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  • 1985-1989
  • 1965-1969  (437)
  • 1955-1959
  • 1967  (437)
  • Physics  (429)
  • Spontaneous diabetes  (8)
  • 1
    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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  • 2
    ISSN: 1432-0428
    Keywords: Spontaneous diabetes ; Chinese hamster ; Cricetulus griseus ; Pancreas in vitro ; Insulin secretion in vitro ; Insulin secretion in diabetes ; Prediabetes ; Preclinical diabetes ; Antibodies to insulin
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé Nous avons mesuré la sécrétion d'insuline du tissu pancréatiquein vitro en présence de glucose chez 22 hamsters chinois normaux, 6 diabétiques et 8 ayant montré une glucosurie intermittente. Les valeurs obtenues ont été comparées avec l'hyperglycémie et l'insulinémie de ces mêmes animaux avant leur mort. Nous avons observé que la sécrétion insuliniquein vitro était proportionnelle au contenu en insuline du pancréas et au quotient de l'insulinémie divisée par le glucose plasmatique indépendamment de l'état métabolique de l'animal. Pourtant, la sécrétion insuliniquein vitro la plus basse a été observée chez les animaux diabétiques, et la plus élevée chez ceux qui avaient présenté une glucosurie intermittente. La relation possible de ces observations avec les théories actuelles du »pré-diabète« est discutée.
    Abstract: Zusammenfassung Die durch Glucose stimulierte Insulinsekretion wurdein vitro am Pankreasgewebe chinesischer Hamster gemessen und mit den Glucose- und Insulin-Plasmaspiegeln derselben Tierein vivo, sowie mit der Granulierung derer Inselzellen (22 normale, 6 diabetische und 8 zeitweise glykosurischer chinesischer Hamster) verglichen. Es bestand eine direkte Korrelation zwischen Insulinsekretion und Insulingehalt des Pankreas, sowie mit dem Verhältnis Insulin/Glucose im Plasma, ohne Rücksicht auf den Stoffwechsel-Zustand der Tiere. Die niedrigsten Werte wurden allerdings bei den diabetischen Tieren, und die höchstens bei denjenigen mit zeitweiser Glykosurie beobachtet. Die Bedeutung dieser Resultate in bezug auf bestehende Theorien des „Pre Diabetes“ wird diskutiert.
    Notes: Summary Insulin secretion by pancreatic tissuein vitro in response to glucose was related to plasma glucose and plasma insulin levels during life, and to the degree of granulation of the islets of Langerhans in 22 normal, 6 diabetic and 8 intermittently glycosuric Chinese Hamsters. Secretion was directly related to the insulin content of the pancreas and to the ratio of insulin to glucose in plasma, irrespective of the metabolic state of the animal, but was lowest in diabetic animals and highest in those with intermittent glycosuria. The relevance of these findings to current theories concerning “prediabetes” is discussed.
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Diabetologia 3 (1967), S. 115-123 
    ISSN: 1432-0428
    Keywords: Spontaneous diabetes ; Chinese hamster ; Cricetulus griseus ; Liver in vitro ; Diaphragm in vitro ; Heart in vitro ; Kidney in vitro ; Adipose tissue in vitro ; Glucose metabolism in vitro ; Pyruvate metabolism ; Bicarbonate metabolism ; Microangiopathy ; Prediabetes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé Nous avons étudié le foie, le diaphragme, le coeur, le rein et le tissu adipeux de 5 hamsters chinois avec diabète plus ou moins sévère, en incubant ce tissuin vitro avec du glucose uniformément marqué au14C, ou marqué en positions 1-, 2-, ou 6-, avec du pyruvate-2-14C, ou avec du bicarbonate-14C, diversement combinés. Nous avons également examiné au microscope électronique le pancréas et le rein de ces animaux. Nous n'avons pas trouvé d'indication histologique d'hypertrophie des îlots pancréatiques, le contenu en insuline du pancréas étant diminué et l'insuline plasmatique relativement diminuée également. Nous n'avons pas non plus trouvé régulièrement une microangiopathie des capillaires des îlots. Lefoie de hamsters diabétiques de type sévère ou léger incorpore moins les carbones du glucose et du pyruvate dans le CO2, le glycogène et les acides gras. De même, lemuscle des animaux avec un diabète sévère oxyde moins de glucose en CO2. Par contre, letissu adipeux des animaux diabétiques ne se distingue pas de celui d'animaux normaux, peut-être à l'exception d'une diminution d'activité du cycle des pentoses. Letissu rénal des hamsters diabétiques incorpore moins de carbbone-2 du pyruvate dans le CO2, mais son comportement est par ailleurs normal. Une réponse à l'insuline a été observéein vitro tant pour le muscle que pour le tissu adipeux, alors que les concentrations d'insuline employées étaient élevées. Malgré le petit nombre de hamsters étudiés, il est permis de conclure que ces altérations sont comparables à celles déjà observées chez des rats souffrant d'une carence insulinique chronique expérimentale. Bien qu'il ne soit pas possible d'exclure qu'il y ait eu une première phase transitoire et non détectée, caractérisée par une hypersécrétion insulinique, nous pensons plutôt que nos observations dans ce petit groupe d'animaux diabétiques sont apparentées à celles faites préalablement chez des rats avec déficience chronique en insuline induite expérimentalement.
    Abstract: Zusammenfassung Leber, Zwerchfell, Herz, Niere und Fettgewebe von 5 chinesischen Hamstern mit Diabetes verschiedenen Schweregrades wurdenin vitro inkubiert. Glucose-U, 1-, 2-, oder 6-14C, Pyruvat-2-14C und Bicarbonat-14C wurden in verschiedenen Kombinationen als Substrat verwandt. Pankreas und Niere wurden elektronenmikroskopisch untersucht. Eine Hypertrohpie der Pankreasinseln war histologisch nicht nachweisbar. Extrahierbares Insulin war vermindert und Plasma-Insulinwerte verhältnismäßig niedrig. Eine regelmäßige Mikroangiopathie der Inselkapillaren konnte nicht beobachtet werden. Sowohl die leicht- als auch die schwer-diabetischen Hamster zeigten einen verminderten Einbau von Glucose- sowie von Pyruvat-Kohlenstoff in CO2, Glykogen und Fettsäuren durch dieLeber. Eine herabgesetzte Oxydation von Glucose zu CO2 durch denMuskel war zumindest in schwer-diabetischen Tieren nachweisbar. Der Stoffwechsel desFettgewebes war durch den Diabetes nicht beeinflußt; die Aktivität des Pentosezyklus war möglicherweise herabgesetzt. DasNierengewebe des diabetischen Hamsters zeigte einen geringeren Einbau vom C-2 des Pyruvats in CO2, jedoch konnten sonst keine biochemischen Veränderungen festgestellt werden. Muskel- und Fettegewebe sprachen imin vitro Versuch auf relativ hohe Insulinkonzentrationen gut an. Die Resultate, die wir aus den Untersuchungen einer begrenzten Anzahl von Hamstern erhielten, entsprechen somit früheren Beobachtungen bei Ratten mit experimentell bedingtem chronischen Insulinmangel. Es besteht allerdings die Möglickeit, daß uns eine vorübergehende frühere Phase mit Hypersekretion von Insulin unbemerkt entging.
