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  • Electronic Resource  (933)
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  • 1
    ISSN: 1432-1351
    Keywords: Key words Olfactory receptor cells ; Olfactory bulbectomy ; Olfactory axotomy ; Electrophysiology ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Abstract This study investigated whether contact with the olfactory bulb was necessary for developing and renewing olfactory receptor neurons (ORNs) to attain normal odorant responsiveness, and whether the anatomical and functional recoveries of the olfactory epithelium were similar in both bulbectomized (BE) and bilaterally axotomized (AX) preparations. In vivo electrophysiological recordings were obtained in response to amino acids, a bile acid [taurolithocholic acid sulfate(TLCS)] and a pheromonal odorant [17α, 20β,-dihydroxy-4-pregnen-3-one (17,20P)] from sexually immature goldfish. Both transmission and scanning electron microscopy indicated that the olfactory epithelium degenerated in BE and AX goldfish. Within 1–2 weeks subsequent to the respective surgeries, responses to high concentrations (〉0.1 mmol · l−1) of the more stimulatory amino acids remained, whereas responses were no longer obtainable to TLCS and 17,20P. At 4 weeks, responses to amino acid stimuli recovered to control levels, while responses to TLCS and 17,20P were minimal. By 7 weeks post bilateral axotomy, the olfactory epithelium recovered to a condition similar to control sensory epithelium; however, the rate of degeneration and proliferation of receptor neurons in BE preparations appeared to remain in balance, thus blocking further recovery of the olfactory epithelium. At 7 weeks post surgery, odorant responses of AX and BE goldfish to TLCS and 17,20P were still recovering.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1432-2307
    Keywords: Key words Bronchioloalveolar lung carcinoma ; Atypical adenomatous hyperplasia ; Surfactant apoprotein ; Urine protein 1 ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  We used immunohistochemistry and electron microscopy to evaluate the differentiation of cells comprising atypical adenomatous hyperplasia (AAH; n = 26), early bronchioloalveolar lung carcinoma (BAC; n = 11), and overt BAC (n = 16), which are assumed to constitute a continuous spectrum of developmental steps of BAC. Surfactant apoprotein (SAP), a marker for type 2 alveolar cells, was expressed in cells from all the lesions of AAH, early BAC, and overt BAC. However, the proportion of SAP-positive cells decreased and their distribution became more heterogeneous with advancing lesion grade. Urine protein 1, which is identical to the Clara cell-specific 10 kDa protein, was expressed in 70% of overt BAC, whereas only 20% of early BAC showed weak reactivity and none of AAH lesions showed any reactivity at all. Ultrastructurally, type 2 alveolar cell differentiation was predominant among cells from AAH and early BAC. Our results suggest that precursor cells of BAC differentiate predominantly towards type 2 alveolar cells. Cells comprising overt BAC retain this differentiation phenotype, but to a reduced extent. In contrast, concomitantly with progression, cells with Clara cell differentiation emerge and their proportion increases. Such phenotypic changes may reflect metaplasia occurring in tumour cells during the development of BAC.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 1432-2307
    Keywords: Key words Adenovirus ; Liver pathology ; Electron microscopy ; AIDS
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  Adenovirus-induced liver necrosis is rare. Before the era of AIDS (acquired immunodeficiency syndrome) this entity was seen predominantly in infants suffering from inborn immunodeficiency syndromes or from iatrogenic immunosuppression because of bone marrow or liver transplantation. Here, we report a case of a 30-year-old woman with AIDS who developed fever and rapidly progressing liver failure. A frozen section from a needle biopsy of the liver allowed a quick diagnosis of viral liver necrosis. The light-microscopic and electron microscopic aspects were typical of adenovirus infection and should be known to the surgical pathologist. The diagnosis was confirmed by immunohistochemistry and DNA hybridization analysis.
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 1432-0533
    Keywords: Key words Astrocytes ; Alzheimer-type dementia ; Electron microscopy ; Glial fibrillary tangles ; Tau protein
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract This report concerns pathological astrocytic tubular structures (astrocytic tubules, As-Tbs) that coexist with glial filaments in astrocytic processes in brains with presenile-onset Alzheimer-type dementia. The formation of As-Tbs appears to be related to the duration of disease and the intensity of Alzheimer histopathology. In three cases in which the disease was of extremely long duration, As-Tbs were found in the frontal and temporal neocortices, the temporal pole and the hippocampus using electron microscopy, whereas they were not found in two cases with a long, but not extremely long, illness duration. As-Tbs were almost exclusively found in the highly devastated neuropil, and we could not find them in regions of moderate neuronal degeneration despite intensive inspection. As reported previously, some As-Tbs was seen adjacent to extracellular neurofibrillary tangles (NFTs) and in perivascular astrocytes. Our novel finding is that they can exist independently from these, in the highly devastated neuropil. Two types of As-Tbs were observed, twisted tubules with periodic constrictions at 50- to 80-nm intervals and non-twisted tubules where no constrictions were seen but which had a 15-nm fuzzy outer contour. They were positively stained by anti-human tau antibody, an antibody that does not recognize extracellular NFTs. Thus, it is most likely that As-Tbs are not the sequestration of extracellular NFTs, and that they are of astrocytic origin. Moreover, As-Tbs showed argyrophilia. As-Tbs appear indistinguishable from dystrophic neurites under the light microscope. The present data suggest that they may be more widely distributed in the damaged cerebral neuropil than previously thought.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    Trees 11 (1997), S. 378-387 
    ISSN: 0931-1890
    Keywords: Key words Pinus sylvestris (L.) ; Electron microscopy ; Heavy metals ; Multi-stress-symptoms ; SO2
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract  Injuries to needles of Scots pines (Pinus sylvestris L.) growing in nutrient-poor soils on the Kola Peninsula collected in April 1991 were studied on a gradient of increasing distances (10 – 115 km) from the Monchegorsk nickel smelter, Russia, which emits SO2, Ni and Cu. The condition of the mesophyll cells was quantified from needles of the two latest age classes using a light and an electron microscope. The damage to the ultrastructure consisted of multistress symptoms caused by excess sulphur, heavy metals, frost, acidic precipitation and ozone. Injuries were most commonly manifested in the form of dark, irregularly shaped chloroplasts with protrusions and light thylakoids and plastoglobuli. These symptoms gradually disappeared with increasing distance and decreasing deposition rate. Concentrations of sulphur, copper and nickel decreased towards more distant sites where normal levels of the latter two elements were reached. Sulphur concentrations remained above background throughout the distance gradient. In the closest plots to the smelter area, cell collapse under the stomata and epidermis related to acute SO2 and heavy metal effects was found, whereas further away symptoms were more diverse, pointing towards the effects of ozone, acidic deposition and thereby decreased frost tolerance. The additive multistress symptoms were clearly seen in the area up to 40 km from the smelter where needle Cu concentration was above 110 ppm, Ni concentration above 39 ppm and S concentration above 1343 ppm.
    Type of Medium: Electronic Resource
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  • 6
    ISSN: 1432-0533
    Keywords: Key words CADASIL ; Electron microscopy ; Granular osmiophilic material ; αB crystallin ; Heat ; shock proteins
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Cerebral autosomal dominant arteriopathy with subcortical infarcts and leukoencephalopathy (CADASIL) is a non-arterio-atherosclerotic, non-amyloidotic arteriopathy affecting preferentially the small arteries and arterioles of the brain. The morphologic hallmark is the presence of a characteristic granular alteration of the arterial media that ultrastructurally corresponds to the accumulation of electron-dense material surrounding the smooth muscle cells. Although the presence of this granular osmiophilic material (GOM) was originally described as limited to brain vessels, identical electron microscopic findings have been demonstrated in the media of peripheral tissue arteries, allowing for a pathologic diagnosis of the disease by a simple skin, muscle or nerve biopsy. We report some atypical features identified in our CADASIL patients that broaden the phenotypic expression of this disease. Firstly, we identified a cortical infarct in an otherwise typical CADASIL patient. Secondly, we observed GOM in skin arteries of a 30-year-old man with hemiplegic migraine, the son of a woman who had died with CADASIL. This confirms that it may be possible to diagnose the disease at a preclinical stage by the ultrastructural evaluation of peripheral tissue biopsy material, particularly for individuals for whom there is a supporting family history. Thirdly, ultrastructural examination of the skin, and subcutaneous and striated muscle of an unrelated and apparently sporadic patient with neuropathologic and neuroradiologic evidence of CADASIL in meningeal and cerebral vessels failed to reveal diagnostic lesions in peripheral arteries. Thus, the possibility of a false-negative pathologic diagnosis in patients with a clinicoradiologic diagnosis of CADASIL, if one relies solely on a peripheral tissue biopsy, does exist. Additionally, we have identified heat shock proteins (Hsp70 and αB crystallin) and ubiquitin in the vascular myocytes of affected arteries. αB crystallin also seemed to be deposited extracellularly, which suggests that GOM also might be immunoreactive for αB crystallin.
    Type of Medium: Electronic Resource
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  • 7
    ISSN: 1432-069X
    Keywords: Key words Atopic dermatitis ; Peripheral nerve ;   ; Electron microscopy ; Protein gene product ; Substance P
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract The density and fine structure of the peripheral nerve system in various skin lesions of 64 patients with atopic dermatitis (AD) was quantitatively analyzed by immunohistochemical staining with antibodies directed against protein gene product (PGP) and substance P (SP). The density of PGP-positive peripheral nerves was 2.5 × 10 3 μm 2 /Δs (Δs = 0.24 mm 2 selected area) in early acute lesions, 3.8 × 10 3 μm 2 /Δs in subacute lesions, 4.9 × 10 3 μm 2 /Δs in lichenified lesions and 7.1 × 10 3 μm 2 /Δs in prurigo lesions of AD. The density of nerve fibers in subacute, lichenified and prurigo lesions was significantly higher than in uninvolved skin of AD patients (2.0 × 10 3 μm 2 /Δs). Electron microscopically, bulging of axons with many mitochondria and a loss of their surrounding sheath of Schwann cells suggests that the free nerve endings in skin lesions of AD are in an active state of excitation. Many pinocytotic vesicles in the periphery of basal keratinocytes facing nerve endings which contained many neurovesicles suggests reciprocal effects between keratinocytes and nerve endings. The number of SP-positive nerve fibers in AD lesions was far less than one-tenth of the number of PGP-positive nerve fibers.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    Development genes and evolution 206 (1997), S. 503-514 
    ISSN: 1432-041X
    Keywords: Key words Preimplantation mouse embryo ; Brefeldin-A ; Monensin ; Golgi ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract  The intracellular trafficking of integral membrane and secreted proteins is likely to be a key element involved in the morphogenesis and differentiation of the early mammalian embryo. In this study, we used transmission electron microscopy (TEM) to analyse the effects of brefeldin-A (BFA) and monensin, well known inhibitors of vesicular protein trafficking in somatic cells, on the structure of preimplantation mouse embryos. Both BFA and monensin distinctively altered the morphology of Golgi compartments in the blastomeres of treated morulae. BFA-treated morulae lacked recognizable Golgi complexes but possessed heterogeneous organelle clusters consisting of an abundance of smooth tubular and vesicular membrane compartments in addition to mitochondria, endosomes and lysosomes. Treatment of morulae with monensin was associated with swelling of Golgi compartments in addition to altering the morphology of mitochondria, lysosomes and the plasma membrane. BFA, and to a lesser extent monensin, inhibited cytokinesis as evidenced by the detection of binucleate blastomeres. In addition, BFA induced morulae to decompact. These latter effects have not been reported previously for these agents in mammalian somatic cell lines or other vertebrate or invertebrate embryos. These results provide the first demonstration of the structural effects of BFA and monensin on cells of the early mammalian embryo, some of which are consistent with the known actions of these agents on components of the vesicular protein trafficking system in mammalian somatic cells. This information serves as a foundation for the further use of these agents in studies of vesicular protein trafficking as an agent of preimplantation morphogenesis.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    Springer
    Der Pathologe 18 (1997), S. 419-424 
    ISSN: 1432-1963
    Keywords: Schlüsselwörter Gangliozytom ; Gangliogliom ; Hypophysenadenom ; Immunhistologie ; Ultrastruktur ; Key words Gangliocytoma ; Ganglioglioma ; Pituitary adenoma ; Immunohistochemistry ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Summary Gangliocytomas or gangliogliomas of the sellar region are very rare tumors. In a great proportion of those cases an adenoma of the anterior pituitary develops from the cell type that is hyperstimulated by the releasing hormone produced from the gangliocytoma. Five GHRH secreting gangliocytomas are reported. Four of these were localized adjacent to a GH secreting adenoma. In one case, no adenoma tissue was found beside the ganglicytoma. As only the adenomas can secrete GH, the adenomas and not the gangliocytomas are directly responsible for acromegaly so that such an adenoma has to be present in cases of acromegaly. A CRH secreting gangliocytoma was combined with an ACTH cell adenoma that had induced Cushing’s disease. A ganglioglioma of the posterior pituitary had led to an inappropriate secretion of Vasopressin. The morphology of the different tumors is presented.
    Notes: Zusammenfassung Intraselläre Gangliozytome/Gangliogliome sind sehr seltene Tumoren, die in einem Großteil der Fälle ein Hypophysenadenom aus dem Zelltyp heraus entstehen lassen, der durch das gebildete Releasinghormon überstimuliert wird. Es wird über 5 GHRH-bildende Gangliozytome berichtet, von denen 4 einem STH-bildenden Hypophysenadenom benachbart waren. Ein Fall enthielt keine Adenomanteile. Diese müssen in Anbetracht der klinisch vorhandenen Akromegalie aber vorhanden sein, da nur das jeweilige Adenom, nicht aber die Gangliozytome für die Überfunktion unmittelbar verantwortlich sind. Ein CRH-bildendes Gangliozytom war mit einem zum Morbus Cushing führenden ACTH-Zelladenom kombiniert. Ein Gangliogliom des Hinterlappens hatte zu einer inadäquaten Vasopressinsekretion Anlaß gegeben. Die Morphologie der Tumoren wird dargelegt.
