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  • 101
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1025-1035 
    ISSN: 0887-6266
    Keywords: polymer thin films ; thermosets ; microelectronics ; moisture ; physical aging ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In polymers for microelectronics applications, moisture is known to have a deleterious effect upon device reliability. In this paper, the moisture transport behaviors of a newly developed family of all-aromatic and aromatic/aliphatic copolyester thermosetting films were described. The moisture uptake as a function of temperature, relative humidity, sample thickness, and processing conditions were presented via conjugate moisture sorption tests.1 It was found that the post curing near but below Tg resulted in an increase in both total moisture uptake and diffusion coefficient due to the effect of physical aging and the generation of sample defect volume. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1025-1035, 1998
    Additional Material: 18 Ill.
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  • 102
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1061-1080 
    ISSN: 0887-6266
    Keywords: polymer blends ; dilatometry ; free volume ; specific volume ; excess volume ; compressibility ; thermal expansivity ; equation of state ; scaling parameters ; crystallinity ; glass transition ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Melt-miscible polymer blends of poly(ethylene oxide)/atactic poly(methyl methacrylate (PEO/a-PMMA)) were prepared by melt-mixing and characterized by pressure-volume-temperature (PVT) dilatometry in the pressure and temperature range of 0 to 200 MPa and 20 to 200°C, respectively. The PVT data were analyzed in terms of two equations of state (EOS). The empirical Tait EOS was applied in the glassy, semicrystalline, and equilibrium melt state, and the Simha-Somcynsky EOS theory was applied in the equilibrium melt and glassy state. The Simha-Somcynsky EOS theory contains a free volume function. The temperature, pressure, and composition dependence of the free volume fraction h calculated from the Simha-Somcynsky EOS theory was studied. As a function of blend composition we observe that the free volume fraction, thermal expansivity, and compressibility all deviate mainly positively from linearity while the specific volume deviates mainly negatively from linearity. These findings are reconciled with composition-dependent free volume parameters, the free volume and cell volume as well as with self- and cross-interaction parameters derived from the Simha-Somcynsky EOS theory as applied to polymer mixtures. Moreover, the pressure dependence of glass and melting transitions as well as crystallization kinetics have been investigated. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1061-1080, 1998
    Additional Material: 18 Ill.
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  • 103
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1201-1209 
    ISSN: 0887-6266
    Keywords: polymer electrolytes ; NMR ; conductivity ; glasses ; Arrhenius and VTF dependences ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We have studied the temperature variation of conductivity and 1H NMR linewidth of (PEG)xNH4ClO4 (x = 20, 30, 46, 100, 200, & 1000) polymer electrolyte systems. The temperature dependence of the conductivity shows two distinct behaviors, the low temperature VTF dependence crossing over to Arrhenius dependence at higher temperatures. The departure from the VTF behavior is found to be composition dependent. NMR spectra indicate the presence of large fractions of crystalline regions that start to melt around the crossover temperature. We understand the deviation from the VTF behavior as a consequence of this crystalline to elastomer transition. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1201-1209, 1998
    Additional Material: 9 Ill.
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  • 104
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1227-1233 
    ISSN: 0887-6266
    Keywords: FTIR spectroscopy ; isotactic polystyrene ; crystallization process ; induction period ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The melt crystallization process of isotactic polystyrene (i-PS) was studied by means of in situ Fourier transform infrared (FTIR) spectroscopy, with a focus on the conformational changes during the induction period. The spectra obtained during the induction period suggested the occurrence of some ordered structure that is characterized by higher regularity and packing of the helical moieties than observed in the melt. This ordered structure was clearly different from the amorphous structure, and close to the crystal structure. The Avrami analysis indicated that the formation process of the ordered structure at the late stage of the induction period is similar to the growth process of the crystallites after the induction period. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1227-1233, 1998
    Additional Material: 10 Ill.
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  • 105
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 237-251 
    ISSN: 0887-6266
    Keywords: segmented ; polyurethanes ; crosslinked ; mechanical ; dielectric properties ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Mechanical and dielectric properties of two series of segmented polyurethanes having soft segment concentration of 50 and 70% and a varying degree of crosslinking through the hard segment were studied. The degree of crosslinking in each series was varied by varying the butane diol/trimethylol propane ratio in the chain extender mixture. Tensile strength, elongation at break decrease, but elastic recovery increases monotonically with increasing crosslinking. The plateau modulus in the dynamic mechanical test decreases and then increases with increasing TMP content. Crosslinking causes broadening of the soft segment glass transition as seen by permittivity and loss factor measurements. It also affects high temperature behavior (above the glass transition of the hard segment); it lowers permittivity, loss factor, and ionic conductivity. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 237-251, 1998
    Additional Material: 15 Ill.
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  • 106
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2379-2391 
    ISSN: 0887-6266
    Keywords: block copolymer ; thermoplastic elastomer ; physical gel ; polymer micelle ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Thermoplastic elastomer gels (TPEGs) composed of a poly[styrene-b-(ethylene-co-butylene)-b-styrene] triblock copolymer and a low-volatility, midblock-compatible mineral oil have been investigated at different oil concentrations to ascertain the effect of composition on TPEG morphology and mechanical properties. The impact of thermal processing is also examined by comparing gels thermally quenched to 0°C or slowly cooled to ambient temperature. Transmission electron micrographs reveal that gels with 70 to 90 wt % oil exhibit styrenic micelles measuring ca. 24 nm in diameter. Variation in composition or cooling rate does not have any perceivable effect on micelle size or shape, whereas the rate at which the gels are cooled influences the extent of microstructural order and the time to rupture (tR) at constant strain. Dynamic rheological testing confirms the presence of a physically crosslinked network at TPEG compositions ranging from 70 to 90 wt % oil, independent of cooling rate. Results presented here suggest that the dynamic elastic shear modulus (G′) scales as tαR where α varies from 0.41 to 0.59, depending on cooling rate. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2379-2391, 1998
    Additional Material: 12 Ill.
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  • 107
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2423-2433 
    ISSN: 0887-6266
    Keywords: gelation theory ; nonlinear polymerization ; nonrandom crosslinking ; molecular weight distribution ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: On the basis of the first-order Markovian statistics, we propose a general matrix formula for the weight-average molecular weight of crosslinked polymer systems, explicitly given by M̄w = M̄w,0 + WX0 (I - X)-1 Sf. This equation is valid for both step and chain-growth polymerizations, including those in a nonequilibrium state irrespective of the reactor types used. In the context of the present theory, the onset of gelation is simply stated as a point at which the largest eigenvalue of the matrix X reaches unity (i.e., det(I - X) = 0). The present theory provides a unified point of view for various types of gelling systems. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2423-2433, 1998
    Additional Material: 3 Ill.
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  • 108
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 555-565 
    ISSN: 0887-6266
    Keywords: polyester ; annealing ; birefringence ; mechanical loss factor ; orientation ; density ; crystalline ; profile ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polyester (Egyptian) fibers were annealed at constant temperature (190°C) with different annealing times. Density, crystallinity, mean square density fluctuation, mechanical loss factor, and molecular orientation were calculated. Densities and mechanical loss factor were determined using an acoustic method. Changes in the molecular orientation were evaluated from the resulting optical data using the polarizing Pluta interference microscope. Correlation of data obtained by one method with another leads to relational changes in optothermal properties and in the molecular orientation. Changes of refractive index profiles of annealed PET fibers are provided. Illustrations using graphs and microinterferograms are shown. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 555-565, 1998
    Additional Material: 9 Ill.
