hydrocarbon, chlorinated hydrocarbon, or ether solvents, but especially well in CCl4. Radical polymerization is probably initiated through the reaction R3Al:Base + CCl4 → R2AlCl: Base + R + Cl3C., to form trichloromethyl radical.
    Additional Material: 8 Tab.
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  • 12
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 11 (1967), S. 57-71 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Copolymerization of unsaturated polyester with styrene in water-in-oil (W/O) type emulsion was carried out with the use of various basic compounds as emulsifiers. It was found that a stable, gellike W/O type emulsion of unsaturated polyester resin is formed only when pKa's of the bases are above 6 and their concentrations are higher than some critical value. In these conditions, water can be dispersed in emulsion up to 900% to the resin. By polymerization, the stable W/O type emulsion is transformed to a white solid copolymer which is dry to the touch and which contains 90-95% of initially added water. It was confirmed that the basic compounds react with the carboxylic group of the polyester to form at the water-resin interface polyester salts, which act as true emulsifying agents. The stabilization mechanism of the emulsion at various concentrations of the polyester salt was investigated, mainly by microscopic observations, and an interpretation of the critical value of emulsifier concentration is proposed.
    Additional Material: 10 Ill.
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  • 13
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 11 (1967), S. 133-136 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Certain homopolymer-polyol mixtures, after treatment with a free-radical generating agent or ionizing radiation, will produce polyurethane elastomers of nearly twice the stiffness and tensile properties compared to control elastomers made with untreated mixtures. Specific examples of these mixtures include the homopolymers of acrylonitrile and vinyl chloride with a poly(oxypropyl) triol of about 3000 molecular weight as the polyol in each case. The marked improvement in the stiffness and tensile properties of elastomers made with the treated mixtures over those of the untreated controls indicates a grafting process occurring between the polyol and homopolymer upon the generation of free radicals. In the present work, grafting could occur by a chain-transfer hydrogen-abstraction mechanism, whereby a free-radical site is generated on both the homopolymer and polyol chains. Coupling of these two free-radical sites would thus result in the establishment of a polymer-polyol graft bond.
    Additional Material: 1 Tab.
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  • 14
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 11 (1967), S. 115-126 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Graft copolymerization of vinyl monomers, mainly methyl methacrylate, in reduced, successively alkylated, or KCN-Treated wool fibers was performed in the redox LiBr-persulfate system without homopolymer. The reduction gives a striking effect in promoting the graft copolymerization. Methylation or ethylene recrosslinking of the reduced wool, especially the former, decreases the graft-on remarkably. By the KCN treatment in which the conversion of disulfide to lanthionine bonds occurs, the grafting is decreased in the bromide-persulfate system but promoted in the system with persulfate alone. Methylation or KCN treatment of wool as well as reduction brings about a great increase in the absorption of persulfate. The grafting of the lanthionine-containing wool in the redox system accompanied by the liberation of bromine might be retarded by the pronounced bromination of monomers over the inhibiting of homopolymerization, because the lanthionine bonds are more stable to bromine than the disulfide bonds. In general, disulfide bonds and the other easily oxidized components of wool may perhaps play an important role in regulating the bromination of monomers and in the graft copolymerization without homopolymer. The molecular weight of graft polymer is decreased distinctly with increasing extent of reduction of wool. From these results, the thiol groups on wool are considered to give predominantly graft centers by the radicalotropy from SO4-·, OH·, and/or Br·.
    Additional Material: 3 Ill.
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  • 15
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 11 (1967), S. 153-153 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 16
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 11 (1967), S. 357-368 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Previous studies by Black and Blomquist on the degradative failure of polymer-metal adhesive bonds have shown that composite failure depends largely on the type of metal substrate employed. In the work reported herein, metal powders of high surface area have been employed to maximize the metal-polymer interface. The composite systems studied consisted for aluminum and iron with polycondensates of bisphenol A-diglycidyl ether, phenol-formaldehyde and poly-2,2′-(m-phenylene)-5,5′-bibenimidazole. The composites were prepared in the absence of air and thermally degraded in a time-of-flight mass spectrometer while the degradation products were continuously monitored from mass 1 to 200. In the polymer and polymer-metal systems investigated, iron accelerated the decomposition of all polymers studied. This was determined by plotting m/e against degradation temperature for the more common mass peaks such as hydrogen and carbon monoxide for the carbon-hydrogen-oxygen-containing polymer and hydrogen cyanide and ammonia for the carbon-hydrogen-nitrogen-containing polymer. This technique offers promise in determining the nature of the interface as well as the effect of the interface on polymer degradation.
    Additional Material: 12 Ill.
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  • 17
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A study was made of the influence of selected chain modifiers on both the molecular weight of grafted polyacrylonitrile and the grafting frequency of the starch-polyacrylo-nitrile graft copolymer. Gelatinized wheat starch was used with ceric ammonium nitrate as the initiator. The organic chain modifiers investigated were ethyl mercaptan, 1-dodecanethiol, methyl ethyl ketone, acetaldehyde, and chloroform. Sodium chromate, cupric bromide, cupric nitrate, cupric acetate, and cupric chloride were also tested as chain modifiers. In the presence of cupric chloride, there was a tenfold reduction in the molecular weight of grafted polyacrylonitrile; however, fewer chains were grafted to the starch backbone than were observed without cupric chloride.
    Additional Material: 4 Tab.
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  • 18
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 11 (1967), S. 475-478 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 19
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 11 (1967), S. 499-514 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The supermolecular structure of mixtures of crystalline polymers (low pressure and high pressure polyethylene, isotactic polypropylene) with an amorphous polymer (atactic polypropylene) from the point of view of the influence of the amorphous component on the morphology of the crystalline component has been investigated. The criterion of changes in the morphological state of larger supermolecular formations was the microscopic image of the samples obtained with an optical microscope, both between crossed nicols and in phase contrast. It has been established that the formation of typical spherulites depends on the amount of admixture of the amorphous polymer and also on the treatment of the samples. Upon crystallization in presence of a small amount of solvent (p-xylene), formation of typical spherulites of the crystalline component of the mixture can be observed while the same mixture in case of evaporation of the solvent presents a granulated refractive structure without typical spherulites, regardless of the rate of cooling. The probable role of the solvent is to facilitate mutual segregation of the microphases of both polymers in consequence of decrease in viscosity of the mixture. It has been further shown that even after briefly heating the mixture to a temperature of 220°C., before crystallization, spherulites do not form; on the contrary, spherulites originally present disappear and a structure consisting of smaller refractive formations of crystalline polymer is obtained. The formation of this structure, emerging after destruction of spherulites, might be attributed to an increase of interpenetration of both polymers and to an increase of the contact surfaces between components of the mixture.
    Additional Material: 9 Ill.
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  • 20
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: An experimental assembly incorporating a capacitance-type, differential pressure transducer, which provides resolutions of 3 × 10-4 torr at pressures extending to 30 torr, has been employed to monitor the effect of hydrogen environmental pressure on the hydrogen yield from x-irradiated polyethylenes. Contrary to the observations of previous investigators, the hydrogen yield is found to be independent of hydrogen environmental pressures extending over the critical range up to at least 30 torr. It is demonstrated that neglecting the temperature and density gradients inherent in closed-volume irradiation assemblies employing cryogenic traps to separate liberated gases into condensable and noncondensable fractions may lead to erroneous conclusions with respect to gas yields arising from the irradiation of materials. A homogeneous, variable-plate separation ion chamber consisting of a polyethylene body and utilizing flowing ethylene as the cavity gas was employed to obtain total volatile G values of 3.6 ± 0.4, 3.8 ± 0.4, and 4.0 ± 0.4 molecules/100 e.v., for Marlex 6002, Dow Ziegler (Q 917.5), and DuPont A-1410 polyethylenes, respectively. A hydrogen contribution of approximately 98 mole-% was obtained with this experimental method.