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  • 10
    ISSN: 1432-1106
    Keywords: Key words Synapse ; Axo-axonic synaptic contacts ; Trigeminal motor nucleus ; Immunogold ; Electron microscopy ; Rat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  Electron-microscopic immunolabelling methods were used to study the relationships between glutamate-immunoreactive and γ-aminobutyric acid (GABA)-immunoreactive synapses on trigeminal motoneurones labelled by the retrograde transport of horseradish peroxidase. Serial sections were cut through the motor nucleus, alternate sections were incubated with antibodies to glutamate and GABA, and the immunopositive nerve terminal profiles were recognized using a quantitative, postembedding immunogold method. Boutons exhibiting high levels of glutamate immunoreactivity and GABA-immunoreactive boutons both formed axo-dendritic and axo-somatic synaptic contacts on labelled motoneurones. Boutons strongly immunopositive for glutamate were not immunopositive for GABA, and vice versa. Strongly glutamate immunoreactive boutons received axo-axonic synaptic contacts but did not form such contacts, while GABA-immunoreactive boutons formed axo-axonic synapses but did not receive them. The presynaptic elements at all axo-axonic synapses on to glutamate-immunoreactive boutons sampled were GABA-immunopositive. These data provide ultrastructural evidence in support of the roles of glutamate and GABA as transmitters at synapses on trigeminal motoneurones, and for presynaptic control of transmission at glutamatergic synapses by GABA acting at receptors at axo-axonic synapses. The vast majority (more than 90%) of strongly glutamate immunoreactive boutons contained spherical synaptic vesicles, in contrast to GABA-immunoreactive boutons, which contained pleomorphic vesicles. Most of the glutamate-immunoreactive boutons (67%) formed asymmetrical synaptic active zones, many of which (47% of total) were associated with subsynaptic dense ”Taxi” bodies (T-terminals), while a smaller population of boutons (21%) formed symmetrical synapses, and a few (11%) made synapses associated with subsynaptic cisternae (C-terminals). The heterogeneity of active zone ultrastructure of boutons identified as being glutamatergic on the basis of their high levels of immunolabelling is discussed in relation to possible differences in co-transmitters released, origins of the synaptic input or post-synaptic receptor subtypes activated.
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  • 11
    Electronic Resource
    Electronic Resource
    Springer
    Archives of gynecology and obstetrics 261 (1997), S. 39-43 
    ISSN: 1432-0711
    Keywords: Key words: Ehlers-Danlos type III ; Pregnancy ; Electron microscopy ; Prenatal diagnosis ; Premature rupture of membranes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract. We report a case of type III Ehlers-Danlos syndrome with a favourable outcome. We review the literature and do not consider that pregnancy in patients with type III Ehlers-Danlos Syndrome represents a high risk situation.
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  • 12
    ISSN: 1432-2307
    Keywords: Key words Naevus of Ota ; Q-switched alexandrite laser ; Light microscopy ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  Melanocytes in the naevus of Ota were destroyed by irradiation using the Q-switched alexandrite laser. This laser is highly selective and highly absorbed by melanosomes. Other cells and tissue components of the dermis remained almost intact. Melanosomes were vaporized or fragmented to subelectron microscopical size, or degenerated. If the irradiated energy was sufficient, melanocytes vanished and large vacuoles several times the size of dermal melanocytes formed at the sites. If it was too weak, dermal melanocytes were also vaporized, but vacuoles formed within them. Nuclei were no longer discernible. Following irradiation macrophages infiltrated the irradiated areas and scavenged degenerated melanosomes and cellular debris. Thus, discoloration of the skin was markedly reduced. Although a few melanocytes and melanophages remained, pigmentation cleared to a satisfactory level. Melanocytes and keratinocytes were also injured in the epidermis; however, the epidermis recovered completely. No scarring was observed.
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  • 13
    ISSN: 1432-0878
    Keywords: Key words: Intracardiac neurones ; Innervation ; Heart ; Neuropeptide Y ; Immunocytochemistry ; Electron microscopy ; Rat (Sprague Dawley) ; Guinea-pig (Dunkin Hartley)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Abstract. Intrinsic neuropeptide Y-containing neurones in rat and guinea-pig hearts were studied at the ultrastructural level by the pre-embedding peroxidase-antiperoxidase immunocytochemical technique. Intracardiac neuronal cell bodies were often weakly or moderately immunostained, and the labelling was usually pronounced in the Golgi complex, multivesicular bodies, some cisterns of granular endoplasmic reticulum and large granular vesicles. Neuropeptide Y-immunoreactive nerve fibres were also observed in association with intracardiac neurones. A subpopulation of neuropeptide Y-immunoreactive granule-containing cells in the rat heart are described for the first time and were very heavily labelled; other granule-containing cells were non-immunoreactive, but were contacted by neuropeptide Y-containing nerves. Preterminal regions of nerve fibres that were located in nerve bundles were only weakly neuropeptide Y-immunoreactive, in contrast to the heavy labelling observed in varicosities that contained many synaptic vesicles. Many neuropeptide Y-immunoreactive nerve fibres were associated with the coronary vasculature and were particularly prominent in the walls of small arteries and arterioles where labelled nerve varicosities were present close to the smooth muscle cells. Immunoreactive nerves were also seen in the myocardium, usually near to capillaries. In axonal varicosities, the central core of large granular vesicles was immunolabelled, and electron-dense immunoreactive material outlined the membranes of small and large clear vesicles. The significance of neuropeptide Y-immunoreactive intracardiac neurones and granule-containing cells and the origin of associated labelled nerve fibres in the heart are discussed.
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  • 14
    ISSN: 1432-0878
    Keywords: Key words: Quinolinic acid ; Interferon-γ ; Kynurenine ; Electron microscopy ; Immunocytochemistry ; Excitotoxicity ; Human
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Abstract.  Quinolinate (QUIN), a tryptophan-derived excitotoxin, was localized ultrastructurally in human peripheral blood monocytes/macrophages (MØ) by immuno-electron microscopy. A combined carbodiimide/glutaraldehyde/paraformaldehyde-based fixation procedure was developed for optimal retention of QUIN in the cell as well as minimal loss of ultrastructure; a silver-enhanced colloidal gold detection system was used for electron-microscopic analysis. Gold particles representing QUIN immunoreactivity were associated with the inner side of the plasma membrane in normal MØ. The number of gold particles increased significantly when QUIN levels were elevated by treatment with its precursor kynurenine, but location of the gold particles remained essentially the same under this condition. Treatment with interferon-γ increased the number of Golgi bodies, vacuoles and pseudopodia, reflecting the activated state of the cell. Significantly increased numbers of gold particles representing QUIN were detectable in approximately the same location as in the case of kynurenine treatment. Combined treatment with kynurenine and interferon-γ maximally increased the number of gold particles at the periphery of the cell. The pseudopodia were intensely stained with gold particles, while they were not detectable in the inner part of the cytoplasm or in any other organelle even under this activated condition. The significance of the specific location of QUIN revealed in the present study and its relation to the release and subsequent actions of QUIN are discussed.
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  • 15
    Electronic Resource
    Electronic Resource
    Springer
    Cell & tissue research 289 (1997), S. 517-526 
    ISSN: 1432-0878
    Keywords: Key words: Neuromuscular junction ; Synaptic vesicles ; Vesicle fusion ; Electron microscopy ; Callinectes sapidus (Crustacea)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Abstract. Neuromuscular terminals of a single motoneuron to four muscles (CPV7a, GM5a, CV2, and CV3) in the stomach of the blue crab Callinectes sapidus showed structural evidence for the exocytotic release of dense-core vesicles exclusively at synapses. The primary evidence was the appearance of dense cores in the synaptic cleft, accompanied by indentations of the presynaptic or postsynaptic membrane. In their simplest form, these consisted of an omega-shaped figure of the presynaptic membrane enclosing one dense core, denoting release of a single dense-core vesicle. A larger indentation of the presynaptic membrane enclosing several dense cores denoted multiple release. A more complex form of multiple release was where the presynaptic membrane was normal, but the postsynaptic membrane elaborated into a sac projecting into the granular sarcoplasm and filled with dense cores. The postsynaptic sac in some instances was compressed into a thin, fingerlike extension, which lacked dense cores and, at its distal end, separated into small cisternae, suggesting a mechanism for membrane recycling. Profiles depicting single and multiple releases of dense-core vesicles were found more frequently at neuromuscular terminals that release relatively large amounts of transmitter with a single stimulus, such as CV2 and CV3, compared to those releasing smaller amounts, such as CPV7a and GM5a. The disparity in release sites among the four muscles of this single motor unit and the fact that many of the multiple-release figures were closely adjacent to the active zones for transmitter release suggest a possible modulatory role for dense-core vesicles in synaptic transmission. Such modulation may be long lasting, as implied by the postsynaptic sacs, which may permit prolonged release of the contents of their dense cores into the synaptic cleft. This is in keeping with the functional role of these stomach muscles, which is to be continuously active for long periods of time.
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  • 16
    ISSN: 1432-0878
    Keywords: Key words: Parietal eye ; Pineal organ ; Retina ; Glutamate ; Aspartate ; Immunocytochemistry ; Electron microscopy ; Lacerta muralis ; Lacerta agilis ; Lacerta viridis (Lacertilia)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Abstract. The fine structure of the organ and the localization of the excitatory amino acids glutamate and aspartate were studied in the parietal eye of lizards by postembedding immunoelectron microscopy. The parietal eye contains cone photoreceptor cells, secondary neurons, and ependymal and lens cells. The photoreceptors form long inner and outer segments, some of them being paired as ”twin-photoreceptors” by zonulae adherentes. Perikarya of neurons bear sensory cilia (containing 9×2+0 pairs of tubules) extending into the intercellular space. No neurohormonal terminals are present in the parietal eye. A higher immunoreactivity to glutamate than to aspartate is found in the photoreceptors and in the secondary neurons of the parietal eye. Glutamate immunogold labeling is more intense in the axonal processes of photoreceptors and neurons and in most of the nerve fibers of the parietal nerve running to the brain stem. Weak aspartate and glutamate immunoreactivity can be detected in the ependymal and lens cells. A similar distribution of immunoreactive amino acids is found in the photoreceptors, secondary neurons, and ependymal glial elements of the pineal organ, and retina of the lateral eye of the same animals. Immunoreactive glutamate accumulates in the axons of photoreceptors and secondary neurons of the parietal eye suggesting that this excitatory amino acid acts as a synaptic mediator in the neural efferentation of the organ. Thus, the efferent light-conducting pathway of the parietal organ is similar to that of the pineal organ and lateral eye retina. As the Mullerian cells of the retina, the ependymal and lens cells of the parietal eye and the ependymal-glial cells of the pineal organ may play a role in the metabolism and/or elimination of excitatory amino acids released by photoreceptors.
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  • 17
    ISSN: 1432-0878
    Keywords: Key words: Liver ; Subcellular fractions ; Immunohistochemistry ; Electron microscopy ; Rat (Wistar)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Abstract. This study, utilizing rats subjected to two-thirds partial hepatectomy or sham operation, was designed (1) to investigate the content of basic fibroblast growth factor (bFGF) in the subcellular fractions of regenerating and sham-operated rat livers by immunoblot experiments and enzyme-linked immunosorbent assay (ELISA), (2) to show that bFGF immunoreactivity and proliferating cell nuclear antigen (PCNA) immunoreactivity are markers for hepatocellular mitosis before and after partial hepatectomy, and (3) to observe the location and fine structure of the bFGF immunoreaction within the regenerating liver with special attention to bFGF immunoreactivity in the nuclei of regenerating hepatocytes. Immunoblot experiments and ELISA showed a transient increase in high-molecular-weight forms of bFGF in the nuclear subcellular fraction of regenerating liver 48 h after partial hepatectomy. By light microscopy, bFGF and PCNA immunoreactivities were detected in the nuclei of regenerating hepatocytes. Electron microscopy demonstrated bFGF-like immunoreactivity mainly in the nuclear euchromatin and rarely in the heterochromatin or nucleoli of regenerating hepatocytes. The transient increase in high-molecular-weight forms of bFGF in the nuclear euchromatin of regenerating hepatocytes, together with the concomitant expression of PCNA in the regenerating liver, suggests an important role of the high-molecular-weight forms of bFGF in hepatocyte proliferation and/or mitosis, although authentic bFGF with a molecular form of 18 kDa is not considered to be involved in hepatic regeneration.
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  • 18
    ISSN: 1615-6102
    Keywords: Chlamydomonas reinhardtii ; Contractile vacuole ; Electron microscopy ; Videomicroscopy ; Osmoregulation ; Osmoregulatory mutants
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary Four independent osmoregulatory mutants,osml, osm3,osm4, and osm7, were isolated on the basis of their requirement for growth medium of high osmotic strength. In normal low-osmoticstrength medium, in contrast to wild-type cells, the mutants grow poorly or not at all; in distilled water mutant cells are immobilized and eventually swell and burst. The mutants were examined by ordinary brightfield and phase-contrast microscopy, videomicroscopy, and electron microscopy. The four mutants showed different defects in the contractile vacuole (CV) cycle. Timing of various stages of the CV cycle showed thatosm1 was affected primarily in the early stage of the cycle when the CV begins to grow,osm3 primarily in midcycle when vacuoles fuse to form the CV proper,osm7 at a late stage of the cycle at docking and fusion of the CV with the plasma membrane, andosm4 during contraction of the CV. At the electron microscopic level, in dilute medium, mutant cells by comparison with wild-type cells had large autophagosomes, swollen mitochondria, and dilated ER cisternae. Although electron microscopy showed general abnormalities of the contractile vacuoles consistent with the videomicroscopic observations of living cells, no obvious vacuole membrane abnormalities were seen which would explain the mutational defects. The mutations help define the separate processes that contribute to the coordinated CV cycle inChlamydomonas, and open the way to eventual isolation of some of the genes responsible for CV function.