    Notes: Summary Liver, diaphragm, heart, kidney, and adipose tissue of five Chinese hamsters with diabetes of varying severity have been studied by incubationin vitro with glucose-U-, 1-, 2-, or 6-14C, pyruvate-2-14C, and bicarbonate-14C in various combinations. The pancreas and kidney were examined by electron microscopy. There was no histologic evidence of hypertrophy of the pancreatic islets; extractable insulin was reduced, and plasma insulin was relatively reduced. There was no consistent microangiopathy of insular capillaries. Both the mild and severely diabetic hamsters had a reduction in the incorporation of the carbons of glucose and of pyruvate into CO2, glycogen, and fatty acids in theliver, and, at least in severely diabetic animals, of oxidation of glucose to CO2 in muscle. There was no change consequent to diabetes in the metabolism ofadipose tissue, except for a possible decrease in pentose cycle activity. Thekidneys of the diabetic hamsters had less incorporation of carbon-2 of pyruvate into CO2, but otherwise no biochemical changes were evident. Both muscle and adipose tissue were responsivein vitro to insulin when tested with greater physiologic amounts. While the possibility cannot be excluded that a transient earlier phase with hypersecretion of insulin escaped detection, the changes in this limited number of diabetic hamsters parallel those previously found in rats with experimental chronic deficiency of insulin.
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Diabetologia 3 (1967), S. 135-139 
    ISSN: 1432-0428
    Keywords: Spontaneous diabetes ; Sand rat ; Psammomys obesus ; Insulin in serum ; Insulin in pancreas ; Insulin resistance ; Adipose tissue in vitro ; Obesity ; Diet and diabetes ; Fasting
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé Nous avons induit par modification du régime chez le rat des sables égyptien un syndrome diabétique plus modéré que celui décrit dans la précédente communication (Miki et al., 1966). Maintenus à un régime végétal pendant une longue période après leur capture, la teneur en insuline du pancréas de ces animaux augmente de façon significative. Par contre, lorsqu'ils sont soumis au régime standard de laboratoire (granuléscomprimés) une hyperglycémie de degré variable s'installe chez environ un tiers des jeunes rats. L'hyperinsulinémie s'est révélée être encore plus élevée chez ces animaux que chez ceux décrits antérieurement et elle persiste même après un retour à la normale de la glycémie au cours du jeûne. Chez les rats hyperglycémiques, le contenu du pancréas en insuline diminue. Le rôle possible de la résistance du tissu adipeux à l'action de l'insuline dans la pathogénèse de ce syndrome est discuté.
    Abstract: Zusammenfassung Eine mildere Form von diätinduziertem diabetischen Syndrom in der Ägyptischen Sandratte wird beschrieben. In Sandratten, die für längere Zeit nach der Gefangennahme mit Gemüse gefüttert worden waren, war der Pankreasinsulingehalt stark erhöht, der Blutzucker aber normal. Ein Drittel der jungen Tiere, hingegen, die mit Labor-Keks gefüttert wurden, entwickelte Hyperglykämie verschiedenen Grades. Hyperinsulinämie war sogar noch stärker ausgeprägt, als in der vorher beschriebenen Gruppe (Miki et al., 1966) und dauerte selbst dann an, wenn der Blutzucker durch Fasten auf normale Werte zurückgebracht wurde. Der Pankreasinsulingehalt hyperglykämischer Sandratten war gegenüber der Norm erniedrigt. Die Insulinempfindlichkeit des Fettgewebes wird im Zusammenhang mit der Pathogenese diskutiert.
    Notes: Summary Compared with our previous report, a milder form of diabetic syndrome induced by diet in Egyptian sand rats is described. In sand rats fed vegetables for a prolonged period after capture, pancreatic insulin content was significantly increased. When fed chow, one-third of young animals developed hyperglycemia to a variable degree. Hyperinsulinemia was even more marked than in the previously reported group (Miki et al., 1966) and persisted even when the blood glucose returned to normal following fasting. Pancreatic insulin content was decreased in hyperglycemic sand rats. Insulin refractoriness of adipose tissue was discussed in relation to the pathogenesis.
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  • 5
    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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  • 6
    Electronic Resource
    Electronic Resource
    Springer
    Diabetologia 3 (1967), S. 65-73 
    ISSN: 1432-0428
    Keywords: Spontaneous diabetes ; Chinese hamster ; Cricetulus griseus ; Retina anomalies ; Testicular function ; Free fatty acids ; Glycoproteins ; Mucopolysaccharides
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé Plusieurs chercheurs ont utilisé les hamsters chinois de notre colonie pour leurs observations expérimentales et nous rapportons ici les résultats de plusieurs études. — Le groupe du Dr. H.R.Hautsler, initiateur de la colonie à Toronto, a étudié les altérations de la rétine chez les animaux présentant un diabète spontané ou un diabète de type métahypophysaire résultant de l'injection d'hormone de croissance et de cortisone. Des anévrismes artériolaires et capillaires sont observés chez quelque 30% des animaux avec diabète métahypophysaire, mais sporadiquement seulement chez les hamsters avec diabète spontané. — Le groupe du Dr. K.Schöffling a étudié les biopsies du tissu testiculaire. Proportionnellement à la gravité du diabète, on trouve chez les hamsters présentant un diabète spontané une inhibition de la spermatogénèse, avec réduction de lépaisseur de l'epithélium germmal et élargissement de la lumière des tubules séminifères. Les cellules de Leydig sont également réduites en nombre. L'apparence histologique ressemble à celle du tissu testiculaire de diabétiques humains. — Le groupe du Dr. J.Campbell a mesuré les taux d'acides gras libres (AGL) du sérum de hamsters chinois non-diabétiques. Ceux-ci dépassant de 4 à 9 fois (3 à 5 mEq/l) les taux observés chez le chien, le rat ou l'homme, des taux semblables ayant pourtant été mesurés chez le hamster doré. Le tissu adipeux épididymaire de hamsters chinois ne diffère pas de celui du rat par son contenu en lipides, mais il libère davantage de AGL dans le milieu d'incubation. Les hamsters chinois non-glucosuriques sont sensibles à l'action diabétogène de la cortisone, mais non pas à celle de l'hormone de croissance de mouton. La cortisone s'est montrée très active quant à son action hyperglycémique, accompagnée d'une élévation des taux d'insuline sérique et des taux d'AGL. — Dans notre propre laboratoire, nous avons mesuré les concentrations en glycoprotéines du plasma et le contenu en mucopolysaccharides de la peau de hamsters non-diabétiques, avec glycosurie intermittente, ou franchement diabétiques. Nous n'avons pas observé, de différences entre ces trois groupes d'animaux quant au profil immuno-électrophorétique, ou la concentration en composantes hydrocarbonées des protéines plasmatiques. La substance basale de la peau de hamster diabétique contient davantage de mucopolysaccharides que celle des animaux non-diabétiques du même âge. C'est ainsi que le contenu en acides uroniques de la peau d'un groupe de hamsters, avec un sucre sanguin à jeun de 60 mg% en moyenne, était de 579 μg par g de tissu sec, alors qu'il était de de 882μg pour un groupe d'animaux avec un sucre sanguin à jeun de 107 mg% en moyenne.