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  • 109
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 595-606 
    ISSN: 0887-6266
    Keywords: IR ; perfluoro(sulfonate/carboxylate) bilayer ; sol-gel reactions ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: [Perfluoro-organic]/[silicon oxide] hybrids were formed by conducting sol-gel reactions of tetraethylorthosilicate within a perfluoro(carboxylate/sulfonate) bilayer membrane in the Co+2 form. FTIR and 29Si solid-state NMR spectroscopies were used to probe general aspects of molecular structure within the silicon oxide phase as a function of its relative content. The internal gel structure is considerably unconnected in terms of the population of Si—O—Si groups in cyclic vs. linear substructures and degree of Si atom coordination about bonded SiO4 units. In situ (HO)xSiO2[1-1/4x] intrastructure become increasingly less connected and more strained with regard to bonding geometry with increasing percent silicon oxide. Structural differences are seen between the silicon oxide component incorporated in carboxylate and sulfonate layers. These inorganically modified perfluorinated ionomers have potential as fast-proton conducting membranes for fuel cells and as permselective membranes in liquid pervaporation cells. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 595-606, 1998
    Additional Material: 11 Ill.
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  • 110
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 607-615 
    ISSN: 0887-6266
    Keywords: ternary phase diagram ; binodal curve ; Flory-Huggins theory ; interaction parameter ; membrane formation ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In this work, the ternary phase diagrams in three nonsolvent/solvent/PMMA systems (n-hexane/n-butyl acetate/PMMA, water/acetone/PMMA, and n-hexane/acetone/PMMA) were constructed by theoretical calculation and experimental measurement. Binodal curves were calculated by using the Flory-Huggins theory for three-component systems and measured by titrating the PMMA solution with nonsolvent until the onset of turbidity. By using concentration-dependent nonsolvent/solvent and solvent/PMMA interaction parameters and constant nonsolvent/PMMA interaction parameters, good agreement has been obtained between the calculation and the measurement. The values of nonsolvent/solvent interaction parameters were taken from the literature sources, and the values of solvent/PMMA and nonsolvent/PMMA interaction parameters were measured by vapor sorption and swelling equilibrium, respectively. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 607-615, 1998
    Additional Material: 5 Ill.
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  • 111
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    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 143-154 
    ISSN: 0887-6266
    Keywords: polymer simulation ; stress relaxation ; molecular dynamics ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We have been developing a physical picture on the atomic level of stress relaxation in polymer melts by means of computer simulation of the process in model systems. In this article we treat a melt of freely jointed chains, each with N = 200 bonds and with excluded-volume interactions between all nonbonded atoms, that has been subjected to an initial constant-volume uniaxial extension. We consider both the stress relaxation history σ(t) based on atomic interactions, and the stress history σe(t; NR) based on subdividing the chain into segments with NR bonds each, with each segment regarded as an entropic spring. It is found that at early times σ(t) 〉 σe(t; NR) for all NR, and that, for the remainder of the simulation, there is no value of NR for which σ(t) = σe(t; NR) for an extended period; by the end of the simulation σ(t) has fallen just below the value σe(t; 50). The decay of segment orientation, 〈P2(t; NR)〉, and of bond orientation 〈P2(t; 1)〉, is computed during the simulation. It is found that the decay of the atom-based stress σ(t) is closely related to that of 〈P2(t; 1)〉. This result may be understood through the concept of steric shielding. The change in local structure of the polymer melt during relaxation is also studied. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 143-154, 1998
    Additional Material: 11 Ill.
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  • 112
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 181-190 
    ISSN: 0887-6266
    Keywords: dynamics ; rigid-rod ; semidilute ; birefringence ; rotational diffusivity ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dynamics of rigid-rod-like molecules are studied using rheo-optical techniques. Measurements of flow birefringence as a function of shear rate are utilized to understand the scaling behavior of rotational diffusivity with respect to concentration and temperature. The concentration scaling exponent increases with increasing concentration and the scaling laws are valid in narrow concentration windows. The Doi-Edwards (DE) scaling law Dr ∼ c-2, holds at very high concentrations (cL3 〉 150). The concentration scaling exponent decreases dramatically with increasing temperature at concentrations, cL2d 〉 1. Scaling of rotational diffusivity, with respect to temperature and solvent viscosity in the semidilute regime, does not follow the predictions of DE theory (and related caging ideas). On the contrary, a model proposed by Fixman was found to explain both the temperature and concentration dependence of the rotational diffusivity. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 181-190, 1998
    Additional Material: 11 Ill.
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  • 113
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 221-235 
    ISSN: 0887-6266
    Keywords: segmented ; polyurethanes ; crosslinked ; properties ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Two series of segmented polyurethanes, one containing 50% soft segments and the other with 70% soft segments were synthesized. Chemical crosslinks were introduced through the hard segment in a controlled way. Chemical polyurethane networks were characterized by swelling. The effect of the degree of crosslinking on properties was examined. It was found that chemical crosslinks in the hard segment reduce the mobility of the soft phase and destroy the crystallinity of the hard phase, but they improve heat stability of the hard domains. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 221-235, 1998
    Additional Material: 13 Ill.
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  • 114
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 281-288 
    ISSN: 0887-6266
    Keywords: side-chain liquid-crystalline polymer membrane ; pervaporation ; benzene/cyclohexane mixture ; state-transformation ; benzene permselectivity ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: When a benzene/cyclohexane mixture of 10 wt % benzene was permeated through side-chain liquid-crystalline polymer (LCP) membranes by pervaporation at various temperatures, the permeation rate increased with increasing permeation temperature. The LCP membranes also exhibited a benzene permselectivity. The permselectivity for the benzene/cyclohexane mixture through the LCP membrane was different in the glassy, liquid-crystalline, and isotropic states. The LCP membrane had different apparent activation energies for permeation at each state. LCP membrane in the liquid-crystalline state had the highest apparent activation energy of the three states. Results suggest that the benzene permselectivity was influenced by changes in the LCP membrane structure, i.e., a state-transformation. It was found that a balance of the orientation of mesogenic groups and the flexibility of the siloxane chains was very important for benzene permselectivity. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 281-288, 1998
    Additional Material: 7 Ill.
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  • 115
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 325-335 
    ISSN: 0887-6266
    Keywords: dispersion polymerization ; styrene ; water-ethanol mixtures ; partitioning behavior ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A simulation model has been developed to predict the partitioning behavior of styrene in dispersion polymerization in ethanol-water mixtures. The composition of both the continuous phase and the dispersed phase are quantitatively estimated throughout the polymerization process. The presence of water in the system causes a considerable increase of the styrene partitioning in favor of the particles. Thus, at 70°C and for an initial composition of ethanol/water/styrene = 63.3/26.9/9.8, the concentration of styrene in the particles is about 4.8 times higher than that in the serum instead of about one in pure ethanol. The higher the polymerization temperature, the lower the styrene concentration in the particles; the higher the initial styrene concentration, the higher the styrene concentration in the particles, whereas the partition coefficient is not largely effected. In contrast, neither the interfacial tension nor the final particle size do significantly alter the simulation results. The predicted data from this model have been successfully applied to clarify the mechanisms involved in dispersion polymerization, in terms of stabilization and of kinetic events. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 325-335, 1998
    Additional Material: 13 Ill.