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  • 19
    Electronic Resource
    Electronic Resource
    Springer
    Protoplasma 198 (1997), S. 73-84 
    ISSN: 1615-6102
    Keywords: Chlamydomonas reinhardtii ; Contractile vacuole ; Osmoregulation ; Videomicroscopy ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary The contractile vacuole (CV) cycle ofChlamydomonas reinhardtii has been investigated by videomicroscopy and electron microscopy. Correlation of the two kinds of observation indicates that the total cycle (15 s under the hypo-osmotic conditions used for videomicroscopy) can be divided into early, middle, and late stages. In the early stage (early diastole, about 3 s long) numerous small vesicles about 70–120 nm in diameter are present. In the middle stage (mid-diastole, about 6 s long), the vesicles appear to fuse with one another to form the contractile vacuole proper. In the late stage (late diastole, also about 6 s long), the CV increases in diameter by the continued fusion of small vesicles with the vacuole, and makes contact with the plasma membrane. The CV then rapidly decreases in size (systole, about 0.2 s). In isosmotic media, CVs do not appear to be functioning; under these conditions, the CV regions contain numerous small vesicles typical of the earliest stage of diastole. Fine structure observations have provided no evidence for a two-component CV system such as has been observed in some other cell types. Electron microscopy of cryofixed and freeze-substituted cells suggests that the irregularity of the profiles of larger vesicles and vacuoles and some other morphological details seen in conventionally fixed cells may be shrinkage artefacts. This study thus defines some of the membrane events in the normal contractile vacuole cycle ofChlamydomonas, and provides a morphological and temporal basis for the study of membrane fusion and fluid transport across membranes in a cell favorable for genetic analysis.
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  • 20
    ISSN: 1615-6102
    Keywords: Electron microscopy ; UV-induced cell damage ; Photoreceptor ; Eye ; Lepidoptera
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary A technique that allows the specific inactivation of short-wavelength-sensitive photoreceptive cells has been needed for a long time. Such a technique could be useful in studies on the role(s) of UV-receptors in circadian rhythmicity, recognition of floral patterns, homing behaviour, and mate selection in arthropods. We provide ultrastructural evidence that short-wavelength receptor cells can be selectively damaged without affecting other spectral-cell types. Since the method does not require the killing of the experimental animal, the latter can be used in behavioural or other follow-up tests.
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  • 21
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    European archives of oto-rhino-laryngology and head & neck 254 (1997), S. 230-235 
    ISSN: 1434-4726
    Keywords: Paranasal sinus mucosa ; Collagen type VII ; Subepithelial connective tissue ; Electron microscopy ; Immunofluorescence microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract The morphology of the mucosa from the human paranasal sinuses was investigated by electron microscopy. A total of 27 specimens was taken from 11 patients following midfacial fractures. All tissue samples were biopsied during surgery after informed consent had been given. In accordance with light microscopic investigations, the mucosa represented a highly prismatic epithelium consisting of kinocilia-carrying and mucus-producing (goblet) cells. Other cell types, such as those occurring in the respiratory epithelium of other areas, could not be demonstrated. Electron microscopic and immunomorphological investigations revealed collagen type VII beneath the lamina densa of the basal lamina. According to findings obtained to date, this collagen type accompanies only a multilayered epithelium. Another peculiarity was the small number of basophils and eosinophils. Pronounced acute reactions of the mucosa in this area cannot be expected, which is in contrast to that of the nasal mucosa.
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  • 22
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    European archives of oto-rhino-laryngology and head & neck 254 (1997), S. 255-258 
    ISSN: 1434-4726
    Keywords: Electron microscopy ; Inner ear ; Utricle ; Cholesteatoma ; Acoustic neuroma
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract The morphological characteristics of the vestibular sensory cells of the macula utriculi obtained during surgery in a patient with a petrous apex cholesteatoma were examined using scanning and transmission electron microscopy. Findings were compared to cells studied in a patient with acoustic neuroma. Scanning electron microscopy showed that compared to the apparently normal cells in the acoustic neuroma case, most sensory cells in the cholesteatoma case had large cuticular plates, irregular locations of cilia and no clear polarizations. Supporting cells showed profuse short microvilli on the whole surface. With transmission electron photomicrographs, type I hair cells were not seen and certain morphological changes were observed in type-1I-like cells and supporting cells. We presume that the degenerative changes in the vestibular epithelia were due to circulatory disturbances and/or direct pressure applied to the vestibular nerve at the internal auditory canal, with subsequent involvement of the macula utriculi.
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  • 23
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    European archives of oto-rhino-laryngology and head & neck 254 (1997), S. 396-400 
    ISSN: 1434-4726
    Keywords: Guinea pig hair cells ; Electron microscopy ; Immunocytochemistry ; Nitric oxide synthase ; Sound transduction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Nitric oxide synthase (NOS) activity has been detected previously in the mammalian cochlea at a light microscopic level. Here we present results of electron microscopic analysis for post-embedding immunoreactivity of neural-type NOS I in the cochlea of the guinea pig. Strong enzyme immunoreactivity was identified in the cytoplasm of inner and outer hair cells. Gold-labeled NOS I antibodies were mainly located in electron-dense areas of the cytoplasm, whereas electron-lucent regions of the receptor cells were nearly free from any immunoreactivity. In both types of hair cells anti-NOS I antibodies were also visible in the cuticular plates, hair bundles and nuclei. Further ultrastructural analysis revealed that the submembranous cisternae of the outer hair cells were nearly free from any reaction product, demonstrating that the whole cytoplasm of this hair cell was not immunoreactive. Other NOS I immunoreactivity was identified in the cuticular plates of the inner and outer pillar cells and in the cytoskeletal elements located in the apical parts of Deiter cells, forming the lamina reticularis or in cytoskeletal-containing regions in basal Deiter cells. Anti-NOS antibodies were visible in the nuclei of various cell types. Our findings suggest that nitric oxide produced by NO I synthase in the organ of Corti may act as a modulator of hair cell physiology during the processes of signal transduction with frequence selectivity.
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  • 24
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    European archives of oto-rhino-laryngology and head & neck 254 (1997), S. 196-199 
    ISSN: 1434-4726
    Keywords: Nasopharyngeal angiofibroma ; Ultrastructure ; Myofibroblast ; Immunohistochemistry ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Twenty-eight cases of nasopharyngeal angiofibroma were studied immunohistochemically for cytoskeletal phenotyping of stromal cells. Electron microscopy was also used to study the ultrastructure of five of the tumors. All typical stromal cells showed intensive immunostaining for vimentin, but were negative for smooth muscle actin and desmin. Ultrastructurally, most of these cells appeared to be exclusively fibroblasts. However, in some areas stromal cells were seen that morphologically resembled myofibroblasts by their shapes and arrangement, and were characterized by the coexpression of vimentin and smooth muscle actin. Electron microscopy confirmed their myofibroblastic nature. The present study showed that the typical stromal cells in nasopharyngeal angiofibromas were fibroblasts and not myofibroblasts. In these tumors myofibroblasts occurred only focally, in connection with fibrotic areas and exclusively as a vimentin+/actin+ cytoskeletal phenotype. This indicates that myofibroblasts are not primary stromal tumor cells in nasopharyngeal angiofibromas, but occur due to regressive changes.
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  • 25
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    Medical molecular morphology 30 (1997), S. 25-30 
    ISSN: 1860-1499
    Keywords: Mast cell ; Culture ; Electron microscopy ; Carbohydrate cytochemistry ; Peroxidase
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Mast cells were cultured from human umbilical cord blood CD34-positive cells in the presence of interleukin (IL)-6 and stem cell factor (SCF). Electron microscopically, a particulate or beaded structure, the prominent structure of tryptase-positive mast cell (T mast cell) granules, was frequently observed in 54-day cultures. Straight or coiled lamellae, often observed in the granules of tryptase-and chymase-positive mast cells (TC mast cells), were observed in the granules in 75-day cultures. Cytochemically, the peroxidase activity of the granules was positive but decreased during the term of culture. Glycogen particles were abundant in 54-day cultures, and scarce in 75-day cultures. These findings suggest that the mast cells matured and changed in phenotype during the culture's term.
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  • 26
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    Medical molecular morphology 30 (1997), S. 48-54 
    ISSN: 1860-1499
    Keywords: Pemphigoid vegetans ; Lamina densa ; Mast cell ; Vegetation ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Ultrastructural changes in the skin lesions of pemphigoid vegetans were observed by transmission electron microscopy. Two significant changes were recognized at the vegetating site: (1) The basal lamina was sometimes interrupted and detached from the basal cells, protruding into the dermis to form folds. In the basal cells, hemidesmosomes were not decreased in number but tonofilament bundles were fewer than normal. Occasionally, basal cell processes extended beyond the basal lamina through its gap. These features resembled the epidermal growth factor-induced morphological changes of cultured skin. It was suspected that the abnormal attachment of the basal lamina to the basal cell was associated with keratinocyte proliferation. (2) Mast cells were encountered in the epidermis abutting on the basal lamina. It is uncommon to find mast cells in the epidermis. Mast cells in the epidermis were reported at the erythematous regions which were adjacent to the bullae of bullous pemphigoid, and were thought to have an important role in forming blisters. It was suggested that early changes in blister formation occur at the vegetating site.
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  • 27
    ISSN: 1860-1499
    Keywords: c-Fos ; VIP ; Electron microscopy ; Immunocytochemistry ; Cerebral ischemia
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract We investigated morphological changes in neurons with c-Fos-like immunoreactivity (c-Fos-LI) after cerebral ischemia by light and electron microscopic immunocytochemistry. Strong c-Fos-LI was observed in layers II–VI of the cerebral cortex with an especially abundant distribution in the nuclei of layers II, IV, and VI ipsilateral to the lesioned side. Reperfusion after ischemia had a greater effect on the expression of c-Fos-LI than did permanent ischemia. Vasoactive intestinal peptide (VIP)-positive neurons were seen scattered in layers II–V of the cerebral cortex. Some VIP-positive neurons showed c-Fos-LI after ischemia. Electron microscopy revealed c-Fos-LI in euchromatin in the nuclei of c-Fos-positive cells. Dilatation of the cisternae of the rough endoplasmic reticulum and the presence of numerous secondary lysosomes were found in neurons on the lesioned side after 12h of reperfusion. Some VIP-containing neurons revealed c-Fos-LI with reperfusion after ischemia by a double immunostaining method on the same tissue section. These findings suggest that ischemia potentiates c-fos expression in VIP- or other transmitter- or modulator-containing neurons, thereby protecting from neuronal cell death.
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  • 28
    ISSN: 1860-1499
    Keywords: Helicobacter pylori ; Electron microscopy ; Three-dimensional reconstruction ; Eradication ; 13C-urease breath test ; Coccoid form
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract To investigate the effect of morphological change ofHelicobacter pylori on gastric mucosal inflammation,H. pylori was examined by means of an electron microscope and computer-assisted three-dimensional reconstruction before and after antibacterial therapy. The results showed that the bacterium was usually present in different forms and sizes. Most of these variations are helicobacter shaped, 3–5 μm long (43%), or campylobacter shaped, 1–3 μm long (38%); fewer are round or coccoid (19%), and only 0.5–1 μm long. Active inflammation and an abnormal amount of mucus in the epithelial cells are the main changes seen in gastric mucosa withH. pylori infection. In some cases, 6 weeks after antibacterial therapy,H. pylori could still be observed by toludine blue, with slight positive results withH. pylori-antibody-labeled immunostaining. In contrast to the bacteria before antibacterial therapy, in mostH. pylori-positive cases usually only a minute number of bacteria were seen in coccoid form. These surviving coccoid-form bacteria showed thickened walls, and the surrounding periplasmic space was reduced or nonexistent. The epithelial cells were almost normal and13C-text negative. Although neutrophil infiltration was seldom seen, there were still some surviving bulblike cells with excess amounts of mucus in the gastric pits. It is suggested that the coccoid form ofH. pylori may be a static bacterium without urease production. For therapeutic decisions, it may be more important to identify whether there is an active inflammation in the gastric mucosa than to detectH. pylori.
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  • 29
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    Medical molecular morphology 30 (1997), S. 163-169 
    ISSN: 1860-1499
    Keywords: Dermatofibroma ; Aneurysmal ; (angiomatoid) fibrous histiocytoma ; Immunohistochemistry ; Electron microscopy ; Skin
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract We present a rare case of aneurysmal (angiomatoid) fibrous histiocytoma (AAFH) of the skin on the back of a 40-year-old Japanese man. Histologically, the tumor was characterized by massive proliferation of fibroblastic and histiocytic cells, prominent aggregation of hemosiderin pigment, and the presence of blood-filled tissue spaces devoid of an endothelial lining within a capillaryrich stroma. Immunohistochemically the tumor cells were immunoreactive for vimentin and for Factor XIIIa or Mac387. Ultrastructural study revealed that the tumor was composed mainly of fibroblast-like cells intermingled with histiocyte-like cells and intermediate cells with combined features of the two types of cells. These findings support the fibrohistiocytic origin of aneurysmal (angiomatoid) fibrous histiocytoma. In addition, ultrastructural examination seems quite useful to differentiate from other cutaneous neoplasms with architectural and cytological similarities to this tumor.
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  • 30
    ISSN: 1860-1499
    Keywords: Osteoclast-like giant cell tumor ; Pancreas ; Immunohistochemistry ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract We report a rare case of osteoclast-like giant cell tumor of the pancreas in a 70-year-old Japanese woman. The tumor was composed of a proliferation of ovoid to spindle-shaped mononuclear cells admixed with osteoclast-like giant cells. The tumor cells were immunore-active for vimentin, ±1-antitrypsin, and CD68. In ultrastructural examination, the giant cells resembled osteoclasts, and the mononuclear stromal cells had fibroblastic and histiocytic features. No elements of epithelial differentiation were found in this tumor. These findings suggest that this tumor had a derivation similar to giant cell tumor of bone.
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  • 31
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    Medical molecular morphology 30 (1997), S. 209-215 
    ISSN: 1860-1499
    Keywords: Merkel cell carcinoma ; Dense core granule ; Chromogranin A ; Electron microscopy ; Immunohistochemistry study
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Two cases of Merkel cell carcinoma (MCC) were examined by electron microscopy and immunohistochemistry. Histologically, tumor cells, which extended from the dermis into the subcutis, showed anastomosing bands with partial trabecular pattern. The ultrastructural study showed tumor cells in case 1 with numerous neurosecretory granules. The number of granules in case 2, however, was smaller compared with that in case 1. Perinuclear bundles of filaments were present in case 2, but few bundles were observed in case 1. By immunohistochemistry, cytokeratin (CK)-8, -18, -19, and -20 and epithelial membrane antigen were stained positively within tumor cells in both cases. It was interesting that staining patterns of chromogranin A and of neuron-specific enolase were different in the two cases. These data indicated that CK-20 is a useful marker for diagnosing MCC and that ultrastructural and immunohistochemical differences in both cases were the result of phenotypic variation.
