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  • 1
    Electronic Resource
    Electronic Resource
    Reaction mechanisms of polyacrylonitrile on thermal treatment (1993)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 33 (1993), S. 1452-1457 
    Details
    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: A high-temperature radical scavenger, 2,2-diphenyl-l-picryl hydrazyl (DPPH), has been used to study the reaction mechanisms of polyacrylonitrile (PAN) on thermal treatment. The effect of DPPH on the cyclization reaction of PAN in both air and nitrogen, investigated by differential scanning calorimetry (DSC), helped to verify the proposed reaction mechanisms, i.e., the free radical and the ionic ones. For PAN homopolymer, the peak temperature of the reaction exotherm shifted to higher temperatures and the heat of reaction was decreased with increasing DPPH concentration. For PAN copolymer with methylacrylate and itaconic acid, however, the effects of DPPH on DSC thermograms were insignificant. The effects of IPPH suggest that the reaction of the nitrile groups proceeds by free radicals for the homopolymer while by ions for the copolymer. The activation energies for the thermal reactions of PAN in both air and nitrogen were also estimated by the dynamic DSC method, and they proved to be highly dependent on reaction mechanism, environment of thermal treatment, and DPPH concentration.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760332203
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  • 2
    Electronic Resource
    Electronic Resource
    Temperature dependence of the nucleation effect of sorbitol derivatives on polypropylene crystallization (1993)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 33 (1993), S. 1445-1451 
    Details
    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 temperature dependence of the nucleation effect of three sorbitol derivatives on the crystallization of isotactic polypropylene (iPP) was studied by means of isothermal crystallization kinetic analysis. Isothermal crystallization thermograms obtained by differential scanning calorimetry (DSC) were analyzed based on the Avrami equation. The Avrami analysis for the nucleated iPP was carried out with DSC data collected to 35% relative crystallinity, and the rate constants were corrected assuming the heterogeneous nucleation and three dimensional growth of iPP spherulites. A semi-empirical equation for the radial growth rate of iPP spherulites was given as a function of temperature and was used to determine the number of effective nuclei at different temperatures. The number of effective nuclei in the nucleated samples was estimated to be 3 × 102 ∽ 105 times larger than that in the neat iPP. The logarithmic numbers of the effective nuclei decreased linearly with decreasing degree of supercooling in the range of crystallization temperatures tested. The temperature dependence of the effect of the nucleating agents on iPP crystallization was given quantitatively in terms of the deactivation factor defined as a fraction of the particles that are active at a particular temperature but inert at the temperature one degree higher. The nucleation activity and its temperature dependence are considered to be cooperative effects of many factors, including the dispersion and the physical or chemical nature of the agent as well as the interaction between the agent and the polymer. It is suggested that the temperature dependence of the effect of a nucleating agent should be treated as a characteristic of a given polymer/ nucleating agent mixture.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760332202
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  • 3
    Electronic Resource
    Electronic Resource
    Effect of drying conditions on the glass transition of poly(acrylic acid) (1991)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 31 (1991), S. 867-872 
    Details
    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: Systematic changes of drying conditions of poly(acrylic acid) were tested to study their effect on the glass transition of the material. The materials were synthesized in two different mediums of water and benzene, respectively. The glass transition temperatures of the samples were determined by thermal analysis using DSC. The samples were also characterized by IR spectra. The glass transition of poly(acrylic acid) was found to be significantly dependent on the drying conditions and also dependent on the medium in which poly(acrylic acid) was prepared. The anhydride formation in poly(acrylic acid) was increased as the drying temperature was raised, resulting in the increase of the glass transition temperature. The “bound” water involved in the preparation of poly(acrylic acid) in water medium could affect significantly the glass transition of the sample. A significant discrepancy in the previously reported values of the glass transition temperature of poly(acrylic acid) seems to be due to the differences in the drying conditions of the materials.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760311205
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  • 4
    Electronic Resource
    Electronic Resource
    Crystallization characteristics of isotactic polypropylene with and without nucleating agentsParts of this paper have been presented at the IUPAC international Symposium, Seoul, Korea, June 1989. (1991)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 31 (1991), S. 1009-1014 
    Details
    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: Nucleation effects of two sorbitol derivatives on the crystallization of isotactic polypropylene (iPP) were studied by means of differential scanning calorimetry (DSC) and polarized optical microscopy (POM). A nonisothermal crystallization kinetic equation was employed to analyze the crystallization characteristics of iPP with or without the nucleating agents from DSC crystallization thermograms. The equilibrium melting temperature of iPP necessary for the kinetic study was obtained by the extrapolation method to be 209°C. The nonisothermal crystallization kinetic analysis for the unnucleated iPP at different cooling rates was possible by assuming the spherulite growth initiated simultaneously by heterogeneous and homogeneous nucleation. On the other hand, the crystallization kinetics of the nucleated iPP could be described by the heterogeneous nucleation and growth process alone. The addition of the nucleating agents up to their saturation concentrations in iPP increased the crystallization peak temperature by 17°C, and the number of effective nuclei by three orders of magnitude. A high concentration of the nucleating agents caused agglomeration of the agents to lower the number of effective nuclei.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760311403
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  • 5
    Electronic Resource
    Electronic Resource
    Analysis of reaction injection molding process of polyurethane-unsaturated polyester blends. Part II: Mechanical properties (1987)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 27 (1987), S. 1252-1257 
    Details