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  • 116
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 357-371 
    ISSN: 0887-6266
    Keywords: gelation theory ; nonlinear polymerization ; molecular weight distribution ; branched polymers ; polymer modification ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A Markovian model is proposed for nonrandom branching reactions, by using free-radical polymerization that involves chain transfer to polymer as an example. Free-radical polymerizations are kinetically controlled; therefore, each primary polymer molecule experiences different history of branched structure formation. By assuming that the primary chains with the identical birth time conform to the same chain connection probabilities, the nonlinear structural development can be viewed as a system in which the primary chains formed at different birth times are combined into nonlinear polymers in accordance with the first-order Markov chain statistics. An explicit formula for the weight-average chain length is derived in a matrix form. The onset of gelation is simply stated as a point at which the largest eigenvalue of the transition matrix X reaches unity, i.e., det(X - I) = 0. This criterion for the onset of gelation can be considered as an extension of the Flory/Stockmayer theory to a nonequilibrium reaction system. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 357-371, 1998
    Additional Material: 11 Ill.
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  • 117
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2811-2819 
    ISSN: 0887-6266
    Keywords: PTFE/hexafluoropropylene copolymers ; crystal ; disorder ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A series of new copolymers of tetrafluoroethylene (TFE) and hexafluoropropylene (HFP) containing up to 50 mol % of the hexafluoropropylene comonomer have been investigated with respect to chain conformation and crystal structure using wide-angle X-ray diffraction (WAXD). Increasing HFP content leads to significant departures from the highly ordered crystalline structure of the homopolymer PTFE; the helical conformation of the chain relaxes and untwists to accommodate the larger —CF3 pendant group in the HFP unit. Simultaneously the lateral hexagonal packing of the helices becomes less ordered and the a-dimension of the hexagonal cell increases. The above effects are progressive with increasing HFP content. At 50 mol % HFP incorporation the structure is a disordered crystalline phase. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2811-2819, 1998
    Additional Material: 4 Ill.
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  • 118
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2865-2868 
    ISSN: 0887-6266
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: No abstract.
    Additional Material: 3 Ill.
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  • 119
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2877-2886 
    ISSN: 0887-6266
    Keywords: ionomers ; NIR ; chemometrics ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Near Infrared (NIR) spectroscopy coupled with chemometrics techniques were utilized to study the composition and properties of styrene-sodium methacrylate ionomers. Predictive models were obtained for mol % ionic content, as well as for the ionic cluster glass transition temperature, storage modulus, and tan δ peak parameters. The results illustrate the feasibility of using NIR and chemometrics algorithms as a property predictive tool, as well as the potential for the development of full calibration models. The chemometric parameters are discussed based on correlations with ionomer NIR spectral features and the role water molecules play as a probe for the associated structure of the ionomer. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2877-2886, 1998
    Additional Material: 11 Ill.
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  • 120
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2905-2910 
    ISSN: 0887-6266
    Keywords: polyalkylthiophenes ; heterojunction ; BF3-diethyl ether ; electropolymerization ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A new kind of all-organic heterojunction consisting of polythiophene and its derivatives was prepared by the electrochemical method in the presence of boron trifluoride diethyl ether as supporting electrolyte on indium-tin oxide glass electrode. It was observed that sequential-different oxidation potential among layers of polythiophenes is a prerequisite for the heterojunction to show rectification effect. The carrier-flow of the three semiconductors for PBrT/PT/PMT heterojunction was discussed in detail. Its rectification ratio, barrier height, and ideality factor were 392 (±2 V), 0.89 eV, and 8.1, respectively. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2905-2910, 1998
    Additional Material: 8 Ill.
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  • 121
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2931-2939 
    ISSN: 0887-6266
    Keywords: associations ; random copolymers ; self-diffusion ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The self-diffusion of four styrene-methylmethacrylate random copolymers dissolved in acetone, a thermodynamically bad solvent for the styrene sequences in the copolymer, were investigated by pulsed-field gradient NMR. The echo attenuations Sinc(q,t) are dominated by diffusion of clusters. At higher concentrations, physical gelation sets in (formation of a transient network), which is manifested in an anomalous, restricted diffusion at short observation times. The measured fluctuations of the positions of the chain segments in the transient network have an amplitude of about 100 nm. The free long-range diffusion attained at long observation times shows a much stronger concentration dependence than in the nonassociating solvent benzene. The results are in accord with light-scattering investigations. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2931-2939, 1998
    Additional Material: 5 Ill.
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  • 122
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 95-104 
    ISSN: 0887-6266
    Keywords: blends ; melting behavior ; miscibility ; FTIR ; hydrogen bond interactions ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The miscibility of poly(4-hydroxystyrene-co-methoxystyrene) (HSMS) and poly(ε-caprolactone) (PCL) was investigated by differential scanning calorimetry and Fourier transform infrared spectroscopy (FTIR). HSMS/PCL blends were found to be miscible in the whole composition range by detecting only a glass transition temperature (Tg), for each composition, which could be closely described by the Fox rule. The crystallinity of PCL in the blends was dependent on the Tg of the amorphous phase. The greater the HSMS content in the blends, the lower the crystallinity. The polymer-polymer interaction parameter, χ32, was calculated from melting point depression of PCL using the Nishi-Wang equation. The negative value of χ32 obtained for HSMS/PCL blends has been compared with the value of χ32 for poly(4-hydroxystyrene) (P4HS)/PCL blends. The specific nature, quantitative analysis, and average strength of the intermolecular interactions in HSMS/PCL and P4HS/PCL blends have been determined at room temperature and in the molten state by means of Fourier transform infrared spectroscopy (FTIR) measurements. The FTIR results have been in good correlation with the thermal behavior of the blends. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 95-104, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 133-141 
    ISSN: 0887-6266
    Keywords: recrystallization rate ; equilibrium melting temperature ; differential scanning calorimetry (DSC) ; poly(butylene terephthalate) (PBT) ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A method is described for measuring the heat and rate of recrystallization following partial melting. The method uses a specific sequence of temperatures with a differential scanning calorimeter, and the melting and recrystallization processes were confirmed by optical observations. The method was applied to poly(butylene terephthalate). The rate of recrystallization was found to be roughly two orders of magnitude faster than isothermal crystallization from the melt. The melting temperatures obtained from recrystallization were used in the Hoffman-Weeks equation to deduce 236°C as the equilibrium melting temperature for poly(butylene terephthalate). © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 133-141, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 3115-3125 
    ISSN: 0887-6266
    Keywords: interfacial thickness ; PPO ; SAN ; SMA ; neutron reflectivity NR ; binary interaction energies ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Estimates for the thickness of the interface between poly (2,6-dimethyl-1,4-phenylene oxide) (PPO) and copolymers of styrene-acrylonitrile (SAN) and styrene-maleic anhydride (SMA) based on the theory of Helfand and Tagami are compared to neutron reflectivity (NR) measurements. Good agreement is found between the NR measurements and theoretical predictions that make use of a mean field binary interaction model and previously reported binary interaction energies. The techniques outlined in this work may be used to understand relationships between the mechanical properties of multiphase polymer blends and the fundamental thermodynamics of polymer interactions. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 3115-3125, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 447-453 