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  • 32
    ISSN: 1861-387X
    Keywords: Microrosette ependymoma ; Spinal cord ependymoma ; Trabecular architecture ; Immunohis-tochemistry ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract “Microrosette ependymoma,” which is ependymoma with numerous microrosettes throughout the tumor, has rarely been reported. We describe an autopsy case of cervical cord ependymoma with two unusual features: the presence of numerous microrosettes and the formation of trabecular architecture. The tumor originated in the C2 segment of a man aged 23 years and gradually expanded over the following 15 years and 10 months until the entire cervical cord was involved. Beside the low grade of malignancy, the tumor cells exhibited a strong tendency to form microrosettes and trabecular architecture, which formed many perivascular pseudorosettes. The microrosettes mostly consisted of only two or a few more cells, in the absence of large rosettes. Thus the constituent cells were those forming perivascular pseudorosettes. Electron microscopy and immunohistochemistry characterized the ependymal properties of the microrosettes, whose lumina frequently contained fibril bundles similar to those of the Reissner's fiber fibrils, in addition to cilia and microvilli. The pathogenesis of the occurrence of numerous microrosettes is unknown; however, a defect in the mechanism of regulation of rosette formation and enlargement is the most likely explanation.
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  • 33
    ISSN: 1860-1499
    Keywords: Gastric carcinoid tumors ; Familial occurrence ; Electron microscopy ; Endocrine granules
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Our report concerns gastric carcinoid tumors in a man and his younger sister who had no endocrine symptoms. The tumors in both cases were multiple, located in the corpus, and showed no significant differences in light microscopic and immunohistochemical examination. In electron microscopic observation, the endocrine granules of tumor cells were roughly classified into four types: granules with fine granular content with low electron density, irregularly striped granules with medium electron density, concentrically laminated or regularly striped granules, or smaller and almost uniformly high electron-dense granules in which it was difficult to recognize the internal structure. From the sequential morphological changes of the granules, we have considered that each type of granule reflects various stages of granulogenesis, although the possibility that they are distinct and contain different hormones or chemical mediators is not absolutely ruled out.
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  • 34
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    Brain tumor pathology 14 (1997), S. 79-83 
    ISSN: 1861-387X
    Keywords: Neurocytoma ; Intraventricular tumor ; Electron microscopy ; Blood vessel ; Tumor cell process
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract A case of central neurocytoma that was confirmed with ultrastructural and immunohistochemical studies has been reported. Ultrastructurally, thin cytoplasmic processes of tumor cells showed differentiation into neuronal cells containing parallel bundles of microtubules and abortive synapses with dense-core vesicles and/or clear vesicles. It was frequently found that the clusters of tumor cell processes were close to or around the microvessels. Microvessels were composed of endothelial cells without fenestrations and had tight junctions in the endothelial clefts. Neurosecretory granules in thin cell processes appeared close to microvessels and may have been secreted around microvessels.
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  • 35
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 1737-1746 
    ISSN: 0887-6266
    Keywords: free volume ; dual mode ; diffusion ; glassy polymer ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The development of a new model for the diffusion of gas molecules in glassy polymers is presented which utilizes concepts from free volume theory and relies on a dual-mode interpretation of sorptive dilation in glassy polymers. Three assumptions are made in the development of the model. First, the free volume available for molecular transport processes is taken as constant below the glass transition temperature. Second, two populations of gas molecules are assumed to exist - one which contributes to the maintenance of an iso-free volume state upon sorptive dilation and one which does not contribute owing to sorption into regions of unrelaxed volume. Third, the former population is assumed to be mobile while the latter is not. The resulting model predicts, at constant temperature, a diffusion coefficient that is independent of solute volume fraction. This is in contrast to the widely used dual-mode sorption model with partial immobilization for gas transport in glassy polymers which leads to a diffusion coefficient that is dependent on solute mole fraction through the molar gas concentration. The new model is used to interpret gas transport data from permeation experiments for carbon dioxide, methane, and ethylene in three polycarbonates. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1737-1746, 1997
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  • 36
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 1793-1805 
    ISSN: 0887-6266
    Keywords: rutile ; surface modification ; diblock copolymer ; inverse gas chromatography ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Various functional diblock copolymers have been used as surface modifiers for rutile pigment in an effort to condition the solid for eventual use in multicomponent polymer systems. Coated surfaces were analyzed by inverse gas chromatography at infinite and finite dilution of the vapor phase, and by XPS. At high coverages (about 10% by weight of the pigment), the diblocks were randomly oriented at the air interface, effectively masking the surface of the rutile. At low diblock concentrations acid/base interactions dominated the orientation of the adsorbed molecule at the rutile interface, thereby also affecting the orientational states at the air interface. In this condition, the performance of the pigment in specified host polymer systems may be expected to vary with the selection of the diblock copolymer modifier. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1793-1805, 1997
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  • 37
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 1843-1854 
    ISSN: 0887-6266
    Keywords: crystallization ; DNA ; fractionation ; gel-electrophoresis ; morphology ; phase transition ; SALLS ; sonication ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polydisperse DNA of reasonable molecular weights was prepared from a mammalian source via sonication and fractionation. A method for characterizing the molecular weight using gel electrophoresis is described. Quiescent crystallization was studied in thin films of one of the fractions induced by rapidly changing the hydration state isothermally. We report the occurrence of the semicrystalline nature of DNA. The crystal growth occurring via aggregates is best described as sheaves and spherulites from DNA gels in the relative humidity range (RH) corresponding to A-DNA. These habits exhibit primary nucleation and secondary growth, which closely resemble those of melt-crystallized, synthetic macromolecules and, in a follow-up report, will be shown to be lamellar in nature. Small, needle-like crystals are observed for B-DNA hydration levels, and are unstable at lower hydration levels. A transformation from needle to lamellar crystals can occur, even when the primary nucleation of lamellar forms is otherwise absent at that hydration level, through a cylindrical phase exhibiting selective reflection of colored bands. The hydration level plays, in part, the role of the supercooling in this system and the long-known hysteresis in the formation and dissolution of the A-DNA (crystals) can now be viewed in light of those factors known to operate in semicrystalline systems. A morphological phase diagram is developed and is in accord with the known physical evidence. Because this preparation and these morphological observations are without precedence, substantial detail into methodology is included for this first article in the series. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1843-1854, 1997
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  • 38
    ISSN: 0887-6266
    Keywords: kraft lignin ; thermoplastics ; polymer association ; poly(vinyl acetate) ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Interest in the development of lignin-containing polymeric materials has been upheld more or less continuously for the past 20 years. Tendencies toward high moduli and poorly defined thermal transitions have been regarded as imposing inevitable limitations upon the use of lignin derivatives for such purposes. Incorporation of more than 25-40% (w/w) lignin had usually resulted in materials that were brittle and weak. For the first time, however, from homogeneous blends containing 85% (w/w) underivatized industrial kraft lignin with poly(vinyl acetate) and two plasticizers, a series of thermoplastics has been fabricated with promising mechanical properties. The tensile behavior of these new polymeric materials depends directly upon the degree of association between the intrinsic kraft lignin components. In extending to values about 25 MPa and 1.5 GPa, respectively, the tensile strengths and Young's moduli vary linearly with the effective M̄w for the kraft lignin species, under conditions where the proportions of the individual molecular components, both associated and discrete, do not change. Moreover, melt-flow index measurements indicate that these polymeric materials are amenable to thermal processing by extrusion molding. Thus a significant step has been taken toward developing a new generation of thermoplastics that are lignin-based in a very fundamental way. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1899-1910, 1997
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  • 39
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 1933-1942 
    ISSN: 0887-6266
    Keywords: self-diffusion ; viscosity ; polymer melt ; entanglement ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dynamic properties in the melt state for two saturated hydrocarbon polymers, poly(ethylene-alt-propylene) (PEP) and head-to-head polypropylene (HHPP), were investigated by viscoelastic and diffusion measurements. Several nearly monodisperse linear samples of each species were used. Zero-shear viscosity η0 and self-diffusion coefficient D varied with temperature in accord with the WLF equation, and they also varied with molecular weight M in a manner that was consistent with the behavior of other species. The product η0D was of particular interest because extensive previous results for two other species, polystyrene and polyethylene, had led Pearson et al. to suggest that η0D/(η0D)Rouse is a universal function of the number of entanglements per molecule M/Me. With values for the Rouse model product for each species calculated from chain dimensions, and entanglement molecular weight from the plateau modulus, we show that the data for PEP and HHPP also support the Pearson universal form. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1933-1942, 1997
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  • 40
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 1963-1971 
    ISSN: 0887-6266
    Keywords: dynamic mechanical analysis ; fluorinated poly(ethers) ; intermolecular cooperativity ; relaxation behavior ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The relaxation behavior of six fluorinated aromatic poly(ethers) was investigated using dynamic mechanical analysis. The glass transition temperature was found to increase as the size and rigidity of linking groups increased and varied between 168°C for a dimethyl linking group and 300°C for a bicyclic benzoate ether-linking group. For the α-relaxation the steepness of time/temperature plots and broadness of the loss curves could be qualitatively correlated with chemical structure in a manner predicted by the coupling model of relaxation. Well-separated sub-Tg transitions were also observed, as a shoulder on the low temperature side of the α-peak, and as a broad, low loss transition around -100°C. The higher temperature process was similar to the structural relaxation often found in quenched glassy polymers, while the position, intensity, and breadth of the subambient process was sensitive to chemical structure. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1963-1971, 1997
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  • 41
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 507-515 
    ISSN: 0887-6266
    Keywords: poly(acrylic acid) ; FTIR ; polyelectrolyte ; conformation ; conformers ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Fourier transform infrared (FTIR) spectroscopic measurements have been undertaken to estimate the conformational energies of poly(acrylic acid) (PAA) cast films in the temperature range of 40-130°C. The temperature dependence of the IR spectra in the C=O stretching region has been analyzed to yield the side-chain and backbone conformational energies. The estimated energies are close to those previously obtained by polarized Raman spectroscopic measurements for PAA solutions. Combining the FTIR value of conformational energy with the simplified rotational isomeric state (RIS) model proposed in the Raman analysis provides a persistence length in accordance with earlier SAXS experiments. The data also agree with the Gibbs-DiMarzio predictions, further substantiating the validity of the analysis. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys, 35: 507-515, 1997
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 2195-2200 
    ISSN: 0887-6266
    Keywords: ESR ; mechanoradicals ; PMMA ; drilling apparatus ; computer simulation ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In this study, initially, we tried to obtain the mechanoradicals of PMMA (poly(methyl methacrylate)). For this purpose, we designed a simple drilling apparatus. Using this apparatus, we prepared some PMMA samples at 77 K in vacuum. Later, by using an ESR (electron spin resonance spectrometer), we observed ESR signals for these samples at 77 K. This means that mechanoradicals have been successfully produced by mechanical fracture in PMMA using our drilling apparatus. Secondly, we tried to identify the radicals from these spectra through using theoretical analyses and, some computer simulations have been done by suggesting two different theoretical models for these ESR signals. Finally, by using experimental and theoretical data, we showed that our simple apparatus could be used to obtain mechanoradicals from polymers. Results were seen to be in very good agreement with the literature. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2195-2200, 1997
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 2219-2231 
    ISSN: 0887-6266
    Keywords: nylons ; crystallinity ; DSC ; x-ray diffraction ; complications ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Differential scanning calorimetry (DSC) is one of the most widely used technique for measuring crystallinity in the polymer industry. The major source of error in the crystalline index (CIDSC) of low crystallinity polymeric articles, is the development of further crystallinity during the DSC scan. Although, this type of cold crystallization is obvious, and thus accounted for in polymers like polyethylene terephthalate, nylons are a difficult class of materials in that respect. The major contributing factors to the failure of DSC in measuring low levels of crystallinity in nylons are identified to be (1) silent crystallization between the glass (Tg) and melting (Tm) transitions, (2) extreme difficulties in packing a moisture-free nylon in the sample pan (the response due to traces of moisture being a broad endotherm competing with a broad exothermic crystallization), and (3) a sub-Tm exotherm, especially in low crystallinity nylons, due to relaxation of the processing-induced stresses. These factors, specific to nylons, mask the observation of cold crystallization and lead to substantially higher than real crystallinities. This manuscript deals with such complications and corrective actions using commercial nylon 6 films of CIDSC = 0-40%. X-ray diffraction measurements have been included to support the validity of our improved DSC methodology. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2219-2231, 1997
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 2281-2292 
    ISSN: 0887-6266
    Keywords: conformation ; phonon dispersion ; α-helix ; normal modes ; poly(L-leucine) ; density of states ; heat capacity ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(L-methionine) (PMet) is one of the two sulfur containing polyamino acids. Raman, FTIR spectra, and heat capacity measurements of PMet have been well interpreted through the normal mode analysis and the density of states derived therefrom. Earlier interpretation of heat capacity data is limited because it is based on the Tarasov model, wherein the concept of group frequency and skeletal similarity are used. A special feature of some dispersion curves is their tendency to bunch in the neighborhood of the helix angle. This has been attributed to the presence of strong intramolecular interactions. Repulsion between the dispersion curves is also observed. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2281-2292, 1997
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 2297-2307 
    ISSN: 0887-6266
