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  • 1
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 44 (1992), S. 2019-2027 
    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: Continuous chemical modification of poly(vinyl chloride) (PVC) with sodium benzene thiolate (NaBT) in a counter-rotating twin screw extruder has been studied. The course of the reaction is analyzed, taking into account the physical changes of the polymer along the length of the screw. From the results, it is concluded that the modification reaction is associated with the fusion-gelation process. The reaction kinetics are determined as a function of the mean residence time with the aid of a UV tracer. Temperature profile, flow rate, and premixing are some of the processing parameters influencing the reaction, kinetics. The continuous modified polymer is analyzed in terms of thermal behavior, molecular weight, and stereochemical structure, and the results are compared with those obtained by a discontinuous melt process (Haake-Rheocord). It is confirmed that the same stereoselective substitution mechanism occurs as that in discontinuous melt with no side reactions.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 53 (1994), S. 1675-1686 
    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 development of the morphology of a reactive blend along a twin-screw extruder has been experimentally studied. A transesterification reaction activated by a catalyst allowed a cross-linking of the dispersed phase during the flow in the extruder. In comparison with the nonreactive system (without catalysts), the resulting morphologies were characterized by larger dimensions. Influence of screw speed and feed rate were similar for both systems, whereas the changes along the screws were more pronounced for the reactive blend. It appeared that the local morphology was strongly dependent on the extent of the reaction. At low extent, the equilibrium between breakup and coalescence was shifted toward coalescence, whereas at high extent, the classical mechanisms were largely modified and replaced by a “coagulation” mechanism. It was shown that, for the fully cross-linked dispersed phase, the final morphology remained remarkably stable during successive extrusion steps. For such products, the observation of a low-frequency plateau of the elastic modulus suggested the formation of a copolymer at the interface with the matrix. © 1994 John Wiley & Sons, Inc.
    Additional Material: 15 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 58 (1995), S. 1393-1399 
    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: Thermorheological properties of an incompatible polymer blend of polypropylene inclusions dispersed in a ethylene copolymer matrix were discussed from the emulsion model developed by Palierne. Due to the different rheological behaviors with temperature of the two phases, such a system proved to be a judicious blend in order to consider the special cases of the model applications: (1) the two phases are viscoelastic liquids, (2) the dispersed phase is a solid elastic assimilated to rigid spheres in comparison with viscoelastic liquid behavior of the matrix, and (3) the two phases are elastic solids. At low frequencies, the rheological behavior of the blend was not correctly predicted by the model. So interactions other than hydrodynamics can exist in the intrafacial region, and physical entanglements between the chains of the two constituents leading to topological interactions may be assumed at the interphase. © 1995 John Wiley & Sons, Inc.
    Additional Material: 6 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 60 (1996), S. 1439-1453 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A poly(vinyl chloride) (PVC)/poly(methyl methacrylate) (PMMA) (80/20 w/w) polymer blend was studied by mechanical spectroscopy. Two relaxations can be distinguished: in the glassy state, a very large secondary relaxation in the range of 100 K to 325 K which results from the combination of secondary relaxations of PVC and PMMA; and only one main relaxation at 364 K associated to the glass rubber transition. The relaxation spectrum in the range of the β relaxation has been described by a relaxation time distribution function based upon a Gaussian function and a series-parallel model. The α relaxation was studied by means of a theoretical approach for the nonelastic deformation of polymers. We found that the miscibility of this blend appears to be a function of the observation scale: the PVC/PMMA blend is heterogeneous at the scale of molecular movements involved for the β relaxation process but homogeneous at the scale of the chain segments responsible for the α relaxation dynamics. © 1996 John Wiley & Sons, Inc.
    Additional Material: 15 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 54 (1994), S. 2083-2089 
    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 transesterification reaction in the molten state of ester groups of ethylene vinyl acetate (EVA) copolymers and ethylene acrylic ester (EMA) copolymers has been used to crosslink the chains of this polymeric system. The relative EVA copolymers (or EMA copolymers) concentration dependence of the network formation by co-crosslinking of EVA/EMA miscible blends has been assessed. EVA/EMA networks were characterized by swelling experiments, rheological measurements, and determination of the extent of the reaction through a chromatographic technique. All results can be compared in a master curve. The influence of the polydispersity and the microstructure of EVA and EMA samples was put in evidence. On the other hand, a scaling law (v2∼Mc-3/5) was observed in agreement with predictions of the Flory-Rhener expression. © 1994 John Wiley & Sons, Inc.