    Abstract: Zusammenfassung Mehrere Forscher haben mit Tieren aus unserer Kolonie gearbeitet, und dieser Bericht betrifft eine Reihe von verschiedenen Resultaten. — Dr. H.R.Hausler und Mitarbeiter haben die Kolonie in Toronto begonnen und sich hauptsächlich mit Veränderungen in der Retina von spontandiabetischen Tieren befaßt. Sie haben ebenfalls Beobachtungen gemacht bei Tieren mit Diabetes von metahypophysärem Typ, also nach Injektion von Somatotropin und Cortison. Aneurysmata der Arteriolen und Kapillaren wurden in etwa 30% der Tiere mit metahypophysärem Diabetes beobachtet, nur vereinzelt aber bei spontandiabetischen Hamstern. — Dr. K.Schöffling und Mitarbeiter haben die Veränderungen in Hodenbiopsien geprüft. In direktem Zusammenhang mit der Schwere des Diabetes findet man bei spontandiabetischen Hamstern verschieden ausgeprägte Hinweise auf inhibierte Spermatogenese, mit Verminderung der Zellzahl des germinalen Epitheliums und Erweiterung der Lumina der Tubuli seminiferi. Auch die Zahl der Leydig-Zellen ist vermindert, und das histologische Bild ist allgemein demjenigen beim Diabetiker ähnlich. — Dr. J.Campbell und Mitarbeiter haben bei nicht-diabetischen chinesischen Hamstern freie Fettsäuren (FFS) gemessen und haben beobachtet, daß deren Konzentration im Serum 4 bis 9 mal höher liegt (3 bis 5 mVa/l) als beim Hund, bei der Ratte und beim Menschen. Ähnlich erhöhte Werte findet man aber auch beim Goldhamster. Epididymales Fettgewebe von Ratten und chinesischen Hamstern enthielt etwa gleich viel Fett, aber das Fettgewebe chinesischer Hamster mobilisiertein vitro mehr FFS. Bei nichtdiabetischen Hamstern war Cortison diabetogen, nicht aber Somatotropin vom Schaf. Die Verabreichung von Cortison führte zu erhöhten Zuckerwerten, zu erhöhtem Seruminsulin und zu sehr hohen FFS-Konzentrationen. — In unserem eigenen Laboratorium haben wir den Gehalt an Glucoproteinen im Plasma und an Mucopolysacchariden in der Haut bestimmt, und zwar in nicht-diabetischen, in nur zeitweise glucosurischen, und in klinisch deutlich diabetischen Hamstern. Zwischen diesen drei Gruppen von Tieren ließen sich keine Unterschiede bezüglich auf immunoelektrophoretische Verteilung oder auf Zuckergehalt einzelner Komponenten der Plasmabestandteile nachweisen. Die Haut diabetischer Hamster enthielt aber mehr Mucopolysaccharide als diejenige nicht-diabetischer Hamster gleichen Alters. Hamster, deren Nüchternblutzuckerwerte bei 60mg% lagen, wiesen einen Uronsäuregehalt von 579 μg per g Trockengewebe auf, während der entsprechende Wert bei Tieren mit durchschnittlich 107 mg% Blutzuckernüchternwert 822μg war.
    Notes: Summary Several investigators have used Chinese hamsters from our colony for experimental work, and results of various studies are reported. — The group of Dr. H.R.Hausler, who initiated the colony in Toronto, studied retinal changes in spontaneously diabetic animals and also in hamsters with the metahypophyseal type of diabetes, following serial injections of growth hormone and cortisone. Arteriolar and capillary aneurysms were found in about 30% of the animals with metahypophyseal diabetes, but only sporadically in spontaneously diabetic hamsters. — The group of Dr. K.Schöffling studied alterations of testicular tissue in biopsy material. Corresponding to the severity of the disease, spontaneously diabetic hamsters showed various degrees of inhibited spermatogenesis, resulting in a reduction of the thickness of the germinal epithelium and widening of the lumina of the seminiferous tubules. There was also a reduction in the number of Leydig cells. The overall histological picture resembled that of the testes of the diabetic human patient. — The group of Dr. J.Campbell measured concentrations of serum free fatty acids (FFA) in nondiabetic Chinese hamsters and found the levels 4 to 9 times higher (3 to 5mEq/l) than in dogs, rats and man, but similar to FFA levels of Syrian hamsters.Epididymal fat pads of rats and Chinese hamsters showed similar lipid contents, but the latter released more FFA into the incubation medium. Nonglycosuric hamsters were susceptible to the diabetogenic effect of cortisone, but not to ovine growth hormone. Cortisone was most effective in producing a high blood sugar and elevated serum insulin and FFA concentrations. — In our own laboratory, the concentration of glycoproteins in plasma and the mucopolysaccharide content of the skin were determined in nondiabetic, occasionally glycosuric and frankly diabetic hamsters. There was no difference amongst the three groups of animals with regard to either the immunoelectrophoretic pattern or the concentration of individual carbohydrate components of plasma proteins. Skins of diabetic hamsters contained more mucopolysaccharide in their ground substance than skins of nondiabetic animals of comparable age. Hamsters with a mean fasting blood sugar value of 60 mg% showed a uronic acid content of 579μg per g of dry tissue, whereas animals with a mean fasting blood sugar of 107 mg% had 822μg.
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  • 7
    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.
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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    Diabetologia 3 (1967), S. 124-129 
    ISSN: 1432-0428
    Keywords: Spontaneous diabetes ; Chinese hamster ; Cricetulus griseus ; Inheritance of diabetes ; Genetics of diabetes ; Polygenic system of inheritance
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé 1. Nous avons analysé les pedigrees et les estimations de glucosurie (Tes-Tape) de plus de 6000 hamsters chinois de la colonie du Best Institute à Toronto et de celle de la maison Upjohn à Kalamazoo. A Toronto, la distribution des estimations au Tes-Tape était de 23%+, de 6%++, 3%+++, et de 5%++++. L'incidence du diabète a augmenté durant les 11 premières générations de consanguinité, elle a légèrement diminué par la suite L'incidence du diabète est plus grande dans la colonie Upjohn, les nichées étant plus petites et le nombre des morts avant sevrage plus grand. Lorsqu'un ou deux parents sont diabétiques, 40% des rejetons ne survivent pas; 14% seulement, lorsque les deux parents ne sont pas diabétiques. Par rapport à tout autre type d'accouplement, les parents non-diabétiques donnent naissance à un nombre légèrement moindre de diabétiques et nettement moindre d'animaux à faible glucosurie. — 2. Nous concluons de ces données que le diabète du hamster chinois est héréditaire mais qu'aucun système simple de transmission n'est à même de cadrer avec elles. C'est pourquoi nous proposons un système composé d'un minimum de 4 gènes dont la coïncidence de deux en homozygocité récessive mène à un diabète patent. Le nombre des possibilités données par un système récessif quadruple associé à la moindre capacité de survie des diabétiques permet de prévoir que le croisement diabétique x diabétique ne produira des diabétiques qu'une fois sur 6. — 3. Les polygènes agissent sur divers systèmes physiologiques et non pas sur un gène diabétique »caché«. Le syndrome diabétique est le résultat de l'action de ces gènes sur la production d'enzymes, la prolifération des cellules, la perméabilité des membranes et le métabolisme de différents tissus. Aussi nous ne devrions pas nous attendre à ce que tous les hamsters diabétiques se ressemblent et soient caractérisés, par exemple, par une rétinopathie ou une hydronéphrose, mais une plus grande fréquence de manifestations semblables est probable pour chaque lignée.