    Keywords: crosslinked polymers ; photopolymerizations ; living radical polymerizations ; mechanical properties ; dynamic mechanical analysis ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Crosslinked polymer networks are used in a wide variety of applications. To use these materials effectively, a fundamental understanding of their structural evolution and the relationship between material properties and structure is essential. In this article, a novel technique employing “iniferters,” i.e., living radical polymerizations, to photopolymerize these networks is utilized to study the property and structural evolution of these highly desirable materials. Living radical polymerizations are used in this work since this technique avoids the problem of carbon radical trapping encountered while using conventional initiators. Dynamic mechanical measurements are performed on highly crosslinked methacrylate networks to glean information regarding their structural heterogeneity. By performing these measurements on homopolymerized samples at various stages of the reaction and on copolymerized samples of multifunctional methacrylates, the mechanical properties are characterized as a function of double bond conversion and comonomer composition. From such analyses, with respect to both temperature and frequency, quantitative conclusions regarding the structure of the networks are drawn. This effort is aimed at exploiting the living radical polymerizations initiated by p-xylylene bis(N,N-diethyl dithiocarbamate) (XDT), to study the mechanical property evolution and structural heterogeneity of crosslinked polymers which is nearly impossible otherwise. Polymers examined in this study include networks formed by homopolymerization of diethylene glycol dimethacrylate (DEGDMA) and polyethylene glycol 600 dimethacrylate (PEG600DMA) as well as copolymers of DEGDMA and PEG600DMA. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2297-2307, 1997
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 771-776 
    ISSN: 0887-6266
    Keywords: Nafion ; positron annihilation ; free volume ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We report a new result on positron annihilation studies in acid- and cation-neutralized (Li+, Na+, K+, Rb+, Cs+, UO22+, Ni2+) Nafion membranes using positron lifetime and Doppler-broadened annihilation radiation (DBAR) measurements. The free-volume structure is characterized using a simple quantum mechanical model of positronium (Ps) in a spherical well. Our studies indicate that formation and expansion of clusters is always associated with a change in free-volume structure resulting in smaller free-volume holes. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 771-776, 1997
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  • 47
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 749-761 
    ISSN: 0887-6266
    Keywords: polycarbonate ; polyglutanimide ; polymer blends ; copolymer ; compatibilization ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Imide units copolymerized with MMA units have been selected in order to improve compatibility between PC and acrylics through specific interaction or internal repulsion. Good dispersion of acrylic inside a PC matrix has been observed upon melt mixing, which can be partially explained by the good rheological agreement between these two polymers. Transmission electron microscopy has shown that the system remains phase separated from 5 to 95 wt % of PC. Phase diagrams for three different imide concentrations have been drawn. Results obtained by DSC (conventional and with enthalpy relaxation) are similar to those obtained by optical cloud point detection. The phase diagrams show the raise of the PC/PMMA demixtion curve (LCST type) when percentage of imide increases in the acrylic phase. Theoretical calculations on binary interaction energy density show a slight improvement of the interaction between acrylic and PC when imide percentage increases. Cloud point measurements on 50/50 PC/acrylic blends varying the imide concentration show that the improvement of compatibility deduced from the raise of the demixtion curve (LCST type) is more related to a kinetic effect (the high Tg of imidized samples is reducing macromolecule mobility) than specific interactions. The calculated favorable interactions are probably too weak to be detected with cloud point measurements. The microstructures obtained after crystallization of the PC phase under solvent vapors in phase separated PC/acrylics blends can also be explained by Tg effects. Moreover, solvent vapor exposure could be a powerful tool to determine the real thermodynamic behavior of the blends at room temperature. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 749-761, 1997
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 777-788 
    ISSN: 0887-6266
    Keywords: PMDA-ODA polyimide ; intrinsic molecular properties ; sheet mapping ; fabrication processes ; three-dimensional orientation functions ; anisotropic coefficient of thermal expansion (CTE) ; anisotropic mechanical moduli ; anisotropic compliances ; anisotropic dielectric constants ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A practical methodology for the correlation and prediction of the process-property performance of advanced materials is developed. The model polymer studied is PMDA-ODA polyimide. The connecting link between the process and the properties is the structural state of the polymer. An essential ingredient for a quantitative characterization of the system is a knowledge of its phase state and intrinsic molecular properties. The intrinsic molecular properties define the limiting performance properties available to the polymer. Anisotropic films and sheets produced by five different fabrication processes are examined. Maps of the molecular symmetry axis, the orientation function, and the thickness distributions of two 50-in.-wide sheets fabricated differently are measured nondestructively for process comparison. Four other film fabrication processes are examined and their three-dimensional orientation states determined and correlated. A three-dimensional orientation function triangular plot permits simultaneous representation of the different fabrication processes on the same figure and allows the investigator to choose the most economic and efficient fabrication route. The structure-property study includes the structural correlation and intrinsic molecular property determination of the anisotropic coefficient of thermal expansion (CTE), the anisotropic mechanical moduli and compliances, and the anisotropic dielectric constants. 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 777-788, 1997
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 831-839 
    ISSN: 0887-6266
    Keywords: polymer blends ; analog calorimetry ; heat of mixing ; mean-field binary interaction model ; polystyrene ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Analog calorimetry is used to study the interaction between styrene and acrylonitrile repeat units. Electrostatic charge calculations were used as a guide to divide the polymer repeat units and analogs into groups. A mean-field binary interaction model was used to evaluate group interaction energies. The enthalpic interaction energy for the styrene-acrylonitrile pair from this study is 7.63 ± 0.12 cal/cm3 which is consistent with values obtained from phase behavior studies of poly(styrene-co-acrylonitrile) blends. The cyano group, C(TRIPLE BOND)N, of the acrylonitrile repeat unit has a permanent dipole. The results of this study suggest that the orientation of this dipole with respect to the backbone of the acrylonitrile unit strongly affects its interaction with styrene repeat unit. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 831-839, 1997
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  • 50
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 849-864 
    ISSN: 0887-6266
    Keywords: ABC block copolymers ; self-assembly ; microphases ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The random phase approximation has been used to extend the Leibler theory for the stability limit of a homogeneous melt of A-B diblock copolymers to examine the onset of microphase and macrophase separation in a variety of ABC block copolymer systems. The stability limit is located by the divergence of the collective structure factor of the melt. We introduce and analyze three models for ABC block copolymers: linear triblocks, random comb copolymers where a fixed number of A and B teeth are placed randomly along a C backbone, and statistical comb copolymers, with A or B teeth spaced regularly, but with sequences constructed using a two parameter Markov process. We compute order-disorder stability boundaries for the segregation strength parameter χABN at threshold as a function of χACN, χBCN, composition, and other model parameters, and compare the results for the three different architectural models. An interesting “reentrant order-disorder transition” is located in several model phase diagrams, and is associated with a peculiar situation in which more incompatibility causes less segregation. In the case of statistical combs, macrophase separation into two liquid phases can be favored over microphase separation. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 849-864, 1997
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 1373-1381 
    ISSN: 0887-6266
    Keywords: PDLC ; LC droplet ; LC configuration ; electro-optical response ; conductance ; dielectric constant ; dielectric loss ; switching voltage ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polymer dispersed liquid crystal (PDLC) films (5CB/PMMA, 60/40) of different droplet size were prepared by a solvent-induced phase separation method under different N2 flow speeds. The effects of droplet size on the thermal transitions of the LC and various dielectric properties such as dielectric constant, conductance, dielectric loss, and the electric field induced in a droplet were examined. The configuration of the LC in the film with smaller droplets can be identified by comparing the dielectric constant of the film with the one predicted by Boettcher's mixture formula. In addition, the effect of droplet size on the electro-optical response of the PDLC film was investigated. Variations of the conductance and the dielectric constant of the film were analyzed under various AC frequencies, with the purpose of elucidating the polarization mechanism of the LC molecules in the droplet. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1373-1381, 1997
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 1415-1421 
    ISSN: 0887-6266
    Keywords: epitaxy ; recrystallization ; high-density polyethylene ; isotactic polypropylene ; morphology ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The recrystallization behavior of high-density polyethylene (HDPE) on the highly oriented isotactic polypropylene (iPP) substrates at temperatures below the melting temperature of HDPE has been investigated by means of transmission electron microscopy. The results obtained by the bright-field observation and the electron diffraction show that upon annealing the HDPE-quenched films on the oriented iPP substrates at temperatures below 125°C, only a small amount of HDPE recrystallizes on the iPP substrate with [001]HDPE//[001]iPP, while annealing the HDPE-quenched films at temperatures above 125°C, all of the HDPE crystallites recrystallize epitaxially on the iPP substrate with [001]HDPE//[101]iPP. © 1997 John Wiley & Sons, Inc. J Polym Sci B: 35: 1415-1421, 1997
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 1433-1438 
    ISSN: 0887-6266
    Keywords: polyelectrolyte gel ; reduced viscosity ; dipole-dipole attraction ; medium polarity ; copolymerization ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Copolymerization of 2-acrylamido-2-methylpropane sulfonic acid (AMPS, monomer 1) with 2-hydropropyl methacrylate (HPM, monomer 2) was conducted in ethylene glycol/water (1 : 1 in weight) at 70°C. The reactivity ratios estimated from the copolymer composition at low conversion are r1 = 2.31 ± 0.25 and r2 = 11.70 ± 1.05. The azeotropic composition was found at the monomer mole ratio AMPS/HPM equal to 8/2. Viscosity of these copolymers was measured in dimethyl sulfoxide (DMSO) and DMSO/tetrahydrofuran (THF) mixed solvent at 25 ± 0.05°C. Polyelectrolyte behavior was observed for all the copolymers, even in the mixed solvent containing 65 wt % of THF. The reduced viscosity at constant polymer concentration decreased with increasing THF content in the mixed solvent. The copolymers having AMPS repeat units more than 42 mol % precipitated in the mixed solvent when the THF was beyond 68 wt %. The viscosity reduction and precipitation in the copolymer solutions with increasing THF can be attributed to the dipole-dipole attraction between ion-pairs formed in less-polar medium. This is helpful in understanding the volume phase transition in highly charged hydrogels caused by mixing solvents. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1433-1438, 1997
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 1261-1267 
    ISSN: 0887-6266
    Keywords: FTIR-ATR spectroscopy ; gravimetric sorption ; diffusion ; polymer ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In this study, vapor sorption FTIR-ATR (Fourier Transform Infrared Attenuated Total Reflectance) spectroscopy was combined with a conventional gravimetric sorption balance to examine diffusion in polymers. Mutual diffusion coefficients of methyl ethyl ketone in polyisobutylene were measured using both methods at various penetrant activities and temperatures in the range 40-60°C. Actual penetrant concentrations were determined from the sorption balance. The diffusion coefficients from the two techniques agree very well with each other. In addition, the diffusivity data from both techniques could be correlated successfully as a function of temperature and concentration with the Vrentas and Duda free-volume model. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1261-1267, 1997
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 1269-1277 
    ISSN: 0887-6266
    Keywords: poly(4-methylpentene-1) ; hydrogenated oligo (cyclopentadiene) ; blends ; miscibility ; mechanical properties ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: This article discusses the influence of the oligomeric resin, hydrogenated oligo(cyclopentadiene) (HOCP), on the morphology, and thermal and tensile mechanical properties of its blends with isotactic poly(4-methylpentene-1) (P4MP1). The P4MP1 and HOCP are found not miscible in the melt state. P4MP1/HOCP blends after solidification contain three phases: the crystalline phase of P4MP1, an amorphous phase of P4MP1, and an amorphous phase of HOCP. From optical micrographs obtained at 150°C, it is found that the solidified blends show a morphology constituted by P4MP1 microspherulites and small HOCP domains homogeneously distributed in intraspherulitic regions. DSC and DMTA results show that the blends present two glass transition temperatures (Tg) equal to the Tgs of the pure components. The tensile mechanical properties have been investigated at 20, 60, and 120°C. At 20°C both the HOCP oligomer and the amorphous P4MP1 are glassy, and it is found that all the blends are brittle and the stress-strain curves have equal trends. At 60°C the HOCP oligomer is glassy, whereas the amorphous P4MP1 is rubbery. The tensile mechanical properties at 60°C are found to depend on blend composition. It is found that the Young's modulus, the stresses at yielding and break points slightly decrease with HOCP content in the blends and these results are related to the decrease of blend crystallinity. The decrease of the elongation at break is accounted for by the presence of glassy HOCP domains that act as defects in the P4MP1 matrix, hampering the drawing. At 120°C both the amorphous phases are rubbery. It is found decreases of Young's modulus, stresses at yielding and break points. These results have been related to the decrease of blend crystallinity and to the increase of the total rubbery amorphous phase. Moreover, it is found that the blends present elongations at break equal to that of pure P4MP1. This constancy is attributed to: (a) at 120°C the HOCP domains are rubbery and their presence seems not to disturb the drawing of the samples; (b) a sufficient number of the tie-molecules and entanglements of P4MP1 present in the blends. In fact, although the numbers of tie-molecules and entanglements decrease in the blends, increasing the HOCP oligomer, they seem to be enough to keep the material interlaced and avoid earlier rupture. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1269-1277, 1997
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 1311-1331 
    ISSN: 0887-6266
    Keywords: branched prepolymers ; hydrosilylation cure ; densely crosslinked polymers ; thermal and mechanical properties ; tough-brittle transition ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The thermal and mechanical properties of two densely crosslinked polycarbosiloxane systems were investigated in relation to the molecular structure. The networks were prepared from functional branched prepolymers and crosslinked via a hydrosilylation curing reaction. The prepolymers having only vinyl functionalities (poly[phenylmethylvinyl]siloxanes) were crosslinked by using crosslinking agents with reactive silicon-hydrogen groups. In prepolymers having both silicon-vinyl and silicon-hydrogen groups (poly[phenylmethylvinylhydro)]siloxanes crosslinking took place intermolecularly. The thermal and mechanical properties of the polymer networks were found to be dependent on the phenyl —Si—O3/2 (branches) content in the prepolymer, the number of elastically effective crosslinks, the elastically effective network chain density and molecular weight between crosslinks, length of the chain segments introduced by the hydrosilylation crosslinking reaction, and the number of dangling ends. As a consequence of the dense crosslinking, the mechanical properties were also strongly dependent on the glass transition temperature. A tough-brittle transition was observed around the glass transition temperature of the polymer networks. The properties of the poly(phenylmethylvinylhydro)siloxane networks were found to be superior to those of the poly(phenylmethylvinyl)siloxane networks. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1311-1331, 1997