    Additional Material: 3 Ill.
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  • 21
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    Journal of Applied Polymer Science 11 (1967), S. 601-602 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 22
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    Journal of Applied Polymer Science 11 (1967), S. 629-638 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Castor oil has been used to prepare millable elastomers by using 2,4-toluene diisocyanate, 4,4′-diphenylmethane diisocyanate, and 1,5-naphthalene diisocyanate, respectively. These elastomers are vulcanized with sulfur and 4,4′-diphenylmethane diisocyanate separately by using the standard methods of rubber technology, and the properties of these vulcanizates are reported.
    Additional Material: 4 Ill.
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  • 23
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    Journal of Applied Polymer Science 11 (1967), S. 673-685 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A model nucleating agent for polypropylene crystallization is described. A series of compounds consisting mainly of organocarboxylic acid salts is evaluated as heterogeneous nucleating agent for polypropylene crystallization by measuring their effect upon the polymer supercooling. Sodium benzoate and basic aluminium dibenzoate were among the best nucleating agents found. The nucleating abilities of the various compounds are discussed in terms of their structural features.
    Additional Material: 7 Tab.
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  • 24
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    Journal of Applied Polymer Science 11 (1967), S. 705-718 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: We have shown by two separate measurements that polypropylene when melted after irradiation undergoes crosslinking from the inception of irradiation. The first proof was an immediate increase in the solution viscosity of a narrow molecular weight fraction of polypropylene. The second proof was the marked change in melt-flow properties on irradiation of a broad molecular weight distribution polypropylene. These findings tend to support one of the two currently held views on the action of radiation on polypropylene. In addition we have confirmed previous reports that melting after irradiation contributes to the overall crosslinking reaction.
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  • 25
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    Journal of Applied Polymer Science 11 (1967), S. 751-751 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 26
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    Journal of Applied Polymer Science 11 (1967), S. 811-815 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The preparation of polyisocyanurates by the polytrimerization of isocyanate prepolymers in the presence of organometallic catalysts leads to an increase in adhesive strength at 400°F. for bonding aluminum-to-aluminum. The trimerization efficiency of several other catalysts is briefly described.
    Additional Material: 2 Tab.
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  • 27
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    Journal of Applied Polymer Science 11 (1967), S. 1283-1288 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Dry mixtures of starch with various bases were roasted in air. The effects of roasting were determined by a viscosity method. The results suggest that roasting at alkaline pH's produces covalent crosslinks. The author speculates that the crosslinks result from a combination of autoxidation and aldolization.
    Additional Material: 3 Ill.
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  • 28
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    Journal of Applied Polymer Science 11 (1967), S. 1333-1343 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Five examples are discussed showing how gel permeation chromatography was applied to studies of polymer systems. The calculation of molecular weights from the curves was not pertinent to the studies. The only requirement was that the seperation be a size separation and the results be reproducible.
    Additional Material: 11 Ill.
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  • 29
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    Journal of Applied Polymer Science 11 (1967), S. 1387-1407 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A heterogeneous cellulose reaction was studied by reacting cotton fiber in pyridine medium with propionyl chloride at different initial molar concentrations and at different temperatures. It has been observed that the kinetics of reaction does not follow Sakurada's diffusion equation closely, and the deviation is more noticeable at lower initial concentrations of the reagent and at lower temperatures. A non-uniform reaction rate is also evident from the time-substitution curve. The rate of substitution changes twice during the reaction, the latter change being associated with the loss of cellulose I crystal structure. In an attempt to treat the data according to simple chemical kinetics, the order has been found to decrease continuously from the beginning, suggesting thereby an autocatalytic type of behavior. However, at the finàl stages of the reaction, when the cellulose I structure was completely lost, the reaction behaved as a pseudo first-order type. The x-ray diffractograms of the reacted samples indicate that cellulose I crystallinity decreases from the beginning of the reaction and that a new crystalline lattice develops gradually. The formation of this new crystal lattice is hindered in the cellulose crystalline region due to the lack of freedom of the chains. The diffusion equation has been modified by substituting a crystallinity index for the rate of diffusion of solvent in a solvent-gel system and thus extending Sakurada's equation. A new mechanism has been proposed considering the simultaneous reactions in the amorphous and crystalline regions. This mechanism can explain the deviation of Sakurada's equation. The kinetics expressions are derived, based on the proposed mechanism. The kinetics of decrystallization of cellulose I is also presented. A satisfactory theoretical explanation is given for the fact that the fall of reaction rate occurs at the conclusion of decrystallization of the cellulose I structure.
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  • 30
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    Journal of Applied Polymer Science 11 (1967), S. 1439-1448 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: It is shown that the glass temperature (Tg) for homopolymers of the type —CH2—CXY—can be expressed by a simple additive equation involving two terms: (1) a parameter E which is directly related to the molar cohesion energy and (2) a parameter Es* which is a measure of restricted rotation about valence bonds. Es*, at least for a large number of polymers, is related to the Mark-Houwink Kθ value (as measured in θ solvents at Tθ) via anti-log Es* ∝ 1/Kθ2/3. It is also shown that for homologous series [e.g., poly(n-alkyl methacrylates)], there is a constant relationship between E and antilog Es*. The Tg values for copolymers may be estimated by a simple weighted (via mole fraction) summation of the E and Es* values of the components. When used in this form, a linear variation between Tg and composition is assumed, which may not be strictly correct but still yields useful approximations.
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  • 31
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    Journal of Applied Polymer Science 11 (1967), S. 1483-1494 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Lattice spacings perpendicular to the molecular chain axes and crystallite orientation of dried and moist (boiled in water) bulk nylon 6 were determined by x-ray diffraction under tension of 30-300 kg./cm.2. The deformation of the specimen was also measured. The lattice spacings are changed reversibly by the presence of water in nylon 6, but the elastic moduli of the lattice are not affected. The lattice elastic modulus in the direction of the hydrogen bonds is approximately double its value in the direction normal to the hydrogen bonds. The elastic modulus of the dried nylon 6 approaches the value of the lattice elastic modulus in the direction normal to the molecular axes, while the modulus of the moist nylon 6 is several times lower. From these facts, and especially from the relations between the lattice deformation, crystallite orientation, and specimen deformation, the principal differences in the deformation mechanism of dried and moist nylon 6 were deduced. The results obtained have also made possible some general conclusions about the crystalline structure of nylon 6 and the deformation mechanism of linear polymers.
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  • 32
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    Journal of Applied Polymer Science 11 (1967), S. 1529-1538 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Graft copolymerization of methyl methacrylate and acrylamide onto ovalbumin was carried out with redox system with ceric ion. Initiation of grafting occurred very rapidly, and the number of grafting sites reached a maximum after about 2 min. regardless of initial ceric ion concentration. The grafted polymer chains were separated by selective hydrolysis of the protein backbone with hydrochloric acid or protease in order to characterize the graft copolymers. The grafted polyacrylamide separated by the proteolytic digestion contained a carbohydrate residue at the end of the polymer molecule. The problem of grafting sites on ovalbumin is discussed.
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  • 33
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    Journal of Applied Polymer Science 11 (1967), S. 1553-1562 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A process for adhering polyethylene to aluminum was developed which involves treating the aluminium substrate successively with chromic acid and then a selected organic acid. Certain organic acids utilized in this process appeared to produce a synergistic effect on the adhesion. This process, which required no modification or treatment of the polymer, resulted in peel strengths forty times greater than that obtained on untreated aluminum. Tensile shear values for the polyethylene-aluminum bond were greater than 2800 psi. The materials used for treating the metal in this system produced a maximum in the obtainable peel strength. Furthermore, minor changes in the etching acids resulted in drastic changes in the adhesion values.