    Abstract: Zusammenfassung 1. Von über 6000 Hamstern der Kolonie des Best Instituts in Toronto und der Upjohn-Kolonie in Kalamazoo wurden die Stammbäume und Tes-Tape-Ergebnisse geprüft. Dabei ergab sich, daß in der Best'schen Kolonie mit Tes-Tape 23%+, 6%++, 3%+++ und 5%++++ reagierten. Während der ersten 11 Generationen Inzucht stieg das Vorkommen von Diabetes an und fiel danach leicht ab. In der Upjohn-Kolonie, wo das Auftreten von Diabetes häufiger war, waren die Würfe kleiner und die Sterbeziffer unter den noch nicht entwöhnten Jungen höher. Wenn einer oder beide Elternteile diabetisch waren, starben 40% der Jungen im Gegenteil zu 14% bei anderen Paaren. Normale Eltern hatten im allgemeinen weniger diabetische Junge, und die Zahl der Tiere, die nur Spuren Glucose im Urin aufwiesen, war wesentlich geringer als bei anderen Paarungstypen. — 2. Daraus wurde geschlossen, daß Diabetes beim chinesischen Hamster zwar erblich ist, daß die Ergebnisse aber nicht in ein einfaches Vererbungsschema einzugliedern sind. Es wird ein polygenetisches System vorgeschlagen, mit mindestens 4 Genen, von denen jeweils die Homozygotie von zwei Diabetes hervorruft. Wegen der Möglichkeiten, die sich aus den 4 rezessiven Genen ergeben, sowie wegen der geringeren Überlebenskraft der zu Diabetes Prädisponierten, erzeugt eine Paarung von 2 Diabetikern nur in einem Fall von sechs ebenfalls einen Diabetes. — 3. Die Polygene wirken auf verschiedene physiologische Systeme und nicht auf ein „ruhendes“ diabetisches Gen. Das diabetische Syndrom ist das Ergebnis der Wirkung dieser Gene auf Enzymproduktion. Zellwachstum, Membrandurchlässigkeit und allgemeinen Stoffwechsel in den verschiedenen Geweben. Daher ist nicht zu erwarten, daß alle diabetische Hamster Retinopathie oder Hydronephrose aufweisen, jedoch ist zu erwarten, daß die gleichen Erscheinungsmerkmale innerhalb eines Zuchtstammes gehäuft auftreten.
    Notes: Summary 1. The pedigrees and Tes-tape scores of over 6000 hamsters in the Best colony in Toronto and the Upjohn Colony in Kalamazoo were examined. It was found that the distribution of Tes-tape scores in the Best colony was 23%+, 6%++, 3%+++, and 5%++++. The incidence of diabetes rose for the first eleven generations of inbreeding then fell off slightly. In the Upjohn colony, which had a higher incidence of diabetes, the litter sizes were smaller and the pre-weaning deaths greater. When one or both of the parents were diabetic 40% of the young died as opposed to 14% for other matings. Non-diabetic parents produced slightly less diabetics and significantly less trace animals than did any other type of mating. — 2. It was concluded that diabetes is inherited but that no simple system of inheritance will fit the data. A polygenic system is postulated with a minimum of four genes any two of which when homozygus recessive will cause diabetes. Because of the variety of the quadruple recessive and the lower viability of diabetics, the mating diabetic x diabetic will breed true one mating in six. — 3. The polygenes act on various physiological systems and not on a “dormant” diabetic gene. The diabetic syndrome is the result of the action of these genes on enzyme production, cell proliferation, membrane permeability, and general metabolism, in various parts of the body. Thus one would not expect all diabetic hamsters to exhibit retinopathy or hydronephrosis, but one would expect predominantly the same manifestations within the same subline.
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  • 9
    Electronic Resource
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    New York : Wiley-Blackwell
    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
    Additional Material: 1 Ill.
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  • 10
    Electronic Resource
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    New York : Wiley-Blackwell
    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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  • 11
    Electronic Resource
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    New York : Wiley-Blackwell
    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.
    Additional Material: 3 Ill.
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  • 12
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The crystallization kinetics and morphology of poly(tetramethyl-p-silphenylene)siloxane spherulites have been investigated over a temperature range of 25-130°C. The effect of molecular weight on the spherulitic growth rates, ranging from the monomer to molecular weights about 106, is discussed in terms of conventional rate theory. Surface free energies of crystal growth are computed on the basis of a spherulitic model in which the polymer chains are presumed to be incorporated within the lamellar crystallites which are comprised in the spherulites. Mention is made of the change in mechanical properties with molecular weight.
    Additional Material: 8 Ill.
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  • 13
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    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 113-123 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The depolarized light intensity (DLI) technique detec's transitions in birefringent materials by simultaneously measuring sample temperature and intensity of polarized light roatated by the sample. Most polyolefins in the solid state rotate 30-40% of the polarized light. At any temperature at which the sample exhibits an ordered state, some rotation occurs. Temperatures of transitions and changes in refractive index can be determined in this way. Many of these transitions can also be followed by the well-known method of differential thermal analysis (DTA). A comparison of DLI and DTA curves of polyethylene, polypropylene, mixtures of these polymers, and block copolymers of ethylene and propylene shows the two techniques to be complementary and of use in determining the physical behavior of these polymers. Instrumentation and system variables of the DLI technique are discussed.
    Additional Material: 8 Ill.
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  • 14
    Electronic Resource
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    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 101-112 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The weight-average molecular weights of polymers of acrylonitrile prepared by a free-radical initiator and an organometallic catalyst have been determined by lightscattering measurements in N,N-dimethylformamide, dimethyl sulfoxide, and dimethylacetamide at 25°C. and in dimethyl sulfoxide at 140°C. The apparent molecular weights of the polymers prepared with the NaAlEt3S(i-Pr) catalyst in DMF at -78°C. (referred to as high-melting polymers) changed from 54,800, 82,700, and 480,000 when measured in DMF at 25°C. to 36,000, 41,600, and 225,000 when measured in DMSO at 140°C., whereas the molecular weights of the free-radical polymers remained unchanged. Furthermore, from results obtained in DMSO at 140°C., The intrinsic viscosity-molecular-weight relationships were found to be identical for the high-melting and the free-radical polymer and in substantial agreement with an equation reported by Cleland and Stockmayer. The apparent decrease in molecular weight of the high-melting polymer from 25 to 140°C. indicates rather clearly that the high-melting polymers are associated in DMF at 25°C. The “aggregates,” even though present only at low concentrations, raised the weight-average molecular weight markedly but affected the number-average molecular weight only slightly, thus giving a high M̄w/M̄n ratio. It appears likely that when temperature and solvent are such that association does not occur, linear PAN's will have approximately the same intrinsic viscosity-molecular weight relationship (subject of course to slight change by polydispersity). The often reported abnormal molecular weight of samples prepared by solution polymerization especially at low temperatures, may be attributed to branching, or to an association, as reported here. The nature of association of PAN in dilute solution is also discussed.
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  • 15
    Electronic Resource
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    New York : Wiley-Blackwell
    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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  • 16
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    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 263-270 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The adsorption of iodine by rayon tire yarn samples from aqueous solutions in which the concentration of iodide and triiodide ions is suppressed was studied. Fowler and Guggenheim's model of adsorption on regular localized monolayers appeared to be applicable to the adsorption phenomena considered. It is concluded that adsorption takes place on patches of sites in the cellulose-water gel.