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 1361-1372 
    ISSN: 0887-6266
    Keywords: polymer ; infrared ; attenuated total reflection (ATR) ; dichroism ; molecular orientation ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The orientation of molecular chains in polymers cannot be easily extracted from ATR spectra measurements. One can infer the orientation parameters by using plausible models that describe the type of the statistical distribution of the molecular chains in the sample. In this work, we are interested in the case of weakly aligned polymers. Therefore, we first adjusted the partial axial orientation model usually applied for strongly oriented polymers to the samples under our investigations and second, related the parameters describing the orientation configuration to the dichroic ratios in four particular molecular chain distributions: randomly, totally, partially, and elliptically oriented. A new method that leads to the determination of these dichroic ratios from ATR spectra is presented. This method is based only on the use of three distinct polarizations of the beam. Thus, all the practical difficulties usually encountered in the other methods are eliminated. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1361-1372, 1997
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 1405-1414 
    ISSN: 0887-6266
    Keywords: silk fibroin ; FT-IR spectroscopy ; hydrogen bonds ; polyacrylonitrile ; poly(acrylonitrile-co-methyl acrylate) ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: FT-IR spectroscopy was used to study the specific interactions in polyacrylonitrile-silk fibroin (PAN-SF) and poly(acrylonitrile-co-methyl acrylate)-silk fibroin (PANMA-SF) blends. No specific interaction was found in PAN-SF blends. In PANMA-SF blends, however, a new 1703 cm-1 band, assigned to be hydrogen-bonded carbonyl groups of PANMA, appears, and its intensity depends on the compositions of the blends and the MA contents in PANMA. Furthermore, when the sample was heated, considerable changes in position and intensities of the hydrogen-bonded bands, in both stretching regions of the carbonyl group of PANMA and the hydroxl group of SF, were found, and these changes were irreversible on cooling. Finally, we suggested that the bands of hydrogen bonds in PANMA-SF blends may be the average result of several kinds of possible hydrogen bondings. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1405-1414, 1997
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 1423-1432 
    ISSN: 0887-6266
    Keywords: crystallite ; Kevlar ; moisture sorption ; poly(p-phenylene terephthalamide) ; wide-angle x-ray diffraction ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Wide-angle x-ray diffraction studies were performed for as-spun wet poly(p-phenylene terephthalamide) fiber. The effects of sorbed water on the equatorial diffractions from the (110) and (200) crystal planes and on the meridional diffractions from the (002), (004), and (006) crystal planes were analyzed during desorption and absorption. There was no significant change in the d-spacing from the respective crystal plane irrespective of the moisture (water) regain. The ratio of the diffracted intensity from the (110) diffraction to that from the (200) diffraction remarkably increased by removing the sorbed water. The crystallite size estimated from the (110) diffraction, L110, also increased as the moisture regain decreased, while the L200 did not increase. The longitudinal size of paracrystallite, D001, also remarkably increased with the decrease in moisture regain with the lattice distortion factor, gII, kept unchanged. These results strongly suggested the growth of the crystallite via hydrogen bonds in the lateral (b-axis) direction. The growth of the lateral size of crystallite also accompanied the longitudinal growth of crystallite during desorption. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1423-1432, 1997
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 1449-1461 
    ISSN: 0887-6266
    Keywords: adhesion ; oxide coating ; fragmentation test ; molecular orientation ; substrate temperature ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Fragmentation tests in the uniaxial mode were performed on poly(ethylene terephthalate) (PET) films coated with a 100 nm thin silicon oxide layer. The coating's fragmentation process was analyzed in light of the mechanical behavior of the polymer substrate. It was shown that, upon unloading samples strained to less than 4% nominal strain, strain recovery leads to the closure of coating cracks. The usual fragmentation diagram, which shows the crack density (CD) versus applied strain, was used to identify the various energy dissipation mechanisms controlling the fragmentation process. An alternative presentation of CD versus true stress provided accurate measurements of both fragmentation and saturation onsets. The interfacial strength was modeled from the CD at saturation according to the Kelly-Tyson approach, including a Weibull distribution of the coating strength. The prediction was compared to the substrate shear stress at saturation. Effects of substrate yield, temperature, and molecular orientation are discussed. It was shown that the coating deposition by evaporation on the PET substrate did not induce structural changes at the polymer interface, whereas heat treatments increased the polymer crystallinity in the interfacial zone, resulting in higher interfacial strength. © 1997 John Wiley & Sons, Inc. J. Polym Sci B: Polym Phys 35: 1449-1461, 1997
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 1533-1543 
    ISSN: 0887-6266
    Keywords: polysilane ; lamellar microstructure ; crystal structure ; crystallization kinetics ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The thermal behavior and physical structure of atactic poly(methyl-n-propylsilane) (PMPrS) have been investigated by complementary techniques. Temperature-dependent wide-angle X-ray scattering as well as thermal analysis clearly indicate that atactic PMPrS crystallizes below 40°C in a monoclinic lattice with PMPrS adopting an all-trans planar zigzag conformation. Above 40°C, the polymer is in the isotropic amorphous state. A restricted analysis of the structure factors of PMPrS has been performed, indicating that the zigzag planes most probably lie in (110) planes. The chains pack with little interpenetration, and the crystals may be considered as bundles of long, closely packed prisms. The restricted interlocking of neighboring chains results, in turn, in a poor register of the chains along the c-axis. Moreover, transmission electron microscopy reveals that the crystallized polymer adopts a lamellar microstructure, with parallel lamellae tending to form tight bundles. Both electron microscopy and small-angle X-ray scattering indicate crystal thicknesses of about 60 Å. Finally, PMPrS was found to crystallize with a nucleation-controlled type of kinetics. Avrami exponents were calculated as n ≈ 1, suggesting a fibrillar growth geometry compatible with the absence of spherulitic superstructure. A double-melting behavior is also observed for PMPrS. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1533-1543, 1997
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  • 62
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 1575-1588 
    ISSN: 0887-6266
    Keywords: poly(naphthalic anhydride) ; crystal structure ; electron diffraction ; confined thin film melt polymerization ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Single crystals of poly(naphthalic anhydride) (PNA) have been grown using our confined thin film melt polymerization technique. Lamellae, 70-100 Å thick, are found for the crystals polymerized at 180°C with thinner lamellae for a 200°C polymerization temperature. In addition, irregular lath-shaped crystals are found for both polymerization temperatures, apparently formed by a solid-state polymerization process within the original needle-like monomer crystals. The crystal structure of PNA has been studied by electron diffraction (ED) and computer modeling based on seven different zonal ED patterns. It is found that, in most cases, two or three different zonal patterns are superimposed with a common plane, suggesting variable chain tilting even in individual lamellae. Shearing of the material shortly after the initiation of polymerization, permitted obtaining an additional [010] zone ED pattern. A monoclinic unit cell with one chain, two repeat units is proposed based on measurements of 21 independent reflections; the space group is Pc11; a = 6.26 Å, b = 4.33 Å, c = 18.60 Å, and α = 122.5°. The computer-simulated (Cerius2) molecular conformation and chain packing are described with the corresponding simulated electron diffraction patterns being in good agreement with the observed ones. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1575-1588, 1997
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 1589-1592 
    ISSN: 0887-6266
    Keywords: poly(tetrahydrofurfuryl acrylate) ; poly(2-ethylbutyl acrylate) ; characteristic ratio ; glass transition temperature ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The synthesis, characteristic ratio C∞ and glass transition temperature (Tg) of poly(tetrahydrofurfuryl acrylate) (PTHFA) and of poly(2-ethylbutyl acrylate) (P2EBA) are reported. P2EBA has slightly lower flexibility (C∞ = 9.2) than PTHFA (C∞ = 8.6), mainly because of the higher bulkiness of its side group and the closer proximity to the main chain. The C∞ results compared with the corresponding polymethacrylates show an increase in flexibility due to the absence of the α-methyl group. Comparison with poly(methyl acrylate) clearly shows the influence of the bulkiness of the side group on the chain flexibility. The lower Tg of P2EBA than that of PTHFA may be explained by the higher flexibility of the 2-ethylbutyl side group. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1589-1592, 1997
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  • 64
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 1621-1631 
    ISSN: 0887-6266
    Keywords: pulsed photothermal radiometry ; thermal diffusivity ; polymer films ; chain orientation ; thermal anisotropy ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We have developed a pulsed photothermal radiometry technique for determining the thermal diffusivity parallel to the surface of a polymer film that involves flashing a line-shaped laser beam on the surface of the sample at right angle to its length, and monitoring the temperature change with time at a distance from the line source using an infrared detector. Combining this with our previous laser-flash radiometry method for thermal diffusivity measurement perpendicular to the film surface, we can now measure the thermal diffusivity of a polymer film along all directions. These two techniques have been used to study uniaxially and biaxially oriented poly(ethylene terephalate) and uniaxially drawn ultrahigh molecular weight polyethylene films. For uniaxially oriented poly(ethylene terephalate), the thermal diffusivity along the draw direction is substantially higher than that in the transverse direction, which in turn, is slightly higher than that in the thickness direction. For a polyethylene film with a draw ratio of 200, the axial thermal diffusivity is extremely high, being about five times that of stainless steel. The anisotropy of the thermal diffusivity of this film exceeds 90. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1621-1631, 1997
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 1649-1650 
    ISSN: 0887-6266
    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 B: Polymer Physics 35 (1997), S. 2245-2258 
    ISSN: 0887-6266
    Keywords: poly(1-trimethylsilyl-1-propyne) ; ethanol ; n-pentane ; solubility ; diffusivity ; mobility ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The diffusion coefficient of ethanol and of n-pentane in PTMSP, at 27°C, was measured as a function of concentration up to a penetrant content of about 12% by weight, for polymer samples obtained through different processes; differential sorptions and desorptions with vapor phases were considered. In the case of ethanol a nonmonotonous behavior was observed for the diffusivity, while in the case of n-pentane the same property was found to monotonously decrease with increasing the penetrant content. The sorption isotherms were also reported, indicating that n-pentane exhibits a typical dual mode behavior, while ethanol follows an unusual s-shape curve. The chemical potential of the dissolved penetrants, calculated directly from the isotherms, shows the very different importance of the energetic interactions of the two penetrants with the polymer units. In spite of the remarkably different concentration dependencies observed for both solubility and diffusivity of the two penetrants, the mobility factors are in both cases monotonously decreasing with the penetrant concentration, and follow very similar trends. The significant differences observed for the concentration dependence of the diffusion coefficients are, thus, associated to the thermodynamic contributions, which are very different for n-pentane and ethanol. Different polymeric films, obtained through different solvent evaporation processes, show quite different solubility, diffusivity and mobility for both ethanol and n-pentane. On the other hand, the ratio between the mobility of the two penetrants as well as the slope of mobility as function of the concentration remains the same for all the different samples inspected. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2245-2258, 1997
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 2193-2194 
    ISSN: 0887-6266
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 2385-2389 
    ISSN: 0887-6266
    Keywords: optical polymer films ; nonlinear optical polymer ; crosslinked polymer ; polymer waveguides ; solubility ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: No abstract.
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  • 69
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    Keywords: polyimide membrane ; ultraviolet light irradiation ; crosslinking ; physical changes ; gas permeability ; sorption property ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Two types of polyimide membranes; one crosslinkable and the other noncrosslinkable using ultraviolet light irradiation (UV irradiation), were prepared and investigated concerning the effect of UV irradiation on their gas permeabilities and selectivities. Permeability and diffusion coefficients for O2, N2, H2, and CO2 were determined using the vacuum pressure and time lag method. Sorption properties for carbon dioxide were carried out to evaluate the changes in the free volume in the membranes due to the irradiation. In both membranes, permeability coefficients for all gases used in this study decreased and permselectivity, particularly for H2 over N2, increased with increasing UV irradiation time without a significant decrease in the flux of H2. The coefficients depended on the membrane thickness, suggesting asymmetrical changes in both membranes due to UV irradiation. It was suggested by an attenuated total reflection (ATR) FTIR method and analysis of the gas sorption properties of the membranes that the physical changes due to UV irradiation at the irradiated side in both membranes significantly affected their gas permeation properties compared with the chemical changes, especially the crosslinking in the crosslinkable type. © 1997 John Wiley & Sons, Inc. J. Polym Sci B: Polym Phys 35: 2259-2269, 1997
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  • 70
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 2271-2280 
    ISSN: 0887-6266
    Keywords: polymer ; blends ; interface ; morphology ; interfacial tension ; breaking thread ; coalescence ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The breaking thread and the sessile drop methods have been used to evaluate the interfacial tension between a polypropylene (PP) and a polyethylene-terephthalate (PET). An excellent correlation was found between the two. The breaking thread technique was then used to evaluate the interfacial tension of these blends at various levels of a styrene-ethylene butylene-styrene grafted with maleic anhydride (SEBS-g-MA) compatibilizer. In order to evaluate the relative roles of coalescence and interfacial tension in controlling dispersed phase size reduction during compatibilization, the morphology of PP/PET 1/99 and 10/90 blends compatibilized by a SEBS-g-MA were studied and compared. The samples were prepared in a Brabender mixer. For the 10/90 blend, the addition of the compatibilizer leads to a typical emulsification curve, and a decrease in dispersed phase size of 3.4 times is observed. For the 1/99 blend, a 1.7 times reduction in particle size is observed. In the latter case, this decrease can only be attributed to the decrease of the interfacial tension. It is evident from these results that the drop in particle size for the 10/90 PP/PET blend after compatibilization is almost equally due to diminished coalescence and interfacial tension reduction. These results were corroborated with the interfacial tension data in the presence of the copolymer. A direct relationship between the drop in dispersed phase size for the 1/99 PP/PET blend and the interfacial tension reduction was found for this predominantly shear mixing device. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2271-2280, 1997
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  • 71
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 2379-2384 
    ISSN: 0887-6266
    Keywords: ultrasound degradation ; microwave degradation ; polyamides ; polypeptides ; polyglutamates ; polyaspartates ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: No abstract.
