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  • 1
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The effect of additives (mostly nucleating agents) on the crystallization rate of isotactic poly(1-butene) has been investigated by differential scanning calorimetry. Isothermal crystallization half-times and crystallization temperatures have been measured for polymer-additive blends. The crystallization temperature and the cooling rate at which the ultimate fraction transformed becomes less than 1 is calculated as a function of nucleation density, and this is used to characterize the effect of the additives on crystallization rate. The relationship between the isothermal crystallization half-time and the crystallization temperature is also calculated theoretically and is compared with experimental results.
    Additional Material: 5 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 21 (1977), S. 1751-1762 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Vinyl acetate was batch polymerized at 60°C in t-butanol solution. Conversion and molecular weights were measured as functions of time for several initiator and solvent concentrations. Although the overall rate constant depends somewhat on solvent concentration, the reaction is first order in monomer concentration up to at least 60% conversion and one-half order in the concentration of initiator. Molecular weights were independent of initiator concentration, confirming that the polymerization is transfer dominated. Measurements of M̄w and M̄w versus conversion were used to establish the individual transfer constants. All are independent of solvent concentration, except Cp, the polymer transfer constant, which decreases systematically with increasing solvent concentration.
    Additional Material: 7 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 2385-2390 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In the initial stage of the development of transcrystallinity, nuclei appear sporadically on the substrate. The growth rate and melting temperature of the transcrystalline region are found to be the same as those of spherulites nucleated in the bulk of the polymer. Nucleation densities ns at the interface, and nb in bulk, for the crystallization of isotactic polypropylene, poly(ethylene oxide), and poly(butene-1) in contact with various substrates, have been measured by counting the number of spherulites generated. Despite variations in the results from various causes, the quantities ns and ns/nb are useful parameters for characterizing the nucleating ability of various substrates.
    Additional Material: 2 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 2391-2400 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In the melt crystallization of isotactic polypropylene, poly(ethylene oxide) and poly(butene-1) in contact with substrates, the existence of a fixed number of nucleating sites on the substrate surfaces has been established. When these sites become active successively (the transient in the number of nuclei is long) during crystallization, pseudohomogeneous nucleation on the substrate occurs. Nucleation rates for poly(butene-1) and poly(ethylene oxide) on substrates and in bulk have been measured. These data can be used for comparing the nucleating ability of substrates. Estimates of the variation of bulk nucleation rates from one volume element to another as well as for repeated crystallization within a given volume element have been included. Finally, the temperature coefficients of heterogeneous nucleation rates have been combined with the temperature coefficient of spherulitic growth rate of poly(butene-1), to yield values of the interfacial energy parameters appearing in the theory of heterogeneous nucleation. The quantitative characterization of the nucleating ability of substrates by this method is an improvement over the mere use of nucleation densities or nucleation rates.
    Additional Material: 4 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 2369-2383 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Melt crystallization of isotactic polypropylene (iPP), poly(ethylene oxide), poly(butene-1), and polycaprolactone in contact with various substrates (mostly polymeric) has been studied by hot stage polarizing microscopy. Nucleating abilities of surfaces have been characterized qualitatively by examining the substrate-induced morphologies of the crystallizing polymer. These morphologies have been classified into three groups, depending on whether the substrate is very active (transcrystallinity), moderately active, or inactive as a nucleating agent. The morphologies observed are temperature-dependent, changing from transcrystalline to spherulitic upon increase of the crystallization temperature. At intermediate temperatures, mixed surface morphologies (transcrystalline plus spherulitic) are observed.The concentration of titanium and aluminum catalytic residues in isotactic polystyrene (iPS) samples can be reduced by two methods, i.e., (a) fractionating the polymer and (b) chelating Ti and Al with acetylacetone. The high nucleating ability of iPS samples in the crystallization of iPP has been shown to be due to the polymer (iPS) itself, and not to Ti and Al residues. Apart from iPS, other polymers (low energy surfaces) have also been found to induce transcrystallinity.From a survey of 43 substrate-crystallizing polymer pairs, conclusions have been drawn which are relevant to the following potential factors in heterogeneous nucleation processes: (a) chemical structure, (b) crystallographic unit cell type, (c) lattice parameters, (d) crystallinity of substrate, and (e) surface energy of substrate.
    Additional Material: 5 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1203-1211 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the aqueous polymerization of methyl methacrylate by a ceric-thiourea initiator system in moderately acid solution (pH 2.15) was studied. The rate of polymerization was proportional to 0.41 power of ceric concentration, 0.32 power of thiourea concentration, and 1.18 power of monomer concentration. The degree of polymerization was smaller than expected from the rate of polymerization. Initiation efficiency was less than one. There was no evidence of any ceric ion termination in the concentration range of 2.50 × 10-4-2.00 × 10-3M studied. The results are explained in terms of partial primary radical termination; the principal mode of termination, however, was bimolecular.
    Additional Material: 4 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 2585-2595 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ceric-thiol systems are good initiators for the acid aqueous polymerization of some water-soluble Vinyl monomers although not for styrene (in aqueous emulsion) and vinyl acetate. Thiols used are 2-mercaptoethanol, thioglycolic acid, 2-mercaptoethylamine hydrochloride, and L-cysteine hydrochloride. The polymerization proceeds through a radical mechanism. End-group analysis of poly(methyl methacrylate) obtained by initiation with various ceric-thiol systems has been carried out using Palit's dye testes. Hydroxyl, carboxyl, and amine end groups (to the extent of about one per polymer molecule) were incorporated in poly(methyl methacrylate)s obtained by initiation with 2-mercaptoethanol, thioglycolic acid, and 2-mercaptoethylamine hydrochloride, respectively, each in combination with Ce4+ ions; both amine and carboxyl end groups were obtained using C4+/L-cysteine hydrochloride initiator system. From the end-group results, the initiating species have been identified and the initiation mechanism prooposed. The probable termination mechanism also has been discussed.