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  • 17
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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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  • 18
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 663-670 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Current network theory exhibits inconsistencies which show up particularly clearly in deformation of networks prepared by crosslinking a polymer in solution. A check of theory can be obtained if one knows precisely the number of crosslinks in the network and if a range of deformations is applied to the network. In an effort to explore this problem we have examined the relation of shear modulus to crosslink density, primary molecular weight, and polymer concentration for a series of poly(vinyl alcohol) gels at low to intermediate concentrations. Aqueous poly(vinyl alcohol) solutions were crosslinked to form infinite networks using terephthalaldehyde. We find a large discrepancy with these poly(vinyl alcohol) gels between measured shear modulus and that calculated from classical elasticity theory assuming quantitative reaction of crosslinking. The ratio of measured to calculated modulus is independent of crosslink density for a given primary molecular weight and concentration. It shows linear dependence on polymer concentration prior to crosslinking and extrapolates to a critical concentration which is consistent with the effective sizes of the polymer molecules.
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  • 19
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 671-684 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The rate of water sorption at 25°C. has been determined for a number of polyacetal films differing in structure, density, and orientation induced by extrusion. The equilibrium water uptake was found to be a linear function of density only; no other effect of structure or orientation was detectable. The extrapolated density for zero sorption was 1.51 g./cc., not far from the theoretical crystalline density. The diffusivity of water in unoriented films rose with decreasing density; for linear copolymer, the trend was parallel to that of the area under the dynamic mechanical loss peak associated with long-range chain motions in the disordered regions (β-transition). Less pronounced effects of molecular weight and long chain branching on diffusivity were also noted. Films crystallized while an extruded melt was still oriented showed considerable increases in water diffusivity, but no significant changes in the apparent activation energies of permeation (about 6.6 kcal./mole) or diffusion (about 11.5 kcal./mole). On annealing these films, the diffusivity remained almost constant while the sorption coefficient and retraction on remelting decreased.
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  • 20
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    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 685-696 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The cavity model used in the theory of dielectrics was applied to hydrodynamics to calculate the force exerted by a system of soft dumbbells on a reference dumbbell in a hydrodynamic field. The influence of this force on the viscosity and flow birefringence and its dependence on both the concentration and velocity gradient were calculated. The system of equations has a real solution only for values of β = M[η]η0γ/RT which are smaller than a critical value rapidly decreasing with increasing concentration. At zero concentration the results obtained agree with the theory of a single isolated dumbbell model. The calculated Huggins constant is k′ = 0.4. The extinction angle is connected with the relative viscosity very nearly as derived from experiments. However, the theory fails at higher concentrations and gradients yielding an increase in viscosity with the gradient and infinite zero-shear viscosity for the concentration c = 2.5/[η].
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  • 21
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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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  • 22
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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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  • 23
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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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  • 24
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 1103-1118 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Data on wettability of elastomers should be considered basic to the understanding of all phases of elastomer adhesion. However, no such data in the form of critical surface tensions were available for elastomers other than polydimethylsiloxane. For this study, 18 elastomers were selected to determine the effects of functional groups, of geometrical and structural isomerisms, of copolymerization, and of the induced orientation upon wettability. Most results support the constitutive law of wettability established by Shafrin and Zisman. The effect of structural isomerisms in the form of a vinyl side group and cyclization is discussed. An equation for the calculation of critical surface tension of a copolymer or of a mixture of isomers is proposed as follows: \documentclass{article}\pagestyle{empty}\begin{document}$ \gamma _c {\rm (copolymer or mixture of isomers)} \simeq \sum\limits_1^\infty {N_i \gamma _{c_i } } $\end{document} where Ni is the mole-fraction of the individual monomer in the copolymer and \documentclass{article}\pagestyle{empty}\begin{document}$ \gamma _{c_i } $\end{document} is the critical surface tension of each homopolymer. Most elastomer adhesion studies conducted in the past were concerned with the diffusion theory of adhesion. This study further supports the conclusion on the role of diffusion and adsorption in adhesion advanced in Part I, especially with respect to the physical state of polymer at the time of application. The wettability data in this study could shed some light upon major basic mechanisms involved in elastomer reinforcement.
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  • 25
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 1119-1144 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Experimental data obtained from stress-strain curves of five different textile fibers, at a series of different, constant strain rates covering a range of 61/2 decades have been used to study two methods of nonlinear viscoelastic analysis proposed elsewhere. According to the first of these, time and strain effects are factorizable so that stress σ, strain ε and time t are related by the equation σf1(ε)/ε = f(t),. This is shown to be unsatisfactory with the present materials, but an empirical modification to σf1(ε)/ε = f2(ε) + f(t) is satisfactory. According to the second, general nonlinear viscoelastic behavior can be described by an equation which reduces to the form σ/ε = F1(t) + εF2(t) + ε2F3(t) + when applied to extension at a constant strain rate. This series is shown to be strongly divergent except at fairly small stains. In fact, if it is truncated after about three terms, which are as many as can be estimated with any significance in the present experiments, it is applicable only to strains of about 3-4% and less. Numerical techniques which enable standard statistical procedures to be used have been devised to perform the above analyses and are described in detail.
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  • 26
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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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  • 27
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 1317-1319 
    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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  • 28
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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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  • 29
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 143-156 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The small-strain mechanical behavior of crystalline polyethylene has been studied by using a microstrain technique with strain resolution on the order of 10-6. The strain rate was varied from 10-6 to 10-4 sec.-1, and a temperature range of 17-28°C. was investigated. A strong dependence on strain rate and temperature has been observed for the following parameters which characterize the mechanical response of polyethylene in the microstrain region: the initial modulus of the stress-strain curve, the deviation in strain from ideal linear elastic behavior at a given stress amplitude, and the energy dissipated in a deformation cycle. The Young's moduli that were observed by means of tensile tests in the microstrain region were only about 20% lower than the values reported in other investigations at kilocycle and megacycle frequencies. The experimental method made it possible to isolate a deformation process which was attributed to a crystallographic shear mechanism corresponding to a yield point of 27 psi. This shear mechanism is discussed in terms of the various shear processes, such as slip, twinning, and the orthorhombic-monoclinic phase change.
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  • 30
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 157-164 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The rates of growth of single ozone cracks have been measured for vulcanizates of two butyl rubbers over the temperature range of 20-160°C. Over most of this range the rates are quantitatively related to the segmental mobility of the polymer and depend upon temperature in accord with the appropriate from of the WLF relation. The rates are also proportional to the concentration of ozone. It is therefore concluded that diffusion of ozone into the polymer before reaction is the rate-controlling step. This is contrasted with the behavior of butadiene-styrene copolymers, for which the rates of crack growth are also quantitatively related to the segmental mobility, but the rates are somewhat larger at equivalent mobilities and the dependence upon ozone concentration is smaller. The difference is attributed to different penetration distances before reaction in polymers containing low and high densities of reactive sites.