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  • 34
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    Journal of Applied Polymer Science 11 (1967), S. 1613-1615 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A relatively simple and inexpensive automatic apparatus for chemical relaxation giving good accuracy has been developed for measurement of chemical relaxation in the gaseous phase in high polymers. The apparatus is based on a previously described balance-type stress relaxation apparatus intended for automatic operation.
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  • 35
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    Journal of Applied Polymer Science 11 (1967), S. 1581-1591 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The effect of monomer sequence on physical properties was investigated for butadienestyrene solution copolymers made by organolithium initiation. The polymers varied from random copolymers of uniform composition along the polymer chain to ideal block polymers of specific block sequence arrangement and included rubbers of intermediate degrees of randomness. Uniform composition random copolymers exhibit a single glass transition temperature and a very narrow dynamic loss peak corresponding to this transition. The glass transition can be predicted from the styrene content and the microstructure of the butadiene portion of the rubber. Random copolymers in which composition varies along the polymer chain, and to some extent between molecules, exhibit a single glass transition, but the dynamic loss peak is broadened. The extent of this broadening is shown to be compatible with the sequence distribution, polymer segments of various compositions losing mobility at different temperatures. This indicates a tendency for association between segments of different temperatures. This indicates a tendency for association between segments of different chains which are similar in composition. Block copolymers display two transitions, corresponding to Tg for each type of block. The position and width of the dynamic loss peaks are related to block length and compositional purity of the blocks.
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  • 36
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    Journal of Applied Polymer Science 11 (1967), S. 921-924 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A simple, inexpensive microtome was developed for sectioning polystyrene foam prepuff. The cell structure is well defined and wall thicknesses can be measured easily from photomicrographs prepared with the microtome.
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  • 37
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    Journal of Applied Polymer Science 11 (1967), S. 925-947 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The applicability of Miner's law of cumulative damage to predict lifetimes in experiments involving complex load histories is examined. Lifetimes estimated by Σ ti/(tb)i = 1 are compared with those calculated by the expression for the time to rupture derived by Prevorsek and Lyons assuming that the time to rupture can be approximated by the time to form an unstable crack. For experiments in which the loading conditions became increasingly severe with time, lifetimes predicted by Miner's law are longer than those calculated from the rate of crack propagation, the opposite being found for experiments in which the loading conditions become decreasingly severe with time. Experimental data on hand are in agreement with these findings. Effects of changes in the structural parameters ρ, E, and ΔF* and of variations in the experimental conditions on the accuracy of the lifetime estimates are discussed.
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  • 38
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    Journal of Applied Polymer Science 11 (1967), S. 23-36 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The adduct of Kaolin and 2,2′-azobisisobutyramidine hydrochloride has been used to initiate the polymerization of methyl methacrylate, styrene, styrene-butadiene, vinyl acetate, chloroprene, acrylamide, and acrylonitrile. Both extractable and nonextractable polymers are obtained. The adduct of bentonite and 2,2′-azobisisobutyramidine hydrochloride will initiate the polymerization of methyl methacrylate, acrylamide, vinyl acetate, 4-vinylpridine, and styrene. Both extractable and nonextractable polymers are formed. When the bentonite or the hectorite adducts are more than 99% decomposed prior to the addition of methyl methacrylate, essentially no extractable polymer is formed, but an increased quantity of nonextractable polymer is produced. This is probably due to an increased accessibility of the monomer to the clay's interior surface and a decrease in the rate of chain termination. As is the case of the kaolin adduct, the clay surface of bentonite appears to accelerate the chain growth considerably.
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  • 39
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    Journal of Applied Polymer Science 11 (1967), S. 37-55 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A quantitative characterization of natural rubber, both as the raw polymer, and unaccelerated vulcanized samples containing different proportions of sulfur and ranging from soft to hard rubber, is reported. A value of 86% of the chains of natural rubber could be accounted for against 37% as reported by Harries assuming that levulinic acid is the sole degradation product. About 5% of the chain is present as a 3,4 structure which gives rise to formic acid in the degraded product. A small amount of sulfuric acid is present in the degradation product from the vulcanized samples, which decreases with the increases in the percentage of sulfur in the stock as well as the cure time. A chromatographic technique for the separation of levulinic, acetic, and formic acid in the presence of sulfuric acid is reported. It is observed that the total amount of carbon main chain escaping sulfuration decreases and the amount of insoluble fraction increases with increasing proportion of sulfur in the stock.
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  • 40
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    Journal of Applied Polymer Science 11 (1967), S. 773-790 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Polyacrylonitrile-β-propiolactone (βPL) graft copolymer was synthesized by means of ionic polymerization, in which polymerization of βPL was initiated by polyacrylonitrile containing a small amount of some reactive groups such as —COOK, —COONa, —COOLi, and —COOH. Lower electronegativity of the countercation favored higher total conversion and higher grafting percentage. The grafting percentage increased with the reaction time and concentration of reactive groups in the trunk polymer, but grafting efficiency varied very little under these conditions. In the bulk polymerization at 60°C., grafting efficiency was about 60%, but in the solution polymerization in toluene or dioxane, grafting efficiency was higher than in bulk or nitrobenzene.
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  • 41
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    Journal of Applied Polymer Science 11 (1967), S. 791-810 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Polyacrylonitrile (PAN)-β-propiolactone (βPL) graft copolymer was synthesized by means of the ionic polymerization of βPL in the presence of polyacrylonitrile containing diketene units by using basic catalysts. A graft copolymer was produced by the copolymerization of βPL with the lactone ring in the trunk polymer. In this graft copolymerization method, the grafting efficiency was low. However, grafting efficiency increased with the mole ratio of polymeric lactone to βPL; also higher molecular weight of PβPL favored higher grafting efficiency. The reactivity ratio of polymeric lactone to βPL was estimated to be in the range of 0.1-0.3.
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  • 42
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    Journal of Applied Polymer Science 11 (1967), S. 839-858 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The radiation-induced grafting to cellulose of styrene, methyl methacrylate, vinyl acetate, 2-vinylpyridine, and 4-vinylpyridine in methanol has been studied. All monomers exhibit appreciable grafting at room temperature in either vacuum or air for total doses up to 10 Mrad and at dose rates as high as 1.4 Mrad/hr. in a spent fuel or 60Co facility. The magnitude of the grafting depends upon both the total dose and dose rate. Under certain experimental conditions, the grafting experiences a maximum which has been attributed to the Trommsdorff effect. A novel mechanism involving charge-transfer bond formation is proposed to account for the observed data in the grafting reactions.
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  • 43
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    Journal of Polymer Science: Macromolecular Reviews 1 (1967), S. 119-172 
    ISSN: 0076-2083
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 23 Ill.
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  • 44
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    Journal of Polymer Science: Macromolecular Reviews 1 (1967), S. 173-275 
    ISSN: 0076-2083
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 67 Ill.
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  • 45
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    Journal of Polymer Science: Macromolecular Reviews 2 (1967), S. 115-268 
    ISSN: 0076-2083
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 47 Ill.
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  • 46
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 1327-1328 
    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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  • 47
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 23-35 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polyacrylamide having a fluorescent residue at the chain end was prepared by polymerization of acrylamide in the presence of a fluorescent dye. The segmental motion of the chain end in dilute solution was studied by the fluorescence polarization method on the fluorescent polyacrylamide conjugates thus obtained. The linear relation between 1/p and T/η0 held for every sample studied in aqueous media, where p is the degree of polarization of the fluorescence, T is the absolute temperature, and η0 is the viscosity of the medium. The mean relaxation time 〈ρ〉 of the conjugate was evaluated from these data as a function of the molecular weight of the conjugate. The value of 〈ρ〉 increased slightly with molecular weight, varying from 3.3 × 10-9 to 7 × 10-9 sec. The absolute values of 〈ρ〉 and its molecular weight dependence suggest that 〈ρ〉 represents the mean rotational relaxation time for the cooperative motion of about ten monomeric units at the chain end. The effect of the mean extension of polymer chain on the segmental motion was found to be negligible.