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 2391-2396 
    ISSN: 0887-6266
    Keywords: surface stresses of elastic networks ; modulus ; reduced stress ; polydimethylsiloxane network ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: For thin elastic films of crosslinked polydimethylsiloxane (PDMS), the tensile modulus was found to be an increasing function of reciprocal thickness over the whole range of elongations. PDMS films between 0.052 and 0.018 mm were investigated. With decreasing film thickness, surface properties may be expected to increasingly contribute to the measured modulus. For small elongations, surface tension is expected to have no effect or to decrease the measured modulus compared with that of a bulk sample. If a surface layer with a modulus greater than that of the bulk modulus is assumed to exist, then the observed increase in modulus with decreasing film thickness can be explained. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2391-2396, 1997
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  • 73
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 2409-2419 
    ISSN: 0887-6266
    Keywords: MALDI-TOF-MS ; Matrix Assisted Laser Desorption Ionization ; poly(methyl methacrylate) ; α-methylstyrene ; copolymer ; standard reference materials ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Matrix Assisted Laser Desorption Ionization (MALDI) Time of Flight (TOF) Mass Spectrometry (MS) was used to study the molecular weight distribution (MWD) and the number of α-methyl styrene (α-MeSty) repeat units in SRM 1487, a narrow MWD poly(methyl methacrylate) (PMMA) standard reference material of about 6300 g/mol, which was initiated with α-MeSty. It was found that each PMMA polymer chain had from zero to seven α-MeStys per chain. The MWD of the polymer chains containing a fixed number of α-MeStys was obtained. The MWD, Mw, and the average number of α-MeSty at a given molecular weight from MALDI TOF MS compare well with those obtained from more traditional methods such as ultracentrifugation and Size Exclusion Chromatography (SEC). The implications of the number of α-MeStys per chain is discussed in terms of the chemistry of anionic polymerization. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2409-2419, 1997
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 2435-2445 
    ISSN: 0887-6266
    Keywords: diffusion ; interphase ; composition profiles ; interdiffusion ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An experimental method to determine interphase composition profiles in amorphous polymers pairs and polymer-solvent pairs is presented. The method is based on the measurement of dynamic mechanical properties of slender composite beams, and well-established properties of amorphous polymer homogeneous blends and solutions. The method does not require tracers. A simple calibration procedure is included in the description, and some results for a polystyrene-polystyrene pair are used to illustrate the method application. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2435-2445, 1997
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  • 75
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 2465-2481 
    ISSN: 0887-6266
    Keywords: tensile drawing ; morphology ; polybutylene ; terephthalate ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The concept of the drawing of a molecular network has been employed to derive a total network draw ratio from the combination of the two deformations occurring in the production of poly(butylene terephthalate), PBT, fibers by the consecutive processes of melt spinning and cold drawing. The mechanical properties of PBT can then be more readily explained in terms of increases in this total network draw ratio. However, the preorientation and crystallization that occurs in the melt-spinning process can occur at different strain rates and temperatures, depending on the wind up speed employed, on the extensional viscosity of the polymer, and on the variation of the extensional viscosity with temperature. Therefore, for polymers such as poly(butylene terephthalate), which can exist in two crystalline forms, the morphology of the final drawn fiber might be expected to depend on the first melt-spinning stage of the process as well as on the total network draw ratio. In this work, density, birefringence, mechanical measurements, and WAXD measurements, which have been made on the melt-spun fibers and on the drawn fibers, are described. Small differences in some of the drawn yarn mechanical properties at the same overall network draw ratio are related to the crystallinity and in particular to differences in the proportion of the α and β phases present in the drawn yarn. These in turn are related to differences in the temperature and stress during melt spinning and drawing. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2465-2481, 1997
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 2503-2510 
    ISSN: 0887-6266
    Keywords: rheology ; diffusion ; star-branched polymers ; polyisoprene ; terminal viscosity ; molecular weight dependence ; temperature dependence ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Recent experimental investigation of the terminal relaxation in high molecular weight polyisoprenes by dynamic mechanical measurements (C. A. Bero and C.M. Roland, Macromolecules, 29, 1562 (1996)) has found the terminal relaxation times to be more sensitive to changes in temperature for three-arm stars than for the linear polyisoprenes. Moreover, these measurements, carried out with significantly higher molecular weight samples than heretofore, show that the molecular weight dependence of the terminal relaxation times for three-arm star polyisoprenes is much weaker than the exponential dependence previously proposed (L. J. Fetters, et al., Macromolecules, 26, 647 (1993)). Tracer diffusion of labeled linear and three-arm star polyethylene-like diffusant molecules in a highly entangled linear polyethylene matrix exhibit temperature and molecular weight dependencies similar to those observed spectroscopically from bulk polymers. Both the temperature and molecular weight dependencies for the star-branched polymers are at variance with the predictions of the reptation model. It is shown here, however, that these observations can be reconciled through application of the coupling model of relaxation. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2503-2510, 1997
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 2535-2541 
    ISSN: 0887-6266
    Keywords: hydrogels ; rheology ; crosslinking ; power law ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The rheological behavior of two hydrogels, poly(sodium acrylate) and polyacrylamide gels, synthesized in the presence of the same crosslinking agent molecule, N,N′-methylene bis-acrylamide, has been investigated. The variation of the norm of the complex shear modulus |G*| vs. the monomer concentration (sodium acrylate or acrylamide) exhibited a different power law, depending on the nature of the monomer molecule. This discrepancy was ascribed to the influence of the properties of the monomer molecules on the crosslinked structure of the gelified networks. The analysis of the experimental results have allowed the suggestion that the elasticity exponent value was dependent on the length and on the conformation of the polymer chains connecting the junctions points of the network. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2535-2541, 1997
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 2565-2570 
    ISSN: 0887-6266
    Keywords: Semicrystalline morphology ; lamellar structure ; poly(aryl-ether-ether-ketone) (PEEK) ; poly(ether-imide) (PEI) ; staining ; TEM ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: No abstract.
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 1643-1648 
    ISSN: 0887-6266
    Keywords: block copolymer ; order-disorder transition ; dynamic light scattering ; depolarized scattering ; fluctuations ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 8 Ill.
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  • 80
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 1677-1700 
    ISSN: 0887-6266
    Keywords: x-ray structural analysis ; polymers ; imaging plate ; direct method ; polyethylene ; polyoxymethylene ; isotactic polybutene-1 ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A software and some useful tools have been developed for identifying individual x-ray reflectional peaks recorded with an x-ray imaging plate system. These techniques were applied to analyze the crystal structure of uniaxially oriented polymer samples. Characteristic features of the present method may be summarized as follows. (1) The indexing of the observed reflections and the determination of the unit cell parameters can be made easily on the display of the computer. (2) The integrated intensity of the individual component of the overlapped reflections can be evaluated quantitatively through the curve separation technique. The Rmerge's for the equivalent reflections were 5-6%, indicating the exact evaluation of the integrated intensities. (3) The thus obtained reflectional data were successfully utilized for the extraction of the initial structural models by the direct method. The actual applications have been made for orthorhombic polyethylene, trigonal polyoxymethylene, and isotactic polybutene-1, giving the refined crystal structures including even the positions of hydrogen atoms in some cases. The reliability factors were 12, 5, and 15%, respectively, for these three polymer cyrstals. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1677-1700, 1997
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 1701-1709 
    ISSN: 0887-6266
    Keywords: poly(vinyl alcohol) (PVA) ; syndiotactic PVA ; syndiotacticity ; syndiotactic sequence ; PVA-iodine complex ; aggregation ; microgels ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effect of the dissolved state of poly(vinyl alcohol) (PVA) molecules in water on the color development due to PVA-iodine complexes was investigated at each given PVA and iodine concentration using two kinds of syndiotactic-rich PVA (S-PVA) which are unstable in water because of the formation of intermolecular hydrogen bonds and form the complex easily. In the reaction mixtures prepared by mixing PVA solutions and an iodine solution, the color development was constant and independent of standing time of the PVA solution before the addition of iodine up to a certain time, after which it decreased with the standing time. The color development obtained with use of the PVA solution allowed to stand for a fixed time was higher for S-PVA with a lower s-(diad)%. In the case of the reaction mixture prepared by dissolving PVA in an iodine solution, the color development was higher for S-PVA with a higher s-(diad)%. The initial ratio of the I5-/I3- and the rate of decrease in the ratio of I5-/I3- were larger than those in the preceding case. The color development decreased for the PVA with an s-(diad) % of 58, whereas it increased for the PVA an s-(diad) % of 61.3 with increasing propanol content, an inhibitor of gelation. From these results, the aggregates of PVA molecules have been assumed to play an important role in forming the complexes. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1701-1709, 1997
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 1887-1897 
    ISSN: 0887-6266
    Keywords: dielectric relaxation ; correlation functions ; polymer relaxation ; alpha processes ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Recently, tables of parameters used to represent experimental dielectric relaxation data as well as autocorrelation functions have become available. The experimental and autocorrelation function data were represented with the Havriliak-Negami function using rigorous statistical techniques. These tables include not only parameters and their temperature dependencies, but also the confidence intervals for all of the parameters. The important parameters for this work are the two shape parameters, α and β, which represent the width and skewness of the relaxation process, respectively. A comparison is made between the experimental data and several autocorrelation functions by calculating the minimum distance (in units of standard deviations) between the experimental values of αβ parameters for a specific polymer and the αβ parameters corresponding to the autocorrelation functions reported in these tables. Quantities derived from these minimum distances (a distribution function and an error function) are reported for each of the autocorrelation functions. These results are discussed in terms of the basic assumptions of the mode coupling theory. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1887-1897, 1997
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  • 83
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 107-118 
    ISSN: 0887-6266
    Keywords: polyoxymethylene ; elastomer blend ; drawn fibers ; mechanical properties ; structure relationships ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Superdrawn fibers of an elastomer-poly(oxymethylene) (POM) blend have been prepared and investigated in terms of the structure and mechanical properties. The development of the mechanical properties along the fiber axis and the formation of a higher order structure during drawing were slightly retarded by blending, but the loop tenacity increased greatly with the elastomer content. The blend microtextures had an immiscible and phase-separated morphology in which the elastomer was dispersed in the form of streaks between the oriented POM layers, which allowed the fiber to split into smaller filaments on bending. The high loop tenacity of the blend fibers is due to an increase in the radius of curvature resulting from the filament splitting on bending, because the shear stress at the bending corner becomes higher as the radius of curvature increases. © 1997 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 133-140 
    ISSN: 0887-6266
    Keywords: syndiotactic polystyrene ; polymorphism ; chloroform ; clathration ; sorption ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The analysis of chloroform vapor sorption at 35°C in semicrystalline syndiotactic polystyrene samples shows remarkably different sorption isotherms, depending on the crystalline form of the samples. In particular, “emptied” clathrate (“emptied” δ form) samples are characterized by higher equilibrium sorption levels and the differences are particularly relevant for low vapor activities. Moreover, sorption kinetics detected at a vapor activity equal to 0.5 show that in the case of “emptied” δ form samples the sorption rate is much higher than for the other semicrystalline samples. The larger sorption equilibrium uptakes and sorption rates of the “emptied” δ form samples are essentially due to their ability to absorb chloroform, already for low activities, by clathration in the crystalline phase. The measured equilibrium uptakes and sorption kinetics suggest that “emptied” δ form samples of syndiotactic polystyrene could be suitable for removing polluting chlorinated compounds from vapor and liquid streams. © 1997 John Wiley & Sons, Inc.
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  • 85
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 153-163 
    ISSN: 0887-6266
    Keywords: epoxy resin ; thermoplastic ; dynamical mechanical spectroscopy ; glass transition ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dynamic mechanical spectroscopy has been used to investigate the cure of a thermoplastically modified trifunctional epoxy resin. The complex dissolution, curing behavior, and variations in the glass transition of the thermoplastic (PSF) phase were described, as was the Tg behavior of the epoxy phase. Prereaction of the PSF material with the epoxy resin was found to greatly increase the solubility of the PSF in the epoxy phase with little effect on the concentration of the epoxy monomer dissolving in the PSF phase. The curing behavior of the epoxy component in the thermoplastic phase was also investigated, in addition to changes in the mobility of the network at both gelation and vitrification. © 1997 John Wiley & Sons, Inc.
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  • 86
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 1989-1991 
    ISSN: 0887-6266
    Keywords: hydrodynamics ; crossover ; thermal blob ; apparent exponents ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The scaling predictions for the temperature dependence of the intrinsic viscosity of flexible polymers are briefly reviewed. When the predictions are fit to a power law over a fixed range of chain length, a relation between the exponent and prefactor of the Mark-Houwink-Sakurada equation emerges. In comparing with the experimental data compilation of Rai and Rosen, we conclude that real polymer systems are nowhere near the true good solvent limit, even when the exponent matches the good solvent prediction. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1989-1991, 1997
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  • 87
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 489-505 
    ISSN: 0887-6266
    Keywords: polymer blends ; analog calorimetry ; heat of mixing ; mean-field binary interaction model ; polystyrene ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Analog calorimetry is used as a tool to study the interaction of polystyrene, PS, with bisphenol-A polycarbonate, PC, and with tetramethyl bisphenol-A polycarbonate, TMPC. Electrostatic charge calculations were used as a guide to divide polymer repeat units and analogs into groups. A mean-field binary interaction model was used to evaluate group interaction energies. The enthalpic interaction energy obtained from this study for the PS-PC pair is 0.41 ± 0.13 cal/cm3 while that for the PS-TMPC pair is 0.19 ± 0.34 cal/cm3. The result for PS-PC blends is in good agreement with values obtained from studies using the critical molecular weight approach and the phase behavior of copolymer blends. The value for PS-TMPC does not correctly predict the phase behavior of this blend; however, its standard deviation (on both an absolute and relative basis) is large and the range of possible interaction energies includes the negative values obtained from neutron scattering. The results of this study indicate that the presence of methyl groups on the aromatic ring of TMPC repeat unit is the main factor favoring the miscibility of PS-TMPC blends. © 1997 John Wiley & Sons, Inc.