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  • 31
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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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  • 32
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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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  • 33
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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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  • 34
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 377-390 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The concentrations and the growth rates of high- and low-melting type spherulites of trans-1,4-polyisoprene were measured in the temperature range 39-49°C. It was shown that above about 40°C., the crystallization rate of trans-1,4-polyisoprene is determined primarily by the radial growth rate of high-melting form (HMF) spherulites, whereas the predominance of the low-melting form (LMF) crystals below 40°C. can be attributed to the high rate of formation of LMF primary nuclei at lower crystallization temperatures. Temperature-independent rate parameters were calculated from optical and dilatometric measurements and were found to be in good agreement. Both the change in nucleation habit and spherulite growth rate with temperature can be explained on the basis of a lower end surface free energy of LMF crystals of trans-1,4-polyisoprene compared to that of the HMF crystals.
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  • 35
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 397-397 
    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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  • 36
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 417-424 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The length of the span of the terephthaloyl residue in poly(ethylene terephthalate) guarantees independence of the conformations of successive repeating units of the chain. Interactions within units of the chain are amenable to interpretation by comparisons with related polymers; cis and trans conformations of the terephthaloyl residue are given equal weighting. The mean-square dimension ratio (〈r2〉0/M)∞ estimated on this basis is in substantial accord with the value deduced from experiments.
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  • 37
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 425-429 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The error analysis for the transient vibrating reed test is developed based on a linearized approximation. Tables are given for the efficient utilization of the equations in evaluating the accuracy range of test data.
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  • 38
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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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  • 39
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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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  • 40
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 431-454 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The relationships between molecular weight distribution and structure in polymerizations with long-chain branching were reviewed and extended. Results were applied to an experimental examination of intrinsic viscosity in polydisperse, trifunctionally branched systems. Several samples of poly(vinyl acetate) were prepared by bulk polymerization under conditions of very low radical concentration. The relative rate constants for monomer transfer, polymer transfer, and terminal double-bond polymerization were established from the variation of Mn and Mw with the extent of conversion. Average branching densities were then calculated for each sample and ranged as high as 1.5 branch points/molecule. Intrinsic viscosities [η]B were measured in three systems: a theta-solvent, a good solvent, and one that was intermediate in solvent interaction. These results were compared with calculated viscosities, [η]L, which would have been observed if all the molecules had been linear. The values of [η]B/[η]L were substantially the same in all three solvents. The variation of this ratio with branching density was compared with the theory of Zimm and Kilb as adapted to polydisperse systems. Discrepancies were noted, and the adequacy of present model distribution functions for branched polymers was questioned.
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  • 41
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 455-460 
    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 size and shape of the torsional potential upon the theoretical temperature coefficient (T∂ ln 〈r02〉/∂T) of a polymeric chain was studied. The uncorrelated end-to-end distance equations for isotactic, syndiotactic, and completely atactic chains were differentiated with respect to temperature and the integrals in the resulting equations were evaluated by the method of Gaussian quadrature. The calculated coefficients were found to be nonlinear functions of the energy ratio Umax/KT, where Umax is the maximum potential barrier and possess real roots which critically depend upon the size and shape of the potential. Qualitative anomalies between experiment and theory disappeared when the entire torsional potential was used in the conformational theory. It appears that quantitative agreement between theory and experiment can be established for polymeric materials if the entire potential is used, rotations within bulky side groups are included, and the potential is determined by the method of minimum conformational energy.
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  • 42
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 493-509 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effects of thermal treatment at temperatures in the 177-250°C. range for 2 hr. on solution-grown single crystals of poly-4-methylpentene-1 have been studied by using electron microscopy. Crystals were grown both from 0.02% pentyl acetate solution at 110°C. and from 0.02% toluene solutions at temperatures less than 80°C. A number of distinct types of crystals have been obtained in the same or in separate solutions depending on the crystallization conditions. These crystals have some morphological characteristics in common such as a square outline with well-defined faces. The contrasting features include such things as a marked difference in relative size, with the smaller crystals showing extensive overgrowth and collapse markings. Observations by means of differential scanning calorimetry (DSC) on the melting behavior of these various crystals show the presence of distinct and characteristic melting points. The effects of a given thermal treatment depend on the type of crystals used, with the larger crystals showing greater stability. The first effects are the appearance of lines, notches at the edges, and holes. An increase in temperature results in an increase in these effects with the formation of fibrillar structures. Consideration is given to the influence of molecular conformation and molecular chain folding on the observed results.
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  • 43
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 547-554 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A calibration plot of the intrinsic viscosities of poly(vinyl chloride) fractions against elution volumes gives a good correlation between the first moments, i.e., mean elution volumes, and intrinsic viscosities of poly(vinyl chloride) whole polymers. This is evidence that column permeation of chain macromolecules is governed by some sort of hydrodynamic size in a manner akin to that in which hydrodynamic size affects capillary viscosity measurements.
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  • 44
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 569-581 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Data obtained from the calibration of GPC columns of different permeabilities with standard polystyrenes are reported. For single columns the logarithm molecular weight-elution volume plot is linear for approximately one and one-half decades in molecular weight. GPC separations are such that the separability of two samples of similar molecular weight improves as their mean molecular weight decreases. Because of this the analysis of high molecular weight polymers can best be accomplished on a series of columns in which each column has a high permeability limit. The elution volume for columns in series is shown to be the sum of the elution volumes of the individual columns. As higher molecular weights are eluted a pronounced tailing effect is observed.
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  • 45
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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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  • 46
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 623-631 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The thermodynamic properties of amorphous polyethylene are calculated from a model based on the method of significant structures. The motion of a molecule as a whole is described by the motion of segments, each segment moving independently of all others. It is assumed that on melting, holes appear in the solid lattice and the segments can move into these vacancies, obtaining some gaslike degrees of freedom. The complete frequency distribution for polyethylene is used for the solidlike degrees of freedom, while a corrected classical partition function is used for the gaslike degrees of freedom. The calculated thermodynamic properties are in reasonable agreement with experimentally determined values, assuming each gaslike segment to consist of 20 CH2 groups.
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  • 47
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 633-637 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Equations for the time course of depolymerization of long-chain polymers are derived by the method of randomization of a parameter for the case in which all bonds have equal probability of cleavage. This yields some gain in insight and avoids the necessity for solving systems of differential equations.
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  • 48
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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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  • 49
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 771-780 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The activity coefficient γNa+, of sodium ion, in aqueous solutions of both isotactic and conventional poly(methacrylic acid) (PMA) has been studies throughout the whole range of degree of neutralization α with a Beckman Na electrode and membrane electrodes. The results show that the fraction of sodium ions bound to isotactic PMA is higher than that bound to conventional (or syndiotactic) PMA over the entire range of α. The binding of divalent counterions (Mg+2, Cu+2, Co+2, and Ni+2) by the two forms of PMA (at α = 0.95) has been evaluated from the release of Na+ ions with the Beckman Na electrode. Turbidimetric determinations of the critical amount of various divalent cation chlorides necessary to bring about precipitation of both isotactic and conventional PMA (at α = 0.95) have also been carried out.