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  • 48
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), 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 fluorescence polarization method has been used to study the micro-Brownian motion of a terminal segement of a polymer chain in concentrated solutions. A new apparatus for determining the fluorescence intensity and its polarization degree was designed. By using this apparatus, the rotational relaxation time 〈ρ〉 of the terminal segment of the fluorescent conjugates of polyacrylamide in aqueous polyacrylamide solutions was obtained as a function of polymer concentration from 0 to 65%, molecular weight of the conjugate from 3.5 × 104 to 3 × 105, and temperature from 10 to 30°C. The logarithm of 〈ρ〉 increased approximately linearly with increasing polymer concentration. This increase in 〈ρ〉, amounting to a factor of 20 times, was less marked than that in macroscopic viscosity. At concentrations less than 30%, 〈ρ〉 depended appreciably on the molecular weight of the conjugate.
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  • 49
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 47-61 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polyethylene networks were prepared by γ-irradiation of linear polyethylene, both molten and crystalline. The elastic and photoelastic properties of the networks were studied at high temperatures, i.e., in the molten state. The equilibrium swelling was also measured in several solvents. Values of the crosslinking efficiency G of γ-radiation, the molecular, weight Me between entanglements, the optical anisotropy α of the equivalent random link, and the polymer-solvent interaction parameter μ are deduced. Samples prepared by irradiation in the amorphous state showed markedly non-Gaussian elastic behavior. The presence of a large non-Gaussian term in the optical anisotropy is also deduced. The value of α obtained for swollen samples, which showed substantially Gaussian elastic behavior, was 3.9 × 10-24 cm.3, about one-half of that obtained for dry samples. It corresponds to an equivalent random link of only about 5 CH2 units, on the basis of Denbigh's values for bond polarizabilities. The samples prepared by irradiation in the crystalline state showed lower values for α, which also depended upon the degree of crosslinking. This is attributed to the nonrandom chain configurations prevailing at the time of crosslinking. The same samples were found to show more nearly Gaussian elastic behavior, which is attributed to the same cause.
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  • 50
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 63-81 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Detailed structure analysis of the polyoxymethylene molecule was carried out by the method of three-dimensional Fourier synthesis. The diffraction data were measured on a highly ordered polyoxymethylene sample prepared from a single crystal of tetraoxane by solid-state radiation polymerization. By assuming the anisotropic thermal factors for the oxygen and carbon atoms and taking into account the contribution of the hydrogen atoms, good agreement between the observed and calculated structure factors was obtained; the R factor is 8.8%. The distance between the oxygen atom and the helix axis r(O) = 0.671 A. is slightly shorter than r(C) = 0.691 A. The bond distance C—O = 1.421 A., the angle ∠COC = 112°24′, and ∠OCO = 110°49′. All the internal rotation angles of the skeletal bonds are 78°13′. It is deduced from the experimental results that each crystallite of polyoxymethylene is composed of only one type of helix, right-handed or left-handed.
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  • 51
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 83-87 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The relation of the high-frequency elastic moduli of semicrystalline polymers to volume fraction crystallinity is correctly described by the Hashin-Shtrikman theory, without any disposable constants, as a function of the ratio of the modulus of the amorphous to that of the crystalline phase. Hence the (high-frequency) reduced modulus of semicrystalline polymers is largely a function of the temperature T/Tg. The importance of T/Tm for the modulus of the crystalline phase precludes the existence of a single universal reduced modulus versus temperature curve.
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  • 52
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 239-262 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The infrared absorption spectra of selected crystalline and noncrystalline bands were studied in bulk-crystallized specimens of linear polyethylene which encompassed the extremely wide density range of 0.92-0.99 g./cm.3. The analysis of the data obtained at room temperature yield degrees of crystallinity by infrared methods which are in very good accord with the values deduced from the density measurements. Studies of the infrared spectra as a function of temperature give fusion curves which are in agreement with those obtained by thermodynamic methods. However, in order to obtain these latter results cognizance must be taken of the large negative temperature coefficient of the specific extinction coefficients of the crystalline bands from room temperature to the melting point. The necessary data to account for this phenomena were obtained from studies of the spectra of the n-paraffin, C94H190, where molecular crystals are formed. Analysis of the two gauche bands, at 1352 and 1303 cm.-1, which are assigned to the noncrystalline regions demonstrate that for bulk-crystallized samples of lowest densities the intensity ratio at room temperature is identical to that expected from the pure melt at this temperature. The conclusion is thus reached that the noncrystalline regions in these cases and the pure melt are structurally very similar. For samples of higher density, where the crystallite size is comparable to the extended chain length, the intensity ratio of the two gauche bands is altered. This change could reflect a change in the sequential distribution of gauche bonds. This intensity ratio for crystals formed from dilute solution is very similar to that for the high-density bulk-crystallized material and indicates a similarity in structure of the noncrystalline regions in the two cases.
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  • 53
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 277-288 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: To investigate the solution properties of polyethylene, which has the simplest structure of the vinyl polymers, experiments were made with a magnetically suspended equilibrium ultracentrifuge. Preliminary studies were carried out with a polystyrene-chloroform system at 25°C. and a polystyrene-methylcyclohexane system at 68°C. (which is close to the theta temperature) in order to check the difficulties involved in the flotation equilibrium in the former case and the high temperature measurement in the latter. However, no trouble was encountered in either system, and the results were discussed and compared with earlier results for polystyrene solutions. It was found that chloroform is a good solvent for polystyrene, and the measured weight-average molecular weight is somewhat smaller than the value obtained in a theta solvent. After overcoming some technical difficulties involved in studies at higher temperatures, we carried out experiments on polyethylene in α-chloronaphthalene at 130°C. The results are considered reasonable by comparison with results obtained by other methods. The sample employed, Marlex 50 of melt index 0.7, has a wide molecular weight distribution: i.e., Mz/Mw = 5.2 and Mz+1/Mz = 2.4.
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  • 54
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 289-300 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Accurate measurements of stress relaxation after steady-state flow have been carried out, in the Newtonian flow region, for a polystyrene and a poly(methyl methacrylate) melt, with a cone-and-plate rotational rheometer. From the stress relaxation σ(t) versus t curves the relaxation spectra H were calculated by means of the first approximation equation: \documentclass{article}\pagestyle{empty}\begin{document}$ H = - ({1 \mathord{\left/ {\vphantom {1 {\dot \gamma t)d\sigma {{(t)} \mathord{\left/ {\vphantom {{(t)} d}} \right. \kern-\nulldelimiterspace} d}}}} \right. \kern-\nulldelimiterspace} {\dot \gamma t)d\sigma {{(t)} \mathord{\left/ {\vphantom {{(t)} d}} \right. \kern-\nulldelimiterspace} d}}}\ln t $\end{document}. The shear stress-shear rate curves, σ versus \documentclass{article}\pagestyle{empty}\begin{document}$ {\dot \gamma } $\end{document} were also measured, in large ranges of shear rates, for the same melts, and from these data the relaxation spectra H were obtained by means of equations given by Faucher and Ferry. The Faucher equation, \documentclass{article}\pagestyle{empty}\begin{document}$ H = - \dot \gamma ^2 d{\sigma \mathord{\left/ {\vphantom {\sigma d}} \right. \kern-\nulldelimiterspace} d}\dot \gamma ^2 $\end{document}, has been found to give results which compare satisfactorily with those obtained from the first approximation equation. It has been found that the Ferry equation has to be modified for comparable agreement.