    Additional Material: 4 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 28 (1983), S. 1573-1584 
    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: Whatever the state of the iron compounds as smoke suppressant during the combustion of poly(vinyl chloride), they lead rapidly to native αFe2O3 in the char residue left after dehydrochlorination. It causes incandescence of the char residue and catalyzes its oxidation into carbon monoxide and carbon dioxide that contributes to decreasing the amount of available carbon for the soot formation after self-ignition. FeCl2 and FeCl3 are the precursors of αFe2O3, which is the true compound as smoke suppressant. Nevertheless, as intermediate, iron chlorides are able to modify the degradation processes, and they favor the formation of light tars instead of heavy tars. For that reason the iron compounds cause the formation of smoke at lower temperature than for pure PVC, but, as αFe2O3 is formed, the smoke production levels off and then decreases. The higher the ease of the iron compounds to give chlorides through reaction with HCI and further native αFe2O3, the higher the ease of the additive to cause the oxidation of the char residue sooner and in consequence to decrease the smoke level. In the PVC combustion three main steps may be distinguised: dehydrochlorination step between 200-300°C; tars aerosols formation from the char residue between 300°C and self-ignition; at temperature higher than self-ignition, formation of soot from the previous tars as precursors.
    Additional Material: 14 Ill.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 1011-1015 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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 transesterification reaction catalyzed by dibutyltin oxide has been used to crosslink miscible blends (at about 200°C) of ethylene vinyl acetate (EVA) and ethylene methyl acrylate (EMA) copolymers. Then, microwave heating at 2.45 GHz with the fundamental TE01 mode was used for activation of this crosslinking reaction. The microwave treatment was carried out in a continuous process through a resonant cavity on line with a twin screw extruder equipped with a strip die or a circular die, which imposed the shape of the samples in the waveguide. Therefore, a shape factor due to the geometry of the samples and their orientation with respect to the electromagnetic field was defined. Last, this technique was applied to the microwave crosslinking of an EVA/EMA blend dispersed in a polypropylene matrix and consequently offers a new route to control the morphology of the polymer blends.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 8
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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 linear viscoelastic behavior of commercial broad-distribution polypropylenes is studied. The samples underwent different controlled peroxide degradation rates, so they exhibit different molecular distributions. The relaxation spectrum is obtained by assuming that it takes the shape of a Log-Normal distribution. It is in agreement with the linear viscoelasticity theory by providing limiting values, contrary to other models. Moreover, the ratio τw/τn which takes place in this law is very useful to distinguish the synthesis differences of the samples when the Melt Flow Index alone cannot.
    Additional Material: 4 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 32 (1992), S. 998-1003 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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: Transesterification may be used to crosslink a copolymer such as ethylene vinyl acetate with poly(ethylene acrylate-co-propylene) in the presence of dibutyltin oxide as a catalyst. A rheological study of the mechanism of this exchange reaction has been made: The kinetics of the crosslinking reaction was determined by studying the time and temperature dependence of the dynamic storage modulus G′(t, T)ω. Kinetic curves obtained for different reactive blends (EVA, PP/EVA, and PPf/EVA) allowed for the evaluation of the activation energy of the reaction and, thus, specified the appropriate parameters (temperature and time) for carrying out this reaction in a molten state.
    Additional Material: 9 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 47 (1975), S. 61-77 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: When the ozonisation of bulk or suspension poly(vinylchloride) is carried out in tetrachloroethane solution between 0-120°C the molecular weight decreases continuously and the rate of breaking of chains deduced from the intrinsic viscosity variation is constant under isothermal conditions. Whatever the time and temperature of ozonisation may be, at every breaking, β and α chlorinated acid groups are introduced which have been characterized by infrared spectroscopy, high resolution NMR spectroscopy and potentiometric titration in dimethylformamide. Besides these functions, peroxide groups have also been identified and their concentration has been determined for different times and temperatures of ozonisation.This study permits to propose two mechanisms to explain the breaking of chains. The first implies the previous dehydrochlorination of the polymer and the second the formation of unstable peroxides which by decomposition cause the breaking of chains.
    Notes: Quelle que soit la nature du polychlorure de vinyle (masse ou suspension) l'action de l'ozone en milieu homogène dans le tétrachloroéthane provoque la décroissance continue de la masse moléculaire dans le domaine de température 0-120°C et la vitesse de coupure des chaînes déduite des variations de viscosité est constante en conditions isothermes.Quels que soient le temps et la température d'ozonisation, à chaque point de coupure apparaissent des fonctions acides α et β chlorées qui ont été caractérisées par spectroscopie infra-rouge, RMN haute résolution et dosage potentiométrique en milieu diméthylformamide. Outre ces fonctions, des peroxydes ont égé également identifiés dans le polymère et on a suivi leur concentration en fonction des conditions d'ozonisation.Cette étude permet de proposer deux mécanismes pour expliquer la coupure des chaînes, l'un suppose une déhydrochloruration préalable du polymère et l'autre la formation de peroxydes instables qui en se décomposant provoqueraient la coupure des chaînes.
    Additional Material: 9 Ill.
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