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  • 50
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It is possible to identify three distinct types of polymer adhesion on the basis of the physical state of adhesive and adherend: (1) rubbery polymer-rubbery polymer (R-R adhesion); (2) rubbery polymer-glassy polymer (R-G adhesion); (3) rubbery polymer-nonpolymer (R-S adhesion). Limitations of the diffusion and adsorption theories and their conflicting results are discussed within the framework of the proposed classification. By defining the physical state of the polymer as an adhesive or as an adherend, it is possible to eliminate many of the discrepancies commonly noted in attempted application of the diffusion and adsorption theories. As predicted by the Bueche-Cashin-Debye equation, the diffusion of a polymer into another should be greatly reduced as it changes from the rubbery to the glassy state. For this reason, diffusion, which depends to a great extent on the physical state of the polymer, is actually a limited, selective process. Assuming a 1013 poise bulk viscosity at glass temperature, self-diffusion constants of forty polymers were calculated to be 10-21cm.2/sec. or 10-5A.2/sec. This slow rate of diffusion is unmeasurable and insignificant. Adsorption, which is less dependent on the physical state of the polymer, is more frequently encountered.
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  • 51
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 957-972 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Drawing of linear polyethylene at 60°C. to an extension ratio of ten drastically reduces the sorption and diffusion of n-pentane, benzene, methylene chloride, and tetrachloroethylene. Methylene chloride was chosen for more detailed study. The sorption is of the normal Fickean type. It is also fully reversible in the temperature range between 25 and 45°C. if the sorbed amount is kept to below 0.5%. At higher concentrations the sample relaxes so that sorption irreversibly increases. The reversible sorption per gram of amorphous component is about 1/6 of that in undrawn polyethylene. The diffusion constant has a larger temperature and concentration dependence than in the undrawn material. At zero concentration the activation energy for diffusion is 34.4 kcal./mole and the diffusion constant at 25°C. is 8 × 10-11 cm.2/sec. as compared with 14.4 kcal./mole and 1.5 × 10-8 cm.2/sec. in undrawn PE. Cold drawing reduces the sorption sites without changing their energy content, but drastically cuts down diffusion and increases the activation energy. A smaller part of the increase of the latter is a consequence of the lower enthalpy of the amorphous material and a larger part is probably due to the increased distance between sorption sites.
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  • 52
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 1055-1059 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A method of evaluating osmotic coefficients of polyelectrolyte solutions is suggested for systems in which a two-phase equilibrium is maintained between the polymer solution and a polymer precipitate so that the “polymer” terms Cpdμp in the Gibbs-Duhem relationship may be neglected. The method is applied to a polybase system, and the osmotic coefficients calculated from the experimental data are discussed in terms of the theory of Alexandrowicz. The results are found to be in line with the above theory but the characteristic parameter φp, the fraction of free counterions, is about twice as large as values previously observed in polyacids.
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  • 53
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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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  • 54
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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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  • 55
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    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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  • 56
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 1320-1322 
    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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  • 57
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 1323-1325 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 2 Ill.
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  • 58
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 1329-1329 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 59
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    Journal of Polymer Science Part A-2: Polymer Physics 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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  • 60
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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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  • 61
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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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  • 62
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 211-223 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetics of radiation polymerization on a solid catalyst is discussed, under the condition that only linear termination of the chain takes place. All the kinetic equations are balance equations of particles of each type adsorbed by unit mass of the catalyst, and this makes it possible to account for the effect on the kinetics of the time dependence of the magnitude of the part of its surface on which the reactions we are considering may take place. Integro-differential equations are used for calculating the molecular weight distribution of the resulting polymer; this ensures higher accuracy of the formulas obtained than when differential equations are used and makes it possible to eliminate a number of limitations generally involved in the transition to differential equations. An expression has been found for the molecular weight distribution of the polymer product which allows for the possibility of radiation-induced catalytic polymerization on the resulting adsorbed polymer. Expressions have been derived for the average molecular weight and yield (weight and molecular) of the polymer formed. Asymptotic formulas have been obtained (for large irradiation times) for all the above values. The conclusions that can be drawn concerning the mechanism of the process based on a comparison of the formulas obtained with kinetic curves plotted from experimental data are given. It is shown how such a comparison can be utilized for calculating the rate constants for polymerization and chain termination reactions.
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  • 63
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 195-210 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A phenomenological theory is presented to extend the method of reduced variables for the effects of both temperature and changing degree of crystallinity on the linear viscoelastic properties of solutions of crystalline polymers. The vertical and the horizontal shift factors, which are both obtainable in the course of analysis of the experimental data, are correlated with the concentration of the solution and the volume fraction of the crystalline phase, and the fractional free volume of the system, respectively. Dynamic mechanical properties of a gel of cellulose nitrate (nitrogen content, 12.6%) in diethyl phthalate with a nominal concentration of 18% by weight were obtained in the transition region from glasslike to rubberlike consistency and also in the rubbery plateau region by employing the Fitzgerald apparatus and a freely oscillating torsion pendulum over the temperature range from -49 to 65°C. Application of the new reduction method to the experimental data was found to be quite successful, and it was shown that in general the degree of crystallinity in the system (and hence also the concentration of polymer in the amorphous phase) can depend on both temperature and thermal history. The dynamic mechanical data of a gel of different nominal concentration (23% by weight) previously obtained by Plazek were reanalyzed in terms of the method herein given.
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  • 64
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 230-234 
    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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  • 65
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 235-236 
    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. 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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  • 67
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 361-375 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The polysaccharide of salep orchid tuber was shown to be a glucomannan with a glucose/mannose ratio of 2.6 and an acetyl content of 2.1%. After extraction from the powdered root with water, the triacetate derivative was prepared and its configurational and hydrodynamic properties examined. The polymer yielded a series of fractions from 615 to 4170 in weight-average degree of polymerization. Light-scattering, viscosity, and osmometry experiments were conducted. Intrinsic viscosity results were interpreted according to the hydrodynamic theory of Eizner and Ptitsyn resulting in a value of ζ/η0 = 20 ± 6 A. for the ratio of monomeric friction coefficient to solvent viscosity and a corresponding value of a = 55 ± 4 A. for the persistence length, closely similar to those reported for other β-1,4-linked polysaccharides. The theoretical Flory coefficient increased with increasing molecular weight but was less than the limiting value of Φ0 = 2.86 × 1023 mole-1. The dependence of the light-scattering radius of gyration of the glucomannan polymer on the contour length showed that the configuration of the heteropolymer was similar to that of other β-1,4-linked polysaccharides which have only glucose or mannose in the main chain. Calculated radii of gyration based on the Porod-Kratky persistence length were found to be smaller than radii found by light scattering on the fractions.
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  • 68
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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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  • 69
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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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  • 70
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 697-704 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Measurements of the spin-lattice relaxation times (T1) of solvent protons have been performed on systems containing mixed solvents with and without polymer. It has been found that the motion of solvent is selectively affected by polymers present in the system. Polyisobutylene (10%) in mixed solvents of carbon tetrachloride (or cyclohexane) and dichloromethane at various proportions produces little effect on T1 values of dichloromethane, but it affects significantly the T1 values of cyclohexane; whereas poly(methyl methacrylate) (10%) in carbon tetrachloride and dichloromethane (or acetone) selectively associates with dichloromethane (or acetone), resulting in an approximate 50% reduction of the T1 values for dichloromethane (or acetone). In systems of poly(methyl methacrylate) and three mixed solvents of carbon tetrachloride, dichloromethane, and cyclohexane, the polymer (10%) has a negligible effect on the T1 values of cyclohexane, but brings about a 50% reduction of the T1 values of dichloromethane. These phenomena are discussed in terms of local selective interactions between the solvent molecules and the polymeric chain segments.