    ISSN: 0887-6266
    Keywords: polyethylene terephthalate ; low density polyethylene ; isocyanate functional group ; compatibility ; crystallization ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: To evaluate the compatibilizing effects of isocyanate (NCO) functional group on the polyethylene terephthalate/low density polyethylene (PET/LDPE) blends, LDPE grafted with 2-hydroxyethyl methacrylate-isophorone diisocyanate (LDPE-g-HI) was prepared and blended with PET. The chemical reaction occurred during the melt blending in the PET/LDPE-g-HI blends was confirmed by the result of IR spectra. In the light of the blend morphology, the dispersions of the PET/LDPE-g-HI blends were very fine over the PET/LDPE blends. DSC thermograms indicated that PET microdispersions produced by the slow cooling of the PET/LDPE-g-HI blends were largely amorphous, with low crystallinity, due to the chemical bonding. The tensile strengths of the PET/LDPE-g-HI blends were higher than those of the PET/LDPE blends having a poor adhesion. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 447-453, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1401-1417 
    ISSN: 0887-6266
    Keywords: polyelectrolytes ; Brownian dynamics ; shear flow ; extensional flow ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The conformational and rheological dynamics of dilute solutions of polyelectrolyte macromolecules undergoing shear and extensional flow are modeled using Nonequilibrium Brownian Dynamics (NEBD) and Configuration-Biased Monte Carlo (CBMC) simulations. The mathematical model utilizes a bead-spring chain with charged beads that interact through a screened Debye-Hückel potential, and that also interact through stretching and bending forces. The diffusion (or Fokker-Planck) equation for the probability density of the positions of the beads of the chain is converted to a Stochastic Differential Equation (SDE), from which the simulation algorithm for the NEBD is obtained. The CBMC is used in the initial chain generation and in determining steady-state properties in elongational flows. Various conformational and rheological quantities, such as the stress and birefringence, are monitored, under both steady-state and transient conditions, with the primary independent variable being the salt concentration (parametrized through the Debye length) and the strength of interaction q, related to the degree of ionization of the chain. It is found that this model is able to describe qualitatively many of the experimentally observed features in such systems. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1401-1417, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 543-553 
    ISSN: 0887-6266
    Keywords: polyacrylonitrile ; polyimine ; isotacticity ; dynamic mechanical analysis ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polyacrylonitrile (PAN) films have been “grafted” onto copper electrodes by cathodic polarization and analyzed by infrared spectroscopy and dynamic mechanical thermal analysis (DMTA). The dynamic mechanical response shows two or three transitions depending on the film thickness and the potential deposition. The viscoelastic properties of “ungrafted” PAN films, e.g., solvent cast films of commercially available PAN, are deeply different from those of “electrografted” films. The experimental data support that “ungrafted” chains are paracrystalline in contrast to the “grafted” ones which are essentially amorphous. Moreover, the irreversible transformation of the “grafted” PAN chains observed beyond 225°C is confirmed by Fourier transform infrared (FTIR) analysis and ascribed to an intramolecular cyclization of PAN into polyimine. This reaction occurs rapidly and at a comparatively low temperature with respect to “ungrafted” PAN, which suggests that the “grafted” chain configuration might be predominantly isotactic. The isotacticity and the amorphous structure appear to decrease as the thickness of the PAN film is increased. Literature data and the herein reported observations would suggest a dependence of the amorphous structure of PAN on the chain isotacticity. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 543-553, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 583-593 
    ISSN: 0887-6266
    Keywords: enthalpy relaxation ; differential scanning calorimetry ; peak-shift method ; polymethyl(α-n-alkyl)acrylates ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In this work, we have investigated by DSC the structural relaxation of amorphous polymethyl(α-n-alkyl)acrylates in which it is possible to change the length of the alkyl chain. We have evaluated the Narayanaswamy parameter, x, which controls the relative contribution of temperature and of structure to the relaxation time, the apparent activation energy, Δh*, and the nonexponentiality parameter, β, of the stretched exponential response function. The results suggest that x increases while Δh* decreases and β remains constant as the length of the side chain increases. This allows us to comment on the effect of chemical modification on the relaxation kinetics. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 583-593, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 641-653 
    ISSN: 0887-6266
    Keywords: impedance spectroscopy ; chemical and physical changes ; glass formers ; reactive polymers ; in situ monitoring ; dielectric properties ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A study was conducted aimed at establishing the nature of chemical and physical phenomena in polymeric and nonpolymeric glass formers that can be observed by impedance measurements. Various systems were investigated that undergo a temporal evolution of structure as a result of chemical reactions and physical processes such as crystallization, vitrification, or phase separation. Distinct and systematic changes in impedance during crystallization and vitrification confirmed that these events could be monitored by impedance spectroscopy. Of particular interest was the potential use of impedance measurements in detecting gelation in crosslinking polymers. It was shown that the experimentally observed “knee” in imaginary impedance during reaction shifts with frequency and, hence, cannot be used to measure gelation. But a new insight at the molecular level was obtained by employing a novel experimental approach based on simultaneous dielectric-infrared measurements. Evidence was generated to support the formation of a hydrogen-bonded complex in the vicinity of gel point in polymer networks, which affords a vehicle for the migration of intrinsic charges and provides a contribution to the overall conductivity. This finding should be explored further because it suggests the possibility of correlating dielectric response with gelation. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 641-653, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 665-671 
    ISSN: 0887-6266
    Keywords: clustering ; water ; wood ; adsorption ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Clustering behavior of water molecules during adsorption of water in wood was studied using the Zimm-Lundberg theory. The average cluster size of water molecules was determined with the help of wood adsorption isotherms at five temperatures. The effects of both relative humidity and temperature on average cluster size were studied. Average cluster size progressively increased with an increase in humidity. At humidities corresponding to fiber saturation, larger clusters were formed. Cluster size increased sharply with an increase in temperature at humidities close to saturation. Formation of large clusters at high temperature and humidities close to saturation is attributed to increased fraction of weakly bonded water and capillary condensation in such conditions. A description of adsorption of water in wood was provided in terms of average cluster size. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 665-671, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 705-714 
    ISSN: 0887-6266
    Keywords: molecular weight distribution ; comb copolymer ; branching ; grafting ; nonlinear polymerization ; modeling ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Grafting one type polymer onto a different polymer type may yield a comb-branched copolymer. The branching density has a significant effect on its overall molecular weight distribution. A general model is derived to describe the bivariate distribution of molecular weight and branching density for such comb copolymers. The model is applicable for various grafting mechanisms provided the side chains are randomly grafted onto the backbone. The determining parameters are the molecular weight distributions of backbone and side chains, and the branching density. Analytical expressions are obtained for the cases of the side chains having uniform and Schulz-Zimm distributions. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 705-714, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 715-725 
    ISSN: 0887-6266