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  • 88
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 523-534 
    ISSN: 0887-6266
    Keywords: polymer solutions ; supercritical fluids ; non-Newtonian viscosity ; free volume ; polydimethylsiloxane ; carbon dioxide ; capillary rheometer ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Viscosity curves were measured for polydimethyl siloxane (PDMS) melts swollen with dissolved carbon dioxide at 50 and 80°C for shear rates ranging from 40 to 2300 s-1, and for carbon dioxide contents ranging from 0 to 21 wt %. The measurements were performed with a capillary extrusion rheometer modified for sealed, high-pressure operation to prevent degassing of the melt during extrusion. The concentration-dependent viscosity curves for these systems are self-similar in shape, exhibiting low-shear rate Newtonian plateau regions followed by shear-thinning “power-law” regions. Considerable reduction of viscosity is observed as the carbon dioxide content is increased. Classical viscoelastic scaling methods, employing a composition-dependent shift factor to scale both viscosity and shear rate, were used to reduce the viscosity data to a master curve at each temperature. The dependence of the shift factors on polymer chain density and free volume were investigated by comparing the shift factors for PDMS-CO2 systems to those obtained by iso-free volume dilutions of high molecular weight PDMS. This comparison suggests that the free volume added to PDMS upon swelling with dissolved carbon dioxide is the predominant mechanism for viscosity reduction in those systems. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys, 35: 523-534, 1997
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  • 89
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 553-562 
    ISSN: 0887-6266
    Keywords: agglomeration ; ABS ; thermodynamics ; domain ; particles ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A thermodynamic theory incorporating Flory-Huggins thermodynamics was developed to elucidate the observed rubber particle agglomeration phenomena in ABS molded under a severe condition. When the particle size of ABS is smaller than a thermodynamically stable domain size (Ds), rubber particle agglomeration can occur. Based on this criterion, rubber particle agglomeration can be explained semiquantitatively, especially for materials which do not have too insufficient graft level and nearly no compositional acrylonitrile mismatch. This finding suggests that the agglomeration results mainly from a driving force produced by thermodynamic incompatibility between components. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys, 35: 553-562, 1997
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 2103-2119 
    ISSN: 0887-6266
    Keywords: non-Fickian diffusion ; viscoelastic diffusion ; nonlinear diffusion ; polymer solution ; polystyrene ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Nonlinear gradient-driven diffusion was studied in concentrated polystyrene (PS)/ethylbenzene (EB) solutions using vapor sorptions with a finite driving force. The nonlinear sorptions were carried out on thin films (≅2.05, 3.50 μ thick) at conditions where non-Fickian, “viscoelastic” effects appear. These data were modeled with the nonlinear diffusion equation studied by Tang. Four dimensionless material parameters in the model were determined from a limited amount of linear-response, differential sorption data on PS/EB mixtures measured in the same range of experimental conditions as for the nonlinear sorptions. The nonlinear model successfully predicts the observed nonlinear response either above or below the glass transition (Tg). In order to simultaneously capture the nonlinear response both above and below Tg, the abrupt change in the concentration dependence of physical properties at Tg must be accounted for. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2103-2119, 1997
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 2141-2150 
    ISSN: 0887-6266
    Keywords: cure kinetics ; diffusion control ; free volume theory ; TGDDM epoxy ; polycarbonate ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Reaction kinetics with diffusion control mechanisms are investigated to model the later-stage cure progressing in a co-cured epoxy network that was formed by blending and heating bisphenol-A polycarbonate (PC) with tetraglycidyl-4,4′-diaminodiphenylmethane (TGDDM), which together were cured with an aromatic amine hardener. Our earlier studies have demonstrated that the epoxy reacts not only with the amine hardener but also with the PC polymer to eventually form a homogeneous network, and that the initial polymerization and cure for this system can be described by an n-th order kinetics. Using the free volume theory, the effect of diffusion control on the kinetics in the gel/vitrified regimes has been modeled successfully, and a more precise kinetic description for the PC/TGDDM/DDS network systems in the full cure range is resulted. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2141-2150, 1997
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  • 92
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 2183-2191 
    ISSN: 0887-6266
    Keywords: epoxy ; blend ; polycarbonate ; transesterification ; transamidation carbamate ; urea ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The transamidation reaction converts the carbonate and amine into N-aliphatic aromatic carbamate and urea, causing the equivalent of oxirane and amine nonstoichiometric in the primary cure stage. After postcure, the substitution reaction takes place and results in a more tightly crosslinked structure. Such a higher crosslinking density is responsible for higher Tg, tensile strength, and tensile modulus in the postcure stage than that in the primary and secondary cure stages. This trend is more pronounced in those PC-epoxy blends containing higher molecular weight aliphatic amine or a higher content of PC. This phenomenon is due to the difference in the fraction of amino group of aliphatic amine consumed in the transamidation. PC-epoxy/aliphatic amine blends show minor improvement in the high strain rate Izod impact tests, while toughness improvement for some blends is substantial at low strain rate tensile tests. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2183-2191, 1997
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  • 93
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 639-653 
    ISSN: 0887-6266
    Keywords: plasticized ethyl cellulose ; sorption and diffusion coefficient of oxygen ; degree of substitution ; plasticizer content ; cohesive energy density ; unoccupied volume and partition of ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Plasticized films cast from ethyl cellulose were examined to evaluate the effect of the degree of substitution, DS, and the plasticizer content on the sorption and diffusion of oxygen. Sorption and permeation measurements were performed over a temperature range of 25-65°C on three different types of ethyl cellulose in the DS range 1.7-2.5 that had been plasticized with organic esters of comparatively low molecular weight. Sorption coefficients were determined by the pressure decay method, and permeability coefficients were measured independently according to ASTM D-1434-66. The diffusion coefficients were calculated assuming Fickian transport, and were compared to the values directly obtained from the evaluation of the sorption kinetics. The permeability coefficient indicates that there is a significant improvement of the barrier properties of the materials when the DS is reduced and when the plasticizer content is at the absolute minimum required. It was found that the variation in the magnitude of the permeability coefficient is related to the value of the diffusion coefficient, which is governed by the chemical composition of the mixtures. In contrast, the solubility of oxygen was determined by the physical state of the polymer matrix and increased rapidly at temperatures significantly below the glass transition temperature. Using an ergodic model, the diffusion coefficients obtained were related to the size distribution of microvoids in the materials and relative values for the diffusion coefficient were computed as a function of DS and temperature. The model calculates the concentration (number per volume) of voids that are large enough to be occupied by a penetrant molecule. It was assumed that the unoccupied volume fraction as a function of the cohesive energy density follows a Boltzmann distribution. The cohesive energy density and the unoccupied volume fraction of the polymer-plasticizer mixtures were calculated by fitting the Simha-Somcynsky equation of state to pressure-volume-temperature data. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys, 35: 639-653, 1997
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  • 94
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 689-697 
    ISSN: 0887-6266
    Keywords: tensile force ; electric field ; chain conformation ; birefringence ; scattering ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effect of a tensile stress or an electric field on the conformation of a flexible polymer chain has been studied by combining theory with numerical simulation. In the presence of such external agents, the macromolecule experiences the action of two opposite forces at the chain ends. Two models are considered: the Gaussian bead-and-spring chain, and the freely jointed chain with segments of fixed length. From simulated Brownian trajectories we calculate steady-state properties of the polymer under the continuing action of the external forces. Thus, we compute the chain deformation and expansion, measured by the square radius of gyration, and analyze the influence of the external force on low-angle scattering of radiation. The effect of the link orientation in the optical anisotropy or birefringence is also analyzed. From existing theories, we predict very simple relationships between expansion, low-angle scattering, and birefringence, valid for Gaussian chains of any length, and for long freely jointed chains. The simulation results confirm those relationships. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys, 35: 689-697, 1997
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  • 95
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 675-688 
    ISSN: 0887-6266
    Keywords: nylons ; lamellar crystals ; diffraction ; Brill transition temperatures ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Four members of the even-even nylon 2 Y series, for Y = 6, 8, 10, and 12, have been crystallized in the form of chain-folded lamellar single crystals from 1,4-butanediol and studied by transmission electron microscopy (imaging and diffraction), x-ray diffraction, and thermal analysis. The structures of these 2 Y nylons are different from those of nylon 6 6 and many other even-even nylons. At room temperature, two strong diffraction signals are observed at spacings 0.42 and 0.39 nm, respectively; these values differ from the 0.44 and 0.37 nm diffraction signals observed for nylon 6 6 and most even-even nylons at ambient temperature. Detailed analyses of the diffraction patterns show that all these 2 Y nylons have triclinic unit cells. The diamine alkane segments of 2 Y nylons are too short to sustain chain folds; thus, the chain folds must be in the diacid alkane segments in all cases. On heating the crystals from room temperature to the melt, the triclinic structures transform into pseudohexagonal structures and the two diffraction signals meet at the Brill transition temperature which occurs significantly below the melting point. The room temperature structures of these 2 Y nylons are similar to the unit cell of nylon 6 6 at elevated temperature, but below its Brill temperature. The room temperature structures and behavior on heating of the nylon 2 Y family is noticeably different from that of the even-even nylon X 4 family, although the only difference between these families of polyamides is the relative disposition of the amide groups within the chains. The results show that in order to understand the structure, behavior and properties of crystalline nylons, especially as a function of temperature, the detailed stereochemistry needs to be taken into account. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys, 35: 675-688, 1997
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 725-734 
    ISSN: 0887-6266
    Keywords: swelling ; sorption ; diffusion ; natural rubber ; interaction parameter ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The sorption and transport of four aliphatic hydrocarbons into natural rubber crosslinked by different vulcanization systems [conventional (CV), efficient (EV), peroxide (DCP) and a mixed system consisting of sulfur and peroxide (mixed)] were investigated in the temperature interval of 28-60°C. Of the four systems, natural rubber vulcanized by DCP exhibited lowest penetrant uptake. It was observed that the kinetics of liquid sorption in every case deviates from the regular Fickian trend, characteristic of sorption of liquids by rubbers. The diffusion coefficient, activation energy of sorption, enthalpy, entropy, and the rubber-solvent interaction parameter were evaluated for the four systems from the swelling data. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 725-734, 1997
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  • 97
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 1013-1024 
    ISSN: 0887-6266
    Keywords: screening length ; clusters ; dynamic light scattering ; melt ; concentrated solutions ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dynamic light-scattering measurements have been made on the “soft” polymer: poly(n-laurylmethacrylate) (PLMA) in solution in ethyl acetate over the concentration range 0.1 〈 C 〈 0.9 g/mL as well as melt PLMA. With the concentrated solutions, the hydrodynamic screening length (ξh) scales with an exponent of -0.7 below C ≈ 0.3 g/mL. Importantly, ξh decreases above 0.3 g/mL, and the concentration dependence increases strongly above this concentration. The latter contrasts with the behavior in a variety of well-studied poly(styrene) solutions, which are inevitably investigated close to the glass point, and for which there is a pronounced increase of ξh over the same concentration range. In PLMA solutions, the decrease in ξh parallels the behavior of the static screening length (ξs) which has been observed in other flexible polymer systems.Dynamic “clusters” (also termed “long-range density fluctuations”) contribute a large part of the scattered intensity above the concentration 0.6 g/mL and also in melt PLMA which contrasts with poly(styrene) systems in which they are absent. In common with the clusters recently observed in another polymeric melt, poly(methyl-p-tolylsiloxane) (ref. 9) this component is diffusive. While, however, in the latter system the clusters “melt out” at 90°C, we find in the well-matured PLMA systems that the cluster amplitude is temperature-independent (within the temperature-time range studied) in the solutions up to at least 80°C and up to at least 150°C in the melt, which were the highest temperatures examined. The clusters in the PLMA systems have a correlation length of the magnitude 65 nm in the melt, whereas in the solutions this dimension varies between 73 nm at 0.9 g/mL to 126 nm at 0.7 g/mL. In PLMA the clusters are presumed to arise from local segregation owing to the large paraffinic side groups on the chain. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1013-1024, 1997
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 1077-1093 
    ISSN: 0887-6266
    Keywords: nucleation ; crystallization kinetics ; polypropylene ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A nucleation rate function is proposed for use in analyzing the overall crystallization kinetics of polymers. This function allows for the possibility that the nucleation rate varies substantially during the crystallization. This feature is particularly useful in analyzing nonisothermal crystallization, but it can be used to analyze isothermal crystallization as well. The nucleation rate function was used in the derivation of a modified transformation kinetics equation of the Avrami type. The modified Avrami equation was found to be suitable for kinetics analysis for the data obtained from nonisothermal crystallization at rapid cooling rates. Kinetics parameters used to describe nonisothermal crystallization under rapid cooling rates are presented and discussed. These include crystallization induction time, plateau (crystallization) temperature, crystallization half-time, crystallization rate constant, Avrami index, and newly defined quantities called nucleation index, geometric index, and nucleation rate constant. The procedure used to obtain the nucleation rate constant and nucleation index for the nucleation rate function is described and illustrated by application to the analysis of the crystallization kinetics of polypropylene. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1077-1093, 1997
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 1107-1116 
    ISSN: 0887-6266
    Keywords: enthalpy relaxation ; conformational energy ; free volume ; glass transition ; side chains ; physical ageing ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The enthalpy changes ΔH∞ between a poly(vinyl acetate) glass formed by rapid cooling and the corresponding fully relaxed glass have been estimated at four temperatures below the glass transition. The values obtained were different to those expected by extrapolating liquid behavior below the glass transition and were found to agree well with the predictions of a simple expression for the combined main chain conformational and free volume contributions to enthalpy. Conformational contributions from the side chain alone were also considered but were not required to obtain agreement with experiment. It can be concluded that the side chains remained mobile below the glass transition and do not contribute to the heat capacity discontinuity at Tg. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1107-1116, 1997
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 1127-1133 
    ISSN: 0887-6266
    Keywords: excimer ; fluorescence ; molecular dynamics ; naphthalene ; polyester ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Steady-state fluorescence measurements and molecular dynamics simulations have been used to study the intramolecular formation of excimers in five model compounds for polyesters containing naphthalene groups separated by flexible spacers. The model compounds are derived from 2-hydroxynaphthalene and HOOC—(CH2)n—COOH, n = 2-6. The ratio of the intensity of excimer and monomer emissions, ID/IM, is nearly independent of the viscosity of the medium, η, over the range covered in dilute solution. Although ID/IM is always very small, it shows an odd-even effect for the first four members of the series, with maxima when n is odd. Molecular dynamics simulations provide an explanation for the small values of ID/IM, their weak dependence on η, and the trend of ID/IM with n. The results for the present series of model compounds are compared with previous work, which reported larger values of ID/IM, and a stronger dependence of ID/IM on η, for bichromophoric compounds derived from 2-naphthoic acid and aliphatic glycols, where the direction of the ester groups is reversed. The origin of the difference in the behavior of ID/IM in the two series is identified. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1127-1133, 1997
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