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  • 71
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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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  • 72
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    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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  • 73
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 711-742 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A general method is presented for taking into account changes in volume in several types of calculations concerned with spherulite deformation in semicrystalline polymers. The method is applicable at large strains for which the low-strain limiting form of the equation defining Poisson's ratio is no longer valid. Applications are made to calculations of the three crystal orientation functions for models of spherulite deformation based on those proposed by Wilchinsky, Stein et al., and Oda et al. The effects of changes in volume are considered in detail and are compared with previous results in which the volume change was neglected. Calculations of spherulite birefringence are considered in a similar manner, as are the equations for determining spherulite deformation by means of low-angle light-scattering measurements. Results indicate that in several cases details of deformation mechanisms previously proposed should be revised in light of the effect of the change in volume on the calculated orientation functions. The equations in each case are presented in terms of a parameter β, the square root of the third strain invariant of the deformation tensor. Results are presented in numerical form for many of the basic parameters. Equations for all such results are expressed in explicit form and, in most cases, are displayed graphically together with available experimental data.
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  • 74
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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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  • 75
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 781-790 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A description is given of a modified cone-and-plate apparatus suitable for the measurement of the streaming birefringence of molten polymers. Some results are given of measurements on a polystyrene and a poly(dimethyl siloxane). Those on polystyrene are compared with solution measurements of the same material by use of the well-known Bueche-Harding parameter. Measurements on the silicone oil have been compared with measurements of the dynamic moduli on the same material, after ascertaining the validity of the stress-optical law for this system as well.
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  • 76
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 791-794 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 1 Ill.
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  • 77
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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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  • 78
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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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  • 79
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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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  • 80
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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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  • 81
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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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  • 82
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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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  • 83
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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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  • 84
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 929-938 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Free radicals produced in irradiated polypropylene were studied by the electron spin resonance method. Two temperature regions in which the free radicals decay rapidly were found at around 170°K. and 260°K. The first temperature region corresponds to the γ-dispersion of polypropylene and the second to the β-dispersion. Steric configurations of the free radicals were investigated, and it was concluded that the free radicals trapped in polymer, conformation of which is appreciably twisted from the stable 31-helical structure, decay with small-scale motion of the matrix polymer. The decay of free radicals trapped in polymer of less twisted conformation is associated with the large-scale motion of the matrix polymer. Activation energies of decay were found to be 11 kcal./mole at the lower temperature and 48 kcal./mole at the higher temperature. Time constants of the decay reactions were compared with those for molecular motion of the matrix, with results reflecting the relations of the decay of the polymer radicals to molecular motion in the matrix.
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  • 85
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 939-955 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The deformation of fresh and aged polybutene-1 spherulitic samples has been investigated by microscopic observation, interferometry, studying macroscopic and spherulitic birefringence changes, and study of light-scattering patterns. The spherulite deformation is not affine, the microscopic deformation ratio being less than the macroscopic deformation ratio of the sample and greater in the equatorial regions of the spherulite than in the polar regions. The deviation from affine deformation is less for fresh spherulites than for the aged, where void formation occurs in the equatorial part of the spherulite. This gives rise to large scattering by this part of the spherulite and to form birefringence. The spherulite birefringence and its change with elongation is dependent upon the degree of aging of the sample. The spherulite birefringence is more negative for the aged sample. In the polar regions of the spherulite, this negative birefringence decreases and turns positive at higher elongations, characteristic of a reorientation of the crystals with their optic axes turning from being perpendicular to parallel to the spherulite radius. The spherulite birefringence in the equatorial direction becomes somewhat more negative on stretching a fresh sample but less negative on stretching an aged one. Spherulite distortion and orientation changes are apparent from the light-scattering patterns of films possessing small spherulites. The changes in Vv and Hv scattering patterns upon stretch are different for the fresh and aged samples. The Vv patterns of the fresh samples decrease in intensity with time after stretching a fresh sample with the Hv patterns do not.
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  • 86
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 987-988 
    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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  • 87
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 989-989 
    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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  • 88
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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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  • 89
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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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  • 90
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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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  • 91
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 1087-1101 
    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 on the size of low-density polyethylene molecules in solution is demonstrated through solution viscosity and molecular weight measurements on fractionated samples. These well-characterized fractions are analyzed by gel permeation chromatography (GPC), and it is shown that the separation of the polymer molecules by this technique is sensitive to the presence of long-chain branching. By using fractions of branched polyethylene possessing differing degrees of branching, one observes that a single curve is adequate in relating elution volume to molecular weight. This calibration curve is applied in the GPC analysis of a variety of commercial low-density polyethylene resins and it is shown, by comparison with independent osmometric and gradient elution chromatographic data, that realistic values for molecular weight and molecular weight distribution are obtained. The replacement of molecular weight M by the parameter [η]M as a function of elution volume, leads to a single relationship for both linear and branched polyethylenes. This indicates that GPC separation takes place according to the hydrodynamic volumes of the polymer molecules. The comparison of data for polyethylene and polystyrene fractions suggests that this volume dependence of the separation will be observed for other polymer-solvent systems.
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  • 92
    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.
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  • 93
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 1293-1295 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 2 Ill.
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  • 94
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 1283-1292 
    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 microstructure on crystallizability of polyoctenamers prepared by R3Al-WCl6 catalyst was studied. The results indicate that polyoctenamers with a broad range of trans-vinylene content do crystallize. The measured melting points are dependent on the trans-vinylene content. From the dependence of melting temperature on copolymer composition, a value of 73 ± 2°C. for the melting point and a molar heat of fusion ΔHu of 3520 cal./mole are calculated for 100% trans-polyoctenamer. From the melting point depression in the presence of diluent, a value for ΔHu of 4800 cal./mole is obtained.
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  • 95
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Current theories of polymer flow processes often sacrifice realistic molecular models for simplicity of their mathematical equations. An analysis of what might happen to molecules of more realistic sizes and shapes under shear flow, shows the importance of the rapid Brownian motion of chain segments, the elastic deformations of polymer random coils, and the dissipation of this elastic random coil energy by the relatively slow slippage of the chains past each other at a few entanglements where steric hindrance causes long relaxation times. This makes the energy loss depend on the time at each local deformation, and not on the overall shear rate. At high shear rates this model leads to “cluster flow” and low loss cyclic deformations, rather than the high loss processes of steady-state shear. This model gives reasonable qualitative explanations for many anomalous flow properties, and it has predicted new effects that have since been observed.
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  • 96
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 1305-1308 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 7 Ill.
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  • 97
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    Journal of Polymer Science Part A-2: Polymer Physics 5 (1967), S. 1309-1312 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 1 Ill.
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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 theory of the equilibrium distribution of a mixture of different size species of a polymer between two liquid phases is reviewed and used as a basis for the calculation of the dependence of fractionation efficiency on overall concentration, interaction coefficient (hence, choice of solvent and temperature), average molecular weight, and the spread of the molecular weight distribution in the polymer. The special case of a single type of polymer in a single solvent, for which the polymer-solvent interaction coefficient is independent of concentration, is dealt with quantitatively. The ultimate aim is to make it possible to determine systematically the optimum solvent (or mixture of solvents), temperature, and overall concentration for fractionation of a given type of polymer, having a given average molecular weight and molecular weight distribution, considering practical limitations, e. g., the total volume which can conveniently be handled and the time required to achieve a sufficiently close approach to equilibrium.
    Additional Material: 14 Ill.
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