    Keywords: polyethylene ; ion implantation ; surface structure ; wear ; hardness ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polyethylene (PE) film was implanted with 1000-keV Ar+ ions to a fluence of 5 × 1014 ions/cm2 under high vacuum conditions (2.5 × 10-6 torr) and the film surface was investigated by means of microhardness and microwear measurements, and FTIR/ATR, Raman, and XPS techniques. Ion implantation significantly increased the subsurface hardness and also significantly improved the microwear resistance of the polymer. The implanted surface region of the film was found to consist of two distinct layers. One was the outermost carbon layer with a thickness of the order of 10 nm. In this layer, ca. 75% of carbon atoms were combined by graphitic sp2 and diamond-like sp3 bonds, and the remaining 25% had chemical links with oxygen atoms. Spectroscopic data suggested that the sp2-bonded carbons segregated in graphite-like clusters containing imbedded oxygen atoms, interconnected by the sp3-bonded carbons. The other was the subsurface layer resulting from PE oxidation after ion-beam treatment. This layer was characterized by high contents of O—H and C=O groups as well as ester and double bonds. The chemical composition of the layer was uniform and did not vary over the layer thickness of about 1.4 μm. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 715-725, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 783-788 
    ISSN: 0887-6266
    Keywords: poly(ethylene terephthalate) ; sub-Tg ; annealing ; conformation ; infrared spectra ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Using FTIR spectroscopy we have examined conformational changes in the quenched and slowly cooled amorphous PET films during physical aging process. It was observed that the amount of trans conformers for quenched sample decreased upon sub-Tg annealing. For the slowly cooled sample that corresponds to a state closer to equilibrium, the amount of trans conformers hardly decreased, but increased gradually during sub-Tg annealing process. The conformational populations of these two samples tend to be identical with annealing time. These results demonstrate that sub-Tg annealing will lead to closer interchain packing and result in the formation of new cohesional entanglements along the chains. In situ FTIR studies on the conformational changes of these samples were also carried out during heating up of the sample through the glass transition region. The results showed that incremental changes of the amount of trans conformers in Samples Q and SC were gradual, while an abrupt change of trans conformers occurred in the sub-Tg annealed samples. These results were in agreement with the formation of the interchain cohesional entanglement due to sub-Tg annealing. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 783-788, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 841-850 
    ISSN: 0887-6266
    Keywords: specific volume ; Tait equation ; compressibility ; scaling parameter ; hole theory ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The pressure-volume-temperature (PVT) properties of three commercial samples of poly(dimethylsiloxane) are studied experimentally and theoretically in the temperature range 25-150°C and for pressure to ∼ 3 kbar. The Tait equation is employed to represent the data at elevated pressure. Isothermal compressibilities are computed for the three samples. The melt data are analyzed in terms of the Simha-Somcynsky hole theory, and scaling parameters of pressure, volume, and temperature are obtained. Satisfactory agreement between theory and experiment is found over the entire range of experimental pressures. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 841-850, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 851-859 
    ISSN: 0887-6266
    Keywords: poly(aryl ether ketone)s ; dielectric relaxation spectroscopy ; dynamic mechanical analysis ; α-relaxation ; β-relaxation ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The relaxation behavior of four amorphous poly(aryl ether ketone)s was investigated using dielectric relaxation spectroscopy and dynamic mechanical analysis. The temperature dependence of the relaxation times of the glass transition process and the cooperative nature of this process were unaffected by changes in polymer structure. The temperature location of the loss peaks for all polymers progressed smoothly between the low frequency of the mechanical measurements and the higher frequencies of the dielectric probe. Differences were observed in mechanical activation energy and dielectric relaxation strength for one polymer which contained a significant concentration of meta linkages, compared with the para-linked polymers, while relaxation broadness was generally greater in the dynamic mechanical mode. Changes in chemical structure had little effect on the shape, intensity, and location of the β-relaxation peak, the main observation being that the Arrhenius activation energy measured by dynamic mechanical analysis was significantly higher than that calculated from the dielectric data. The dielectric β-relaxation was sensitive to absorbed moisture. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 851-859, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1731-1738 
    ISSN: 0887-6266
    Keywords: poly(p-phenylene sulfide) fiber ; zone-drawing ; zone-annealing ; mechanical properties ; DSC thermogram ; viscoelastic properties ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A zone-drawing and zone-annealing treatment was applied to poly(p-phenylene sulfide) fibers in order to improve their mechanical properties. The zone-drawing (ZD) was carried out at a drawing temperature of 90°C under an applied tension of 5.5 MPa, and the zone-annealing (ZA) was carried out at an annealing temperature of 220°C under 138.0 MPa. The differential scanning calorimetry (DSC) thermogram of the ZD fiber had a broad exothermic transition (Tc = 110°C) attributed to cold-crystallization and a melting endotherm peaking at 286°C. The Tc of the ZD fiber was lower than that (Tc = 128°C) of the undrawn fiber. In the temperature dependence of storage modulus (E′) for the ZD fiber, the E′ values decreased with increasing temperature, but increased slightly in the temperature range of 90-100°C, and decreased again. The slight increase in E′ was attributable to the additional increase in the crosslink density of the network, which was caused by strain-induced crystallization during measurement. The resulting ZA fiber had a draw ratio of 6.0, a degree of crystallinity of 38%, a tensile modulus of 8 GPa, and a tensile strength of 0.7 GPa. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1731-1738, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 937-958 
    ISSN: 0887-6266
    Keywords: thermodynamics ; heteropolymers ; phase diagram ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: On the basis of a variational principle a quantitative theory is developed enabling a thermodynamic description in terms of mean field approximation of heteropolymer mixtures of macromolecules with an arbitrary distribution for both degree of polymerization and composition. Rather simple general equations are derived to calculate compositions and volume fractions of spatially homogeneous macroscopic phases as well as to find the cloud-point curve, spinodal, and critical points. Potentialities of general theory are illustrated for copolymers synthesized by traditional methods. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 937-958, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 983-989 
    ISSN: 0887-6266
    Keywords: positron annihilation ; free-volume ; Nafion ; free-volume size distribution ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We report a new result of free-volume hole size distribution in water and ethanol-swollen Nafion-117 polymer. With the increase in water content, free-volume hole size decreases, but overall the volume fraction increases. The hole size distribution in dry polymer is seen to be distinctly different from hydrated membranes. The narrow and symmetric distribution in hydrated membrane as compared to dry membrane is believed to be a consequence of crosslinking due to cluster formation. In alcohol-swollen membranes, on the other hand, not only are the free-volume size and fraction seen to be higher, the hole size distribution is seen to be broader compared to dry or hydrated membranes, indicating the effect of penetration of alcohol into the hydrophobic backbone region. We have also examined our results vis-a-vis reported gas diffusion studies in Nafion in the framework of existing free-volume model. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 983-989, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1013-1024 
    ISSN: 0887-6266