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  • 55
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 315-322 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effect of polydispersity on liquid-liquid phase equilibrium in systems containing polymer, solvent, and nonsolvent is investigated numerically in the Flory-Huggins approximation for several special cases. The resulting phase diagrams indicate that, except in the immediate vicinity of the critical region, the degree of swelling of a polymer precipitate phase with a given number-average molecular weight is essentially independent of polydispersity.
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  • 56
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 399-415 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The statistical mechanical treatment of polymeric chains in terms of the largest eigenvalue of the product of statistical weight matrices for the rotational interactions of skeletal bonds of the repeat unit becomes excessively complicated if the repeat unit spans more than three or four skeletal bonds. Moreover, such treatment is necessarily limited to chains in which the number of repeat units is indefinitely large. Newer methods are readily applicable to chains of any degree of polymerization comprising repeat units of any realizable length. If interdependence of neighboring bond rotations is confined to bond pairs within a given unit, rotations about a pair of bonds belonging to neighboring units being mutually independent, further simplifications may be introduced without sacrifice of rigor. Polyamides, in which rotation about bonds on opposite sides of the amide group are independent, are polymers of this type. Adherence of the amide group to the planar trans conformation favors a more extended configuration of the chain, but this effect is dominated by the smaller steric repulsions affecting rotations about bonds which are first, second, and third neighbors of the amide group. It is for this reason that the characteristic ratio 〈r2〉0〉/nl2 for poly(hexamethylene adipamide), ca. 6.0 according to experimental results of Saunders, is less than the value, 8.0, for polymethylene at 25°C. The characteristic ratios and molecular dipole moments are computed as functions of the degree of polymerization. The poly(εaminocaproamide) chain also is treated.
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  • 57
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 461-470 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Proceeding from the work of Zimm and Stockmayer and of Benoit, a general formula is derived for the calculation of the radius of gyration of block and graft copolymers. It appears that with linear block copolymers the ratio of the mean-square radius of gyration and the mean-square end-to-end distance is usually not far from 1/6. With a great number of blocks the difference from 1/6 can entirely be neglected. Also the influence of the composition of the molecules on the scattered light intensity has been considered.
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  • 58
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 639-652 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The primary reaction of oxygen with irradiated polyethylene has been followed by observing the rapid disappearance of the ultraviolet absorption bands at 258 and 285 mμ, bands attributed to the allyl and dienyl free radicals. A mathematical theory based on diffusion equations has been developed by means of which a quantitative estimate of the total initial free-radical concentration can be made. From the shape of the free-radical decay curve it can be concluded that the initial oxygen-free-radical reactions occur about three times as frequently in the amorphous regions as in the crystalline.
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  • 59
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 653-662 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Aromatic poly(amic acids) derived from pyromellitic dianhydride and 4,4′,-diaminodiphenyl ether were characterized by dilute solution techniques. Number-average molecular weights M̄n of 13 samples ranged from 13,000 to 55,000 (DP 31-131). Weight-average molecular weights M̄w of 21 samples ranged from 9,900 to 266,000. The ratio M̄w/M̄n was between 2.2 and 4.8. Heterogeneous polymerization yielded higher molecular weight polymer than homogeneous polymerization. The molecular weight could be varied systematically by control of stoichiometric imbalance. Use of very pure monomers and solvent gave polymers of relatively high number-average molecular weight (∼50, 000) and the most probable molecular weight distribution M̄w/M̄n = 2. Impure monomers and/or solvent resulted in lower number-average molecular weight (M̄n ≅ 20,000-30,000) and wider distributions (M̄w/M̄n = 3-5). The Mark-Houwink relation obtained was [η] = 1.85 × 10-4M̄w0.80 The exponent is characteristic of moderately extended solvated coils. The unperturbed chain dimensions (r02/M)1/2 were 0.848 A., and the steric factor σ was 1.24 which is close to the limiting value of unity for an equivalent chain with free internal rotations. The sedimentation constant-molecular weight relation was S0 = 2.70 × 10-2M̄w0.39. This exponent is consistent with the Mark-Houwink exponent.
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  • 60
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 705-710 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Recent precision measurements of the heats of combustion of atactic and isotactic polystyrene permit an unequivocal calculation of the enthalpy difference in the bulk amorphous forms of the two isomers of this polymer. Contributions to this quantity arise mainly from the differences in nonbonded interactions in the two configurations but may also contain terms relating to higher energy conformations and to intermolecular interactions. The thermochemical and NMR data of specific polymers and of simple molecules are discussed in a comparison with model compound calculations. The thermochemical method has potentially important applications in studying molecular interactions in stereoregular polymers.
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  • 61
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The Tian-Calvet microcalorimeter has been used to measure the heat of solution of atactic polystyrene in toluene at 30°C. By using a special technique for polymer sample preparation, it has been possible to measure directly the difference in conformational energy of the polystyrene chain at different temperatures, from 30 to 100°C. and to calculate its contribution to the specific heat.
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  • 62
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 761-769 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The α, β, and γ transitions at temperatures between -200 and +100°C. of crosslinked aromatic and aliphatic epoxy polymers were determined from damping and shear modulus data, and compared with their fluorine containing analogs. Loci of segmental relaxation are suggested at various temperatures, and similarities between aliphatic and fluorocarbon segments, and polyethylene and polytetrafluoroethylene are discussed. Two systems of structurally similar monomers 2,2,3,3,4,4-hexafluoropentane diglycidyl ether-1,5 and 1,4-butane diglycidyl ether, and 2,2-bis(4-glycidyl phenyl ether)hexafluoropropane and 2,2-bis(4-glycidyl phenyl ether) propane were polymerized with the aid of two diamine curing agents, namely, ethylenediamine and m-xylylenediamine. Polymers of the aromatic diepoxides showed transitions with peaks at -56°C. and above +70°C. Three main peaks were registered for the aliphatic and fluorocarbon diepoxides: at -125 and at -100°C., at -56°C., and at 0°C. It is suggested that the Tg is affected by an interdependence of relaxation of all components of the polymer main chain.
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  • 63
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    Journal of Polymer Science: Macromolecular Reviews 1 (1967), S. 35-56 
    ISSN: 0076-2083
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 4 Ill.
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  • 64
    ISSN: 0076-2083
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Heterogeneous olefin polymerization catalysts generally consist of a transition metal compound from groups IVB or VB in combination with an organometallic compound from groups I, II, and III of the periodic table of the elements, but in some instances may contain a third component possessing at least one strongly complexing ligand atom. The composition of a coordination catalyst of this type determines both the rate of polymerization of the α-olefin and the stereoregularity of the polymer produced. In order to predict activity and stereospecificity of catalysts for the polymerization of α-olefins, data from the polymerization of propylene using catalysts of the following types were correlated: (1) titanium(III) chloride catalysts in which the organometallic component was varied, (2) coordination catalysts containinig a ligand third component in which the ligand was varied, and (3) coordination catalysts in which the transition metal component was varied.The electronegativity of an orgariometallic compound is known to be important in determining its reactivity with ethers, hydrogen, and other reagents. Both the ionic size and the electronegativity of the central atom appear to be important in determining the utility of both the organometallic and the transition metal compounds as components for coordination catalysts. In general, organometallic and transition metal compounds having small central atoms with similar electronegativities favor the formation of stereospecific catalysts.The present correlation has made it possible to predict the activity and stereospecificity of coordination catalysts for olefin polymerization.