    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 mechanical properties of polyurethane-unsaturated polyester interpenetrating polymer networks (IPNs) that were prepared by reaction injection molding (RIM) process were measured with variations In composition, cross-link density, and relative reaction rate. From dynamic mechanical analysis (DMA), it was found that the two component polymers had a good compatibility over the whole composition range. The tensile strengths of the blends were greater than those of the pure components and had a maximum value at 50/50 composition. The modulus of elasticity and surface hardness decreased and the impact strength increased as the polyurethane content was increased, but the changes were not high at low polyurethane content, below 50%. For higher cross-link density, the compatibility was enhanced and the mechanical properties were improved. When the reaction rates of the components were different, some extent of phase separation was found in DMA and the properties were affected adversely.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760271608
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  • 6
    Electronic Resource
    Electronic Resource
    Vitrification effect during the reaction injection molding (RIM) process of epoxy resin (1989)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 29 (1989), S. 456-462 
    Details
    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: Vitrification occurs during the reaction injection molding (RIM) of epoxy resin, and the curing reaction rate is reduced as the Tg of the reacting mixture exceeds or approaches the local reaction temperature inside the mold cavity. The effect will be manifested in the distribution of the glass transition temperature across the thickness direction of the molded product. The reaction kinetic equation which includes the vitrification term in the form of the WLF equation is used in the computer simulation of the epoxy RIM process and the effect of the vitrification is shown by comparing with models with no vitrification considerations.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760290705
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  • 7
    Electronic Resource
    Electronic Resource
    Crystallization kinetics of poly(ethylene terephthalate). Part I: Kinetic equation with variable growth rate (1991)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 31 (1991), S. 110-115 
    Details
    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: A new crystallization kinetic equation has been derived considering the decrease in growth rate. The average linear growth rate of spherulite was assumed to be proportional to the m-th order of the uncrystallized fraction of the crystallizing material. A modified Avrami equation, 1 - Vc = exp[-Kf(t)n], was used where f(t) is the integral of the growth function, (1 - Vc)m. The validity of the equation was tested by analyzing the isothermal crystallization kinetic data of poly(ethylene terephthalate) from the melt using differential scanning calorimetry.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760310209
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  • 8
    Electronic Resource
    Electronic Resource
    Rubber modified epoxy resin. I: Cure kinetics and chemorheology (1994)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 625-631 
    Details
    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 curing and vitrification effect during the reaction of ATBN modified epoxy resin was studied through the dynamic differential scanning calorimetry method and a new reaction kinetic equation containing generalized WLF equation was developed to describe the reaction rate at both glassy and rubbery state. An autocatalytic mechanism was found to describe adequately the cure kinetics of the rubber modified epoxy resin and the overall order of reaction was assumed to be 2. The kinetic parameters were determined from the DSC data through the Marquardt's multivariable nonlinear regression method and Runge-Kutta integration technique. The presence of rubber indicated minor effect on the cure kinetics of epoxy resin. The Arrhenius type viscosity function was employed to establish a relationship between viscosity data measured by RMS and chemical conversion calculated from the reaction kinetic equation.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760340803
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  • 9
    Electronic Resource
    Electronic Resource
    Binary blends of nylons with ethylene vinyl alcohol copolymers: Morphological, thermal, rheological, and mechanical behavior (1990)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 30 (1990), S. 341-349 
    Details
    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: Binary blends of ethylene vinyl alcohol copolymers, containing 62 (EVOH-62) and 71 (EVOH-71) mole percent vinyl alcohols, with nylons (nylon-6, nylon-6/12, and nylon-12) have been prepared from melt mixing in a twin screw compounding machine. Morphological, thermal, rheological, and mechanical properties were determined. EVOH-62/nylon-6 and EVOH-71/nylon-6 blends showed homogeneous phase morphologies in the nylon-6-rich region, and fine phase separations (c.a. 2 × 10-7 m) in the EVOH-rich region. Melting point depression, positive deviations in viscosity and flexural modulus, and negative deviation in impact strength from the simple additive rule were generally observed. And the results were possibly interpreted in terms of compatibility and increased nylon/EVOH interactions over the nylon/nylon interactions. On the contrary, clean phase separations in large domains were observed from EVOH-71/nylon-6/12 and EVOH-71 /nylon-12 blends. Fibrillation was also obtained from EVOH rich blends. Probably due to the incompatible nature of these blends, yield at low rate of shear and a mechanical property drop were also observed.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760300605
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  • 10
    Electronic Resource
    Electronic Resource
    Crystallization kinetics of poly(ethylene terephthalate): Cmemory effect of shear history (1993)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 33 (1993), S. 83-91 
    Details
    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 memory effect of shear history was studied with poly(ethylene terephthalate) (PET) prepared under different shear conditions of 11.7 to 1168 s-1 in a capillary rheometer. The shear history of PET resin led to a memory effect, which in turn affected the crystallization kinetics. The crystallization rate increased with increasing shear rate. Double peaks of heating crystallization exotherms and a low value of Avrami exponent appeared at low shear rates, which was attributed to the existence of crystallization processes with different rates; one was the fast process involving the disentangled molecules that persisted during melting, and the other was the slow process involving the highly entangled molecules. The change of instantanenous Avrami exponent and overall crystallization rate constant was in good agreement with the expected trends assuming coexistence of the two crystallization processes. The crystallization kinetics of PET with shear history could be regarded as a growth rate decrease problem to be interpreted by the modified Avrami equation, 1 - Vc = exp[- K·f(t)n], when the fast process dominated the overall crystallization. The effect of shear history was reduced because of the relaxation process as the holding time in melt state before crystallization was increased.
    Additional Material: 15 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760330205
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