    Keywords: nonlinear optical polymer ; pressure ; chromophore reorientation ; poly(alkyl methacrylates) ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Activation volumes for chromophore reorientation were measured for a series of guest-host polymeric materials, indicating a significant coupling between chromophore motion and the glassy α and β relaxation dynamics of the polymer host. The specific systems studied were formed by individually dissolving N,N-dimethyl-p-nitroaniline (DpNA), 4-(dimethylamino)-4′-nitrotolane (DMANT), 4-(diethylamino)-4′-nitrotolane (DEANT), and 1-((4-(dimethylamino)phenyl)ethynyl)-4-((4-nitrophenyl)ethynyl)benzene (DMAPEANT) in poly(methyl methacrylate) (PMMA), poly(ethyl methacrylate) (PEMA), and poly(isobutyl methacrylate) (PiBMA). In each of these systems, the isothermal, sub-Tg decay of the second-order optical susceptibility χ(2) was monitored as a function of pressure using second harmonic generation. In each system, the observed decay of χ(2) was represented by a stretched exponential equation from which the decay time τ0 and decay distribution width βKWW were determined. For each dopant molecule, the decrease in activation volume with the increasing size of the polymer host's alkyl side group and the pressure dependence of βKWW were indicative of partial coupling between chromophore rotation and the glassy β relaxation dynamics of the polymer host. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1013-1024, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1091-1094 
    ISSN: 0887-6266
    Keywords: electrorheological fluids (ERFs) ; poly(dimethyl siloxane) gels ; artificial muscle ; electromechanical actuators ; 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 36 (1998), S. 1115-1128 
    ISSN: 0887-6266
    Keywords: interface structure ; fluorescence energy transfer ; polymer blends ; latex films ; poly(methyl methacrylate) ; poly(butyl methacrylate-co-butyl acrylate) ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Immiscible polymer blend films were formed by air drying aqueous dispersions containing mixtures of a high-Tg latex, poly(methyl methacrylate), and a film-forming low-Tg latex, poly(butyl methacrylate-co-butyl acrylate). Fluorescence energy transfer experiments were used to characterize the interfaces in these films, in which one component was labeled with a donor dye and the other with an acceptor. The quantum efficiency of energy transfer (ΦET) between the donors and acceptors is influenced by the interfacial contact area between the two polymer phases. As the amount of soft component in the blend is increased, ΦET approaches an asymptotic value, consistent with complete coverage of the hard polymer surface with soft polymer. This limiting extent of energy transfer is very sensitive to the total surface area in the film, with correspondingly more energy transfer at constant volume fraction for small hard particles. Some of the details of the energy transfer are revealed through a fluorescence lifetime distribution analysis. The presence of ionic surfactant (sodium dodecyl sulfate) in the dispersion from which the latex blend film is prepared reduces the cross-boundary energy transfer by 30%, which implies that in these films the surfactant decreases the interfacial contact. After annealing the surfactant-free blends above 100°C, we observe an increase in energy transfer, consistent with a broader interface between the two polymers. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1115-1128, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1153-1165 
    ISSN: 0887-6266
    Keywords: even-odd nylons ; lamellar crystals ; structure ; hydrogen-bonding schemes ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Nylon 6 9 has been shown to have structures with interchain hydrogen bonds in both two and in three directions. Chain-folded lamellar crystals were studied using transmission electron microscopy and sedimented crystal mats and uniaxially oriented fibers studied by X-ray diffraction. The principal room-temperature structure shows the two characteristic (interchain) diffraction signals at spacings of 0.43 and 0.38 nm, typical of α-phase nylons; however, nylon 6 9 is unable to form the α-phase hydrogen-bonded sheets without serious distortion of the all-trans polymeric backbone. Our structure has c and c* noncoincident and two directions of hydrogen bonding. Optimum hydrogen bonding can only occur if consecutive pairs of amide units alternate between two crystallographic planes. The salient features of our model offer a possible universal solution for the crystalline state of all odd-even nylons. The nylon 6 9 room-temperature structure has a C-centered monoclinic unit cell (β = 108°) with the hydrogen bonds along the C-face diagonals; this structure bears a similarity to that recently proposed for nylons 6 5 and X3. On heating nylon 6 9 lamellar crystals and fibers, the two characteristic diffraction signals converge and meet at 0.42 nm at the Brill temperature, TB · TB for nylon 6 9 lamellar crystals is slightly below the melting point (Tm), whereas TB for nylon 6 9 fibers is ≅ 100°C below Tm. Above TB, nylon 6 9 has a hexagonal unit cell; the alkane segments exist in a mobile phase and equivalent hydrogen bonds populate the three principal (hexagonal) directions. A structure with perturbed hexagonal symmetry, which bears a resemblance to the reported γ-phase for nylons, can be obtained by quenching from the crystalline growth phase (above TB) to room temperature. We propose that this structure is a “quenched-in” perturbed form of the nylon 6 9 high-temperature hexagonal phase and has interchain hydrogen bonds in all three principal crystallographic directions. In this respect it differs importantly from the γ-phase models. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1153-1165, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1557-1566 
    ISSN: 0887-6266
    Keywords: polyesters ; PET ; PEN ; PEI ; 13C NMR ; dynamics ; nuclear relaxation times ; gas diffusion ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dynamics of amorphous aromatic polyesters consisting of poly(ethylene terephthalate) (PET), poly(ethylene isophthalate) (PEI), and poly(ethylene 2,6-naphthalenedicarboxylate) (PEN) has been investigated by means of solid state CPMAS 13C NMR. Proton T2, 13C T1ρ, and proton T1ρ decays have been measured in particular, and the experimental data fitted to suitable model functions to determine best relaxation parameters. The fitting results show for proton T2 and 13C T1ρ measurements the presence of two components with different relaxation times and intensities, arising from different motional domains. The proton T1ρ, on the contrary, shows a single component which limits the dimensions of the two regions to less than 20 Angstroms. The dependence of 13C T1ρ values on two different irradiating field strengths (H1 = 38 KHz, H1 = 60 KHz) allowed the assignment of each component to relatively rigid and mobile regions. By comparing the three polymers we observe that PEN and PEI have a similar relaxation behavior, while a higher fraction of mobile components was found for PET. These differences are believed to arise mainly from local motions of the aromatic rings. The relaxation measurements have been evaluated to suggest a correspondence to O2 and CO2 gas permeabilities in PET, PEI, and PEN. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1557-1566, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2165-2175 
    ISSN: 0887-6266
    Keywords: temperature-modulated differential scanning calorimetry ; DSC ; heat capacity ; glass transition ; thermal relaxation ; polystyrene ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The glass transition can be measured at different experimental conditions. Using spectroscopic methods at relative high frequency the α-relaxation is measured in the thermodynamic equilibrium. In the caloric case we call this phenomenon thermal relaxation transition (TRT). With a conventional differential scanning calorimeter (DSC) the transition of the equilibrium (the melt) into a nonequilibrium (the glassy state) is measured. This effect is called thermal glass transition (TGT). In contrast to the TGT, the TRT can be described using the linear response approach. The temperature-modulated differential scanning calorimetry (TMDSC) technique superimposes a periodical temperature perturbation upon the constant scanning rate of conventional DSC. This technique combines a spectroscopic method with a linear temperature scan. Both the TGT and the TRT are measured simultaneous. Because the frequencies are relatively low in a TMDSC experiment, the temperature ranges of both transitions overlap. In this case, the experimental results show an influence of the TGT on the TRT. The reason of that is the deviation from the nonequilibrium. In this case, the fictive temperature is different from the external temperature. This effect can be described by means of a Tool-Narayanaswamy-Moynihan model for the TGT. Based on this model, a description of the complex heat capacity close to the thermal glass transition is shown. The influence of the beginning freezing-in process on the thermal relaxation is characterized by the fictive temperature. Using the presented description, a quantitative calculation of the nonlinear effects in the thermal relaxation is possible. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2165-2175, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2177-2189 
    ISSN: 0887-6266