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  • 65
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 1313-1316 
    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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  • 66
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. i 
    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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  • 67
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 1-21 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Light-scattering, viscometric and osmometric studies have been carried out on dilute solutions of polycarbonate fractions both in a good solvent and in theta solvents. The data span the molecular weight interval 5 〈 10-3M 〈 760. It has been concluded that: (1) the overall behavior in dilute solution is consistent with a flexible chain conformation; (2) the ratio of the unperturbed mean-square radius to the molecular weight, or to the number of chain elements, is larger than commonly observed for vinyl polymers; (3) the ratio of the unperturbed radius to the radius calculated for a chain with free rotation about valence bonds has the unusually small value 1.3; and (4) the hydrodynamic behavior of the chain may reflect partical draining affects.
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  • 68
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 125-142 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Degradation of poly(ethylene oxide) (PEO) by violent stirring was studied in various solvents. The chain scission or the limit of the degradation was measured, and the effects of solvents, polymer concentration, stirring speed and degree of polymerization (DP) were investigated. It was found that the number of bonds broken per polymer chain was independent of the concentration but increased with the stirring speed and with decrease in the DP. The rate was much affected by the solvent used, being larger in a poor solvent. It was also found that the rate could be represented either by Jellinek's or Ovenall's rate equations, which have been applied to the ultrasonic degradation of polymers in solution.
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  • 69
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 165-177 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Thermal expansion and dielectric relaxation of polyacrylonitrile were measured in the temperature range from -75 to 152°C. at frequencies from 30 cps to 3 Mc./sec. The thermal expansion curve and the temperature dependence of logarithmic relaxation time both show an inflection at 85°C. An x-ray study by Bohn reveals that this inflection comes from the thermal expansion of the paracrystalline phase of this polymer, and consequently the transition at 85°C. and the associated relaxation are ascribed to molecular motion in the paracrystalline phase. The relaxation strength increases with increasing temperature above this point. The transition is caused by freezing of the bending vibration of chains whereas the relaxation results from rotational vibration. The length of segments in this phase is roughly estimated to be ca. 100 A. by comparing the observed relaxation strength with the theory developed on the basis of the above considerations.
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  • 70
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 179-193 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In order to explain the observed nonvanishing limiting value of dynamic intrinsic viscosity of polymer solutions at ω = ∞ one has considered the necklace model with finite resistance to the rate of coil deformation introduced long ago by Cerf for the study of gradient dependence of intrinsic viscosity and streaming birefringence. The calculation need not take into account change of hydrodynamic interaction as a consequence of coil deformation because the experimental data are always either obtained at very low gradient or extrapolated to zero gradient so that in the experiment the macromolecule has the same conformation as in the solution at rest. The model indeed yields a finite [η]′ω = ∞ in good agreement with experiments on polystyrene in Aroclor. According to the theory [η]′ω = ∞/[η]0 decreases with increasing molecular weight as M-1 and M-1/2 for the free-draining and impermeable coil, respectively. The absolute limiting value [η]∞′, therefore turns out to be nearly independent of M, at least for small values of internal viscosity. From the observed value [η]∞′/[η0] one can obtain the coefficient of internal viscosity of the macromolecule. The value for polystyrene in Aroclor calculated from dynamic experiments on rather concentrated solutions is close to that derived by Cerf from streaming birefringence observations of polystyrene in a series of solvents of widely differing viscosity.
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  • 71
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 225-229 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 5 Ill.
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  • 72
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 301-313 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polarized infrared measurements were made on polymer samples to obtain the structural changes occurring during the orientation process. The absorbances of the infrared bands were measured by determining the three components of the absorbance. Two components were obtained directly with plane-polarized light while the third is obtained by tilting the sample and extrapolating. Corrections were made for machine optics polarization, sample birefringence, polarizer inefficiency, anisotropy of the index of refraction, and scattering from the film surface. Data are reported for polyethylene obtained from cold-drawn specimens as a function of draw temperature. Polyethylene exhibits no strain-induced crystallization as a result of the chain-alignment process. Annealing of the drawn samples reperfects the distorted crystals.
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  • 73
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 323-331 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The diffusion coefficient of 1,1,2-trichlorotrifluoroethane (TTE) in a liquid polybutene was determined at 25°C. as a function of concentration over the range 1.0-19.5 g. TTE/100 cc. The diffusion coefficient increase with increasing TTE concentration, rising continuously from 3 × 10-8 cm.2/sec. at the lowest concentration to 15 × 10-8 cm.2/sec. at the highest. The magnitudes of the diffusion coefficients indicate that the diffusion mechanism for small molecules in polymeric media must afford vastly greater opportunities for diffusion than the Stokes-Einstein relation allows. Similarly, self-diffusion coefficients for the liquid polymer are much lower than the observed mutual diffusion coefficients. An explanation for this behavior is presented.
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  • 74
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 333-342 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effect of long-chain branching must be considered in gel permeation chromatography to evaluate the molecular weight polydispersity of branched polyethylenes. Osmotic molecular weights of fractions of branched polyethylene were correlated with elution volumes; weight-average and number-average molecular weights of a branched polyethylene were determined. Molecular weight changes on crosslinking polyethylene by ionizing radiation are accompanied by branching and cannot be simply interpreted by gel permeation chromatography.
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  • 75
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 343-360 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The results of detailed measurements of osmotic pressure, light scattering, and viscosity of poly(vinyl chloride) solutions are used to establish the molecular weight dependence of [η] and A2, to estimate the unperturbed dimensions of the poly(vinyl chloride) molecule, and to analyze critically the [η]-M correlations published hitherto.
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  • 76
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 391-393 
    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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  • 77
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 555-568 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A simple differential, isothermal calorimeter has been built to study the thermodynamics of interactions associated with a variety of polymer solution processes. The calorimeter is readily operated at temperatures ranging from ambient to about 200°C., temperature adjustments are rapid, and the apparatus is rugged enough to permit application to commercial process studies. Though less sensitive than microcalorimeters, it represents an attractive combination of satisfactory accuracy, speed, and flexibility of operation. The operation of the calorimeter is demonstrated by measurements of the heat of solution of sodium chloride in water and the heats of solution of various polyolefins in Tetralin and α-chloronaphthalene. The latter tend to confirm the presence of polymer aggregates in chloronaphthalene solutions below the thermodynamic melting temperature of the polymer.
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  • 78
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 583-596 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The optical and mechanical properties of poly(vinyl chloride) film were examined by observing both the stress and birefringence during stretching at constant rate, during relaxation at constant length and during a dynamic birefringence experiment. Experiments were also done by varying the temperature at constant length. The changes in birefringence are interpreted in terms of changes in negative distortional birefringence, changes in positive orientation birefringence, and possible reversible changes in birefringence with temperature arising from conformational changes in the polymer chain and changes in the contribution of birefringent crystals.
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  • 79
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 597-613 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dependence of crystalline morphology of isotactic polypropylene crystallized from dilute solutions on its molecular weight and growing conditions and the mechanism of crystal growth were studied by electron microscopy and electron diffraction. Lathshaped lamellar crystals 150-300 A. in thickness are obtained from fractionated polypropylene powders of Mw (average molecular weight) = 600,000 and 240,000, but not from the samples of Mw = 82,000 and 44,000, by means of isothermal crystallization at 130°C. for 20 hr. in dilute α-chloronaphthalene solution (0.005 wt.-%). Precipitation of the fractionated polypropylene sample of Mw = 82,000 from a dilute solution of carbitol gives typical dendritic crystals under the same isothermal crystallizing conditions as mentioned above. The mode of chain folding in these crystals based on the orientation and the crystal structure of the lamellar crystals agrees with that proposed by Sauer, Morrow, and Richardson. From the morphological observations, the mechanism of growth pertinent to polypropylene lamellar crystals is presumed to be as follows: fibrils at first aggregate, then the molecular chains are folded to form small lamellae, and then these small lamellae accumulate compactly to grow to large, lath-shaped, lamellar crystals.