    Additional Material: 3 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 54 (1962), S. 205-217 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Konduktivität, Viskosität und pH-Wert einer „Acacia-Catechusäure“ (ACA), die durch Elektrodialyse aus Acacia-Catechu-Gummi gewonnen wurde, wurden unter verschie-denen experimentellen Bedingungen untersucht. Es wurde ein starker Anstieg von ηsp/C bei sinkender Konzentration festgestellt. Die Viskosität von ACA wird durch die Gleichung (A = 0,4237, B = 1,84) ausgedrückt. Die reduzierte Viskosität von ACA bei Zusatz äquivalenter Mengen an H2SO4 wurde gemessen. Es zeigte sich, daß bei Zusatz von 2·10-4 g äquiv./l der steile Anstieg der ηsp/C gegen C-Kurve verschwindet und ein deginiertes Maximum auftritt. Mit wachsender Schwefelsäurekonzentration wandert das Maximum zu höheren ACA-Konzentrationen, und bei 1,0·10-3 g liquiv./Z H2SO4 ist die graphische Darstellung eine Gerade. Die λ gegen C-Kurve (Phoreogramm) ist viel steiler als die eines vergleichbaren einfachen Elektrolyten. Das Phoreogramm ist stark konkav. Es wird gezeigt, daß die Konduktivität hauptsächlich durch das Wasserstoff-Gegenion hervorgerufen wird. Es wurden Gleichungen aufgestellt, die die Äquivalentleitfähigkeit von ACA in Abhängigkeit von der Konzentration wiedergeben. Der Dissoziationsgrad wurde durch Messung der Leitfähigkeit und des pH-Wertes ermittelt. Es wurde versucht, die Diskrepanz in den Ergebnissen zu erkläiren. Der Dissoziationsgrad sinkt mit steigender ACA-Konzentration. Es wird festgestellt, daß die Leitfähigkeit von ACA/Elektrolyt-Mischungen 5 - 12% höoher ist als der berechnete Wert. Es wurden Gleichungen aufgestellt, die die Konzentrationsabhängigkeit des pH-Wertes von ACA wiedergeben.
    Notes: The conductivity, viscosity and pH of Acacia catechuic acid (ACA), an acid obtained from the electrodialysis of gum Acacia catechu have been investigated under different experimental conditions. It is noted that there is a sharp rise in the reduced viscosity ηsp/C as the concentration of ACA is reduced. The viscosity of ACA follows the expression the value of A = 0.4237 and B = 1.84. The reduced viscosity of ACA has been investigated with dilution in isoionic concentrations of H2SO4. It has been found that by the addition of 2.0·10-4 g. equiv./l., the sharp rise in ηsp/C versus C vanishes, the curve showing a well defined maxima. With increasing concentrations of H2SO4 the maxima shifts towards higher values of ACA concentration, and at 1.0·10-3 g. equiv./l. of H2SO4, the ηsp/C versus C curve is a straight line. The λ (equiv. cond.) versus√C curve (Phoreogram) is much steeper than for a comparable simple electrolyte. The phoreogram is strongly concave upward. It is shown that the conductivity is largely due to the hydrogen counterions. A number of equations have been found to represent the equivalent conductance of ACA with dilution. The degree of dissociation has been determined from measurements of electrical conductivity and of pHXS. A discrepancy in the results has been tentatively explained. The degree of dissociation decreases with increasing concentration of ACA. It is noted that the conductance of ACA/electrolyte mixtures is 5 to 12% higher than the calculated value. A number of equations have been shown to represent the concentration dependence of pH for ACA.
    Additional Material: 6 Ill.
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  • 9
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mechanism of the redox polymerization of methyl methacrylate in acid-aqueous medium was studied for ceric-thiourea initiator system by analysis of polymer end groups using the dye partition method. Polymerization at room temperature and at pH 2.30 with this initiator system incorporates mostly amino end groups in the polymers to the extent of 1.18-1.31 and a small amount of hydroxyl end group not exceeding 0.08 per polymer molecule. Under the same pH condition, a higher polymerization temperature increases the amine end group content to 2.17-2.30 and hydroxyl end group content to 0.14-0.18 per polymer molecule. A lower polymerization temperature (5°C), or a lower pH (ca. 1) of the reaction medium, produces polymers with exclusively amine end groups, hydroxyl end groups being totally absent. At pHs greater than 3, amine end group incorporation decreases significantly, with simultaneous increase in hydroxyl incorporation. On the basis of end group results the initiating radical has been identified and the mechanism of initiation has been suggested. The possible mode of termination has also been discussed.
    Additional Material: 3 Tab.
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  • 10
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Propellants, Explosives, Pyrotechnics 5 (1980), S. 163-167 
    ISSN: 0721-3115
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The combustion behaviour of a cylindrical port burning PVC plastisol hybrid fuel grain in an oxidizing stream of gaseous oxygen has been studied and the effects of grain length and port size on the local regression rate, average regression rate and mass consumption rate have been investigated. Various combinations of grain length and port size have been employed to give a wide range of L/D ratios from 8 to 100. The average regression rate is found to increase with the increase of L/D ratio, whereas the mass consumption rate is found to decrease with the increase of L/D ratio. An attempt has also been made to correlate the fuel mass consumption rate with the Reynolds' number and the total mass flux.
    Additional Material: 5 Ill.
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