    Keywords: yield ; polyethylene ; stem length ; crystal plasticity ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The yield stress behavior of a range of polyethylene materials which differ with respect to their short chain branch content has been studied. Measurements carried out over a wide range of temperatures have shown that there is a sudden transition in the behavior of the yield stress at a temperature which is dependent on both the grade of material and the applied strain rate. These results are in agreement with previous results found from analysis of the yield strain behavior.Above the transition temperature the materials all behave in a nonlinear viscoelastic manner, and the yield process is considered as being propagation controlled. Below the transition temperature the materials all behave in an elastic-plastic manner, and the yield process is considered as being nucleation controlled. Below the transition temperature the temperature dependence of the yield stress is determined by the thickness of the crystalline lamellae. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2177-2189, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2225-2235 
    ISSN: 0887-6266
    Keywords: PEEK ; composite ; stability ; nonisothermal ; crystallinity ; melting ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The thermal stability of a short carbon-fiber-reinforced PEEK composite was assessed by thermogravimetry and by a Rheometrics dynamic analyzer. The results indicated that holding for 10 min at 380°C was a suitable melting condition to avoid the thermooxidative degradation under air. After proving that the heating rate of 50°C/min can be used to evaluate the crystallinity, a heating stage was used to prepare nonisothermally crystallized specimens using cooling rates from 1 to 100°C/min after melting at 400°C for 3 or 15 min. The degree of crystallinity and the melting behavior of these specimens were investigated by DSC at a heating rate of 50°C/min. The presence of three or four regions indicated that the upper melting temperature, Tm, changed with the crystallization temperature. The first region with the highest Tm, which corresponded to the cooling rate of 1°C/min, can be associated with the crystallization in regime II. There was a second region where Tm decreased as the amount of crystals formed in regime II decreased with increasing cooling rate from 5 to 20°C/min. The third region, a plateau region, corresponded to regime III condition in which the crystals were imperfect. In the fourth region, the cooling was so fast that crystallization was incomplete during the cooling for the melting condition of 400°C for 15 min. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2225-2235, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2513-2523 
    ISSN: 0887-6266
    Keywords: block copolymer ; thermoplastic elastomer ; physical gel ; order-disorder transition ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Thermoplastic elastomer gels (TPEGs) composed of a poly[styrene-b-(ethylene-co-butylene)-b-styrene] triblock copolymer and a low-volatility, midblock-compatible mineral oil have been investigated here to ascertain the effects of composition on TPEG morphology, and temperature on mechanical properties. Cryofracture-replication transmission electron micrographs reveal the existence of spheroidal bumps due to copolymer micelles, as well as a network of irregularly shaped, high-aspect-ratio features. Since the density of this network decreases with increasing oil concentration, these features are attributed to copolymer grain boundaries. Micellar periodicities are discerned from small-angle X-ray scattering as a function of copolymer concentration and compared with previously reported data from related systems. Dynamic rheological tests performed up to 140°C indicate that the linear viscoelastic regime for these TPEGs decreases with both increasing copolymer concentration and temperature. A concentration-dependent thermal transition, signified by an abrupt reduction in the dynamic elastic modulus (G′), has also been identified.© 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2513-2523, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2949-2959 
    ISSN: 0887-6266
    Keywords: ultrasound ; crystallization kinetics ; film formation ; polychloroprene ; shear modulus ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We report the application of an ultrasonic shear wave reflection technique for the investigation of film formation and crystallization kinetics of one amorphous and two semicrystalline polychloroprene samples with different gel content. Both isothermal and temperature-dependent measurements of the complex dynamic shear modulus (G* = G′ + iG″) have been performed at a frequency of 5.32 MHz. The process of film formation during the evaporation of water is expressed by a stepwise increase of the shear modulus. For the semicrystalline samples a further increase, which is due to crystallization, can be observed. Film formation and crystallization are delayed for the sample with high gel content and its minor final modulus is explained by a lower degree of crystallinity. The time-dependent increase of the shear modulus due to the growth of spherulites has been analyzed by the Avrami equation combined with the Kerner model for the modulus of a two-phase composite (spherulites in an amorphous matrix). The dynamic shear modulus for the spherulites has been estimated by a model introduced by Halpin and Kardos. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2949-2959, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2981-3000 
    ISSN: 0887-6266
    Keywords: sorption ; diffusion ; acetone ; poly(ethylene terephthalate) ; poly(ethylene 2,6-naphthalate) ; copolymers ; positron annihilation lifetime spectroscopy ; infrared spectroscopy ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Random copolymers of poly(ethylene terephthalate) (PET) and poly(ethylene 2,6-naphthalate) (PEN) were synthesized by melt condensation. In a series of thin, solvent cast films of varying PEN content, acetone diffusivity and solubility were determined at 35°C and an acetone pressure of 5.4 cm Hg. The kinetics of acetone sorption in the copolymer films are well described by a Fickian model. Both solubility and diffusivity decrease with increasing PEN content. The acetone diffusion coefficient decreases 93% from PET to PET/85PEN, a copolymer in which 85 weight percent of the dimethyl terephthalate in PET has been replace by dimethyl naphthalate 2,6-dicarboxylate. The acetone solubility coefficient in the amorphous regions of the polymer decreases by approximately a factor of two over the same composition range. The glass/rubber transition temperatures of these materials rise monotonically with increasing PEN content. Copolymers containing 20 to 80 wt % PEN are amorphous. Samples with 〈20% or 〉80% PEN contain measurable levels of crystallinity. Estimated fractional free volume in the amorphous regions of these samples is lower in the copolymers than in either of the homopolymers. Relative free volume as probed by positron annihilation lifetime spectroscopy (PALS) decreases systematically with increasing PEN content. Acetone diffusion coefficients correlate well with PALS results. Infrared spectroscopy suggests an increase in the fraction of ethylene glycol units in the trans conformation in the amorphous phase as the concentration of PEN in the copolymer increases. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2981-3000, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 3035-3048 
    ISSN: 0887-6266
    Keywords: epoxy ; absorption ; water ; positron annihilation lifetime spectroscopy ; free volume ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Epoxy resins absorb significant quantities of moisture, typically 1 to 7% by weight for various formulations, which can greatly compromise their physical properties. It is known that polarity of the epoxy is a significant factor in determining the ultimate moisture uptake. However, the contribution from molecular topology still remains vague. In this work, the effects of molecular topology are elucidated by synthesizing novel epoxies where the polarity is maintained constant but the topology is systematically altered. The molecular topology is quantified in part via Positron Annihilation Lifetime Spectroscopy (PALS) in terms of the nanometer-sized voids, or nanovoids, that are also commensurate with typical interchain distances. The nanovoids are separated into their absolute zero and thermally fluctuating fractions by performing PALS measurements over a wide range of temperatures. A strong correlation is observed between the absolute zero hole volume fraction and the ultimate moisture uptake. Although the correlation is clear, the absolute zero hole volume fraction alone is not sufficient to predict the ultimate moisture uptake, and network polarity must also be considered. It is surmised that the role of the nanovoids is to open the epoxy matrix and alleviate steric hindrances that may prevent a water molecule from associating with a polar group. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 3035-3048, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 3079-3086 
    ISSN: 0887-6266
    Keywords: diffusion ; block copolymer ; monomeric friction factor ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Monomeric friction factors, Ξ, for polystyrene (PS), polyisoprene (PI), and a polystyrene-polyisoprene (SI) diblock copolymer have been determined as a function of temperature in four poly(styrene-b-isoprene-b-styrene-b-isoprene) tetrablock copolymer matrices. The Rouse model has been used to calculate the friction factors from tracer diffusion coefficients measured by forced Rayleigh scattering. Within the experimental temperature range the tetrablock copolymers are disordered, allowing for measurement of the diffusion coefficient in matrices with average compositions determined by the tetrablock copolymers (23, 42, 60, and 80% styrene by volume). Remarkably, for a given matrix composition the styrene and isoprene friction factors are essentially equivalent. Furthermore, at a constant interval from the system glass transition temperature, Tg, all of the friction factors (obtained from homopolymer, diblock copolymer, and tetrablock copolymer dynamics) agree to within an order of magnitude. This is in marked contrast to results for miscible polymer blends, where the individual components generally have distinct composition dependences and magnitudes at constant T - Tg. The homopolymer friction factors in the tetrablock matrices were systematically slightly higher than those of the diblock, which in turn were slightly higher than those of the homopolymers in their respective melts, when all compared at constant T - Tg. This is attributed to the local spatial distribution of styrene and isoprene segments in the tetrablocks, which presents a nonuniform free energy surface to the tracer molecules. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 3079-3086, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 3087-3100 
    ISSN: 0887-6266
    Keywords: polymer dynamics ; light scattering spectroscopy ; probe diffusion ; coupling model ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We studied translational diffusion of dilute monodisperse spheres (diameters 14 〈 d 〈 455 nm) in aqueous 1 MDa hydroxypropylcellulose (0 ≤ c ≤ 7 g/L) at 25°C using quasielastic light scattering. Spectra are highly bimodal. The two spectral modes (“slow,” “fast”) have different physical properties. Probe behavior differs between small (d 〈 Rh) and large (d ≥ Rg) probes; Rh and Rg are the matrix polymer hydrodynamic radius and the radius of gyration, respectively. We examined the dependences of spectral lineshape parameters on d, c, scattering vector q, and viscosity η for all four probe-size and mode-type combinations. We find three time scale-separated modes: (1) a large-probe slow mode has properties characteristic of particle motion in a viscous medium; (2) a large-probe fast mode and small-probe slow modes share the same time scale, and have properties characteristic of probe motion coupled to internal chain dynamics; and (3) a small-probe fast mode has properties that can be attributed to the probe sampling local chain relaxations. In the analysis, we also attempted to apply the coupling/scaling (CS) model of Ngai and Phillies [Ngai, K. L., Phillies, G. D. J. J. Chem. Phys., 105, 8385 (1996)] to analyze our data. We find that the second mode is described by the coupling/scaling model for probe diffusion; the first and third modes do not follow the predictions of this model. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 3087-3100, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 3137-3145 
    ISSN: 0887-6266
    Keywords: X-ray analysis ; copoly(ester-imide) ; thermotropic liquid crystalline polymers ; random copolymers ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The structure of a thermotropic liquid crystalline copoly(ester-imide) prepared from p-hydroxybenzoic acid (48 mol %), 4,4′-dihydroxybenzophenone (26 mol %), and N,N′-bis(trimellitimide)hexane (26 mol %) has been investigated by X-ray diffraction. X-ray fiber diagrams of as-spun and annealed fibers contain a series of aperiodic layer lines reminiscent of those seen for fibers of other copolymers that have extended chain conformations and completely random monomer sequences. The positions of these layer lines were reproduced approximately in simulation of the X-ray scattering by a fully extended chain of completely random sequence, and the match was improved to within experimental error when we considered a stereochemically acceptable sinuous chain. This agreement was lost when the sequence statistics deviated were completely random. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 3137-3145, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2339-2348 
    ISSN: 0887-6266
    Keywords: epoxy ; curing ; generating function ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The systems of diepoxides cured with primary amine in presence of an monoepoxide, monofunctional reactive, under equal stoichiometric ratio has been analyzed by a generating function method. The average degree of polymerization, which changed with time or conversion, and gel point were calculated. The profiles of the degree of polymerization and critical conversion are dependent on the content of and relative reactivities of epoxy groups. For a system with the same ratio, the critical epoxy conversion increases with increasing reactivity. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2339-2348, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2371-2378 
    ISSN: 0887-6266
    Keywords: liquid crystalline ; polymers ; X-ray diffraction ; fibers ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The synthesis and a partial characterization of segmented liquid crystalline polymers with 3,3′-diallyl-4,4′-dihydroxybiphenyl unit in the rigid moiety is reported. The general formula of polymers is [-p-C6H4-COO-p-C6H3(R)-p-C6H3(R)-OOC-p-C6H4-O-(CH2)nO-]x, with n = 6, 8, 10, 12, and R = —CH2—CH=CH2. All polymers have nematic liquid-crystalline behavior. At room temperature, annealed fiber samples of polymers show a complex polymorphism. Three phases have been isolated with very large unit cells accommodating 6 or 12 chains. The projection of the molecular packing in a plane perpendicular to the c axis is characterized by the organization of chains in a two-dimensional hexagonal or quasi-hexagonal array. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2371-2378, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2413-2421 
    ISSN: 0887-6266
    Keywords: positron annihilation ; polyimide ; ion implantation ; membrane ; permeability ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 6FDA-pMDA polyimide membranes were implanted with 140 keV N+ ions to fluences between 2 × 1014 and 5 × 1015 cm-2. Variable energy positron annihilation spectra were taken and spectral features compared to previously reported changes in gas permeability and permselectivity of these membranes as a function of ion fluence. Positron data corroborate the explanation of these changes in terms of molecular damage caused by the implant: for fluences up to about 1 × 1015 cm-2, the concentration of irradiation-induced defects merely increases with implant fluence; while fluences exceeding this threshold value create a second type of positron annihilation site, thereby marking a distinct change in the structure of the polymer, which is responsible for the vast improvement of gas permselectivity data found at the same threshold fluence. PACS codes: 78.70.Bj - positron annihilation; 61.82.Pv - polymers, organic compounds; 61.72.Ww - doping and impurity implantation. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2413-2421, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 3127-3136 
    ISSN: 0887-6266
    Keywords: block copolymers ; thin films ; patterned surfaces ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We present results from a numerical study of a coarse-grained model of diblock copolymer (BCP) thin films cast on a chemically patterned surface. The patterned surface contains chemical inhomogeneities with a repeat spacing length scale comparable to the linear size of the BCP molecules. We find that the orientation of the lamellae in the thin film and the overlap of the film morphology with the preassigned surface pattern is strongly influenced by the commensurability between the bulk unconstrained lamellar size λ*, and the linear size of the surface inhomogeneities w. PACS Numbers: 64.60.Cn, 61.41.+e, 64.60.My, 64.75.+g. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 3127-3136, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2677-2681 
    ISSN: 0887-6266
    Keywords: sulfonated SEBS ; viscosity property ; molecular aggregation ; freezing-thawing treatment ; shear-thickening ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dilute solution properties of lightly sulfonated hydrogenated styrene-butadiene-styrene block copolymer (S-SEBS) dissolved in tetrahydrofunan (THF) were studied by viscometry. The ring conformation in dilute regime can be deduced from the intrinsic viscosity data. It is believed that this special conformation results from the location of ionic group at both two-end blocks. The intermolecular aggregation can be observed when the solutions undergo the freezing-thawing process in the same concentration region. The extent of aggregation is affected by the freezing-thawing cycle times, water content in THF, and the counterion radii, etc. The properties of the aggregation equilibrium are also discussed. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2677-2681, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2703-2716 
    ISSN: 0887-6266
    Keywords: calorimetry ; dielectrics ; diffusion ; monoamine-triepoxide ; thermoset ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Calorimetry and dielectric relaxation spectroscopy during the growth of a polymer network in the stoichiometric mixture of a triepoxide with 4-chloroaniline have been performed