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  • 80
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 795-798 
    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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  • 81
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 799-816 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The concentration of solvent in the gel phase of a swelling polystyrene-divinylbenzene copolymer bead has been measured as a function of the radius by optical interference techniques. It is found that an appreciable gradient exists even shortly after the core disappears. Results are presented for two cases: a very lightly crosslinked bead that exhibits negligible birefringence while swelling, and a more tightly crosslinked network in which the birefringence must be considered. It is also found that the refractive index of the unswollen bead is considerably less than that found by extrapolation from the swollen state; this effect is reasonable when the “free volume” in the bulk polymer is considered.
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  • 82
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 817-828 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dispersion of birefringence in oriented amorphous polymers is discussed. It is shown that for polystyrene, the birefringence can be considered as the product of an orientation function and a function of the wavelength of the light. This leads to a method for expressing the birefringence dispersion as a function that is characteristic of the polymer. This function is determined for polystyrene, and from it the birefringence at infinite wavelength is found to be 11% lower than that measured with the mercury green line (5461 A.).
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  • 83
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 829-838 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The molecular dimensions of polydipropylsiloxamer were studied by intrinsic viscosity measurements in toluene and in 2-pentanone. The relationships between the molecualr weight and the intrinsic viscosity were found to be: [η]25°C., toluene = 4.35 × 10-4 M0.58; [η]θ(10°C.), toluene = 1.09 × 10-3 M0.5; [η]θ(76°C.), 2-pentanone = 8.71 × 10-4 M0.5. This held reasonably well for molecular weights from 25,000 to 3000,000. The root-mean-square end-to-end length ratio, (r02/M)1/2 as calculated from the constant K, exceeds the free rotation value by approximately 100%. The disparity is greater than that found with polydimethylsiloxamer, indicating a lower degree of flexibility for the polydipropylsiloxamer. This is largely due to the short range steric interaction between near neighboring units of the chain. Gel permeation chromatography was also employed to demonstrate the lower degree of flexibility for polydipropylsiloxamer as compared with polydimethylsiloxamer.
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  • 84
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 839-852 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The present study is concerned with some network properties of polyurethane elastomers in which stability is acheived via physical crosslinkages such as microcrystallites or secondary bonding. The techniques of isothermal, thermo-, and photoelasticity have been used to gain better insight into the mechanisms which occur during the deformation of these materials. It was found that stable networks are obtained only after mechanical and thermal conditioning. The well-known stress lowering which is observed during the second deformation is manifested primarily in the entropy component of the retractive force. This implies that the stress lowering results from a reduction in the number of effective network chains and not from time-dependent effects or crystallinity changes. Depending upon the chemical structure of the material, both positive and negative energy components of the force have been found.
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  • 85
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 875-889 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An extension of the results of a previous to higher molecular weights is made. The viscoelastic parameters ηt, Je, τm, and Em are found experimentally through stress relaxation tests. The predictions of the Rouse-Bueche (RB) theory and its modified Ferry, Landel, Williams (FLW) form concerning the molecular weight dependencies of these perameters are compared with the data. It is found that the RB and FLW predictions are not rigorously obeyed.
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  • 86
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 891-898 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Living polystyrene was grafted on fractions of poly(methyl methacrylate) by an anionic grafting reaction. Unreacted polystyrene was separated by fractional precipitation. The composition of copolymer, i.e., the molecular weight of main chains and side chains, was determined. The influence of molecular weight and structure of graft copolymers on the intrinsic viscosity of solutions was examined. This may be expressed in the form [η] = KMagn. The dependence between a and n in this equation was established.
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  • 87
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 853-874 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In earlier work we have indicated a superposition principle for moderately concentrated mixtures (c ≲ 2/[η]) in good and poor solvents. By an examination of data on a number of vinyl polymers and cellulose derivatives in good as well as poor solvents, the validity of this principle is extended to concentrated solutions (c ≲ 50%). The characteristic concentration factor γ is proportional to M-a1 over the whole concentration range, with 0.47 ≤ a1 ≤ 1.10 being larger for good than for poor solvents, the result obtained earlier. Significant deviations from this relationship are noted in good solvents for those low molecular weights at which deviations from the usual intrinsic viscosity relationship occur. This may be related to the expansion factor of the polymer coil. On the basis of these results, the concentration and molecular weight dependence of the viscosity in the concentrated solution can be related to each other in terms of the parameter a1 and thus to thermodynamic characteristics. In this manner a bridge between the relatively dilute and concentrated regions is established. Currently used semiempirical expressions are analyzed in terms of these results. For the polystyrene-cyclohexane systems and θ - 9 ≦ T ≦ θ + 3, γ can be identified with the critical concentration for phase separation. Provided an “entanglement” concentration ce exists, in the neighbourhood of which the concentration dependence of the viscosity changes reapidly, γ can alternatively be shown to be proportional to ce, or ce ∝ M-a1. The temperature reduction scheme suggested earlier remains to be investigated.
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  • 88
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Molecular weight M and concentration c dependencies of the zero-shear viscosity (η) were measured over wide ranges of M and c for concentrated solutions of linear and branched poly(vinyl acetate) as well as of polystyrene under θ conditions. The log η versus log M and log η versus log c curves for a given system can be superposed by the horizontal shift along the abscissa, giving smooth master curves. From the shift factors the ratio of two exponents β and α, which appear in the following equation, can be evaluated: η = K′(cρ)αMβ, where ρ is the density of the solution and K′ is a constant at constant temperature. The evaluated values of β/α for the systems under θ conditions are equal to or very close to 0.50 as was anticipated from the previous work. The above superposition method was also applied to available viscosity data, and it was found that β/α had a good correlation with a in [η] = KMa. This indicates that the individual molecules in concentrated solutions maintain the same individuality as in dilute solutions, and might be a positive support to the packed sphere model proposed previously by the authors. The effect of solvent on the molecular weight and the concentration dependencies of viscosity was also discussed.
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  • 89
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 915-927 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The homopolymer and many of the copolymers of N-acrylylglycinamide yield thermally reversible gels in water. These systems are uniquely suitable for studying synthetic photographic gelatin substitutes and for understanding the mechanism of the gelation process. Polymerization of N-acrylylglycinamide has been studied under a variety of conditions. The homopolymer is aggregated in dilute aqueous solution and probably molecularly dispersed in 2M thiocyanate solution. At concentrations of several per cent, in water, thermally reversible gels are formed whose melting points rise with increasing concentration and increasing molecular weight. The heat of gelation crosslinking has been calculated to be -8.8 kcal./mole of crosslinks. Introduction of small amounts of carboxyl groups into the polymer raises the melting points of the aqueous gels. The effect of various organic and inorganic reagents on gelation is presented. The ability to prepare copolymers which can be flocculated has been demonstrated as well as the usefulness of the monomer in certain types of photoresist systems. Copolymerization with acrylic acid and β-aminoethyl vinyl ether has been studied, and the r1 and r2 values for these systems have been calculated as well as Q and e values for N-acrylylglycinamide.
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  • 90
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 1013-1028 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The influence of the species of counterion on the polyelectrolyte behavior and the conformation of poly-L-methionine S-methylsulfonium salts in aqueous solution was studied by viscometric, electrochemical, and optical measurements. The degree of binding of small counterions to charged polyions increases in the sequence: chloride ≲ bromide 〈 iodide 〈 thiocyanate. The conformations of chloride and bromide salts are independent of polymer concentration. On the contrary, iodide and thiocyanate salts indicate a conformational transition, probably from a random-coil conformation to an intermolecularly stabilized β-form, with the increase of polymer concentration. The results suggest the existence of a strong specific interaction between counterion and macroion in iodide and thiocyanate salt solutions at high polymer concentration.
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  • 91
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 991-1012 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Single-crystal preparations of polyethylene were treated with the selective oxidizing agent, fuming nitric acid. The degraded products were examined as regards layer thickness (by low-angle x-ray studies), chemical and weight changes, recrystallization and annealing treatments, and by broadline NMR, as part of a systematic investigation aimed at clarifying the nature of disordered material in single crystals. It emerges that there is a disordered-mobile region along the fold surface of the crystals in agreement with other parallel works along similar lines. In a more detailed analysis we can now decompose the nitric acid attack into components affecting the basal and side surfaces, respectively. Taking into account the recrystallization-annealing observations, we infer that the fold surface is heterogeneous with folds of more than one kind. These results were combined with a preliminary molecular weight distribution study by gel permeation chromatography. Taking into account all the available evidence, we are led to suggest a composite structure where surface looseness, coresponding to long loops and hairs, is superimposed on the more regular folded surface. This model is in the process of being tested. The problems concerning the assignment of a value to the amount of surface looseness are being discussed. In addition, a discontinuity in the thermal behavior of the crystals between 75 and 80°C. has been detected.
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  • 92
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 1029-1042 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: This paper is devoted to the determination of the number of intermolecular bonds in a polymer crosslinked according to the following process: (1) crosslinking in the usual isotropic state, (2) additional crosslinking of the strained primary network. The Flory equation for swelling in solvents has been modified in order to take into account the oriented state of the initial network at the time of secondary crosslinking. The combination of this equation with those relating the modulus of elasticity and the dimensions of the relaxed sample to the deformation of the primary network at the time of secondary crosslinking leads to different possible evaluations of the number of intermolecular bonds. Their significance is discussed. The equations thus established are tested with natural rubber samples vulcanized according to the above-mentioned process. The validity of the number of crosslinks thus calculated is discussed; a partial degradation of the primary network occurs during the second crosslinking. Its influence is taken into account by using the approximated equations proposed by Flory. The efficiency of the vulcanizing agent (TMTD) is consequently shown to be practically independent of the deformation of the primary network at the time of secondary crosslinking.
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  • 93
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 1043-1053 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Low-angle light-scattering patterns were obtained on ionotropic gels formed by the diffusion of Ca++ into a polygalacturonate sol. Near the sol-gel boundary, diffraction patterns were obtained which indicated organized structures with repeating units of 1100, 250, and 12.5 μ. Microscopic investigations confirmed that at this gel boundary capillaries run parallel to each other and perpendicular to the direction of diffusion. The diameter of capillaries was 12 μ while their length was in the 1000 μ range. Short interconnecting capillaries were about 200-300 μ in length. Inside the gel, in the more highly crosslinked parts, a disorientation occurs during the aging process with the partial disappearance of capillaries. However, at the gel-sol and gel-semipermeable membrane boundaries, the highly organized structures remain even during prolonged aging. The kinetics of the gel formation was also investigated.
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  • 94
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 1061-1066 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Osmotic pressures of aqueous solutions of poly(diethylaminoethyl methacrylate) hydrochloride, in equilibrium with a precipitate of the un-ionized polybase, at various concentrations of polymer and NaCl in solution and at different values of pH are derived from emf measurements and the “cell” theory for polyelectrolytes. Single-ion activities are evaluated according to two procedures. The first is based on measurements with ion-specific electrodes versus a calomel electrode. The second makes use of a salt bridge, but assumes that the co-ions have activity coefficients equal to the mean activity coefficient of the salt in a polyelectrolyte-free solution of the same concentration. The results show that the calculated values of the osmotic pressures are consistent with those obtained by the exact integration of the Gibbs-Duhem relationship, when the first procedure is employed. If, however, the single-ion activities are evaluated by the second procedure, the osmotic pressures obtained are consistently lower by about 10%. These differences arise because the two methods yield different values of the activity coefficients of the single ions.
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  • 95
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 1079-1086 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dynamic strain-optical coefficient of low-density polyethylene is found to decrease with increasing frequency and increase with increasing temperature (at temperatures up to 60°C.). It is found that a series of curves representing the real, K′, and imaginary, K″, parts of the frequency variation of the strain-optical coefficient obtained at various temperatures up to 60°C. may be superposed by translation along the frequency axis. The temperature dependence of the shift factor corresponds to an Arrhenius type equation with an activation energy of the order of 25 kcal./mole. This may be compared with the similar value obtained by Takayanagi for the αc′ mechanical loss and with the dynamic x-ray diffraction values reported by Kawaguchi et al., but is somewhat lower than the value of 34 kcal./mole reported by Onogi et al. from birefringence relaxation studies. Takayanagi has ascribed the αc′ peak to cooperative motion of crystalline and amorphous regions of the sort that might be involved in the suggested sliding of lamellae over each other. At temperatures higher than 80°C., horizontal superposition is not possible.
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  • 96
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The time-dependent birefringence has been measured simultaneously with the stress relaxation on quenched and annealed low-density polyethylene at various temperatures from 10 to 70°C. The strain-optical coefficient increases generally with increasing time, and approaches the equilibrium value, which depends upon the temperature. When the strain-optical coefficient at a fixed time is plotted against temperature, it first increases and then decreases after passing through a maximum at Tmax with increasing temperature. The higher the degree of crystallinity, the higher are the equilibrium values of the strain-optical coefficient and Tmax. The curves for strain-optical coefficient versus time and relaxation modulus versus time below Tmax can be superposed well by a horizontal shift along the abscissa. The optical shift factor obeys the original WLF equation, while the mechanical shift factor is much larger than the optical one. The molecular mechanisms corresponding to this dispersion of the strain-optical coefficient and viscoelastic αc absorption peak near Tmax are discussed.
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  • 97
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 1145-1156 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The theory of rate processes has been applied by Eyring to the plastic flow of solids, but he considers only the case of simple shear. Some assumptions concerning a generalization of this theory for an arbitrary strain tensor are here proposed and discussed. The components of the deformation and the work done by the deviator of the stress during the elementary flow process are evaluated. According to these results, it can be proved that the yield condition of Huber, Hencky, and von Mises is valid when there is no hydrostatic stress. The discrepancy between the yield stresses corresponding to tensile and compressive tests is explained by the influence of the hydrostatic component and evaluated by taking account of the amount of free volume required for an elementary jump. The calculated value agrees with the experimental data. Measurements of the inclination of Lüder's bands and deformation components on poly(vinyl chloride) flat bars strained by tensile tests are in good agreement with the proposed theory.
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  • 98
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 1157-1175 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Equations are developed for predicting the distributions of degree of substitution and block length in substitution copolymers which result when homopolymers are subjected to substitution reactions. Several different cases are treated differing in complexity from entirely random substitution to substitution affected by substituents already present on the same and on the neighboring repeat units. The equations are then applied to chlorinated polyethylene as an example of their use.
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  • 99
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 1177-1187 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The mechanism of carbon black reinforcement was studied by examining stress-strain properties of preswollen (i.e., cured in the swollen state then deswollen) SBR-1500 vulcanizates and the effect of heat treatment on such samples. It was found that the supercoiling of molecular chains leads to a purely viscous response at low elongations. On heating of preswollen samples, molecular rearrangement at the carbon black surface occurs, leading to a considerable increase in modulus. The activation energy of that process was determined by using the superposition principle.
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  • 100
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The standard methods of measuring the elastic properties of polymer melts are briefly reviewed and a method of measuring another combination of viscoelastic properties, the melt strength, is described. Data are presented on the melt strength of various types of polyethylene resins and on ionomer resins. The effects on various viscoelastic properties of branching or of the addition of fine fibrils of Teflon perfluorocarbon resin are reported.
    Additional Material: 8 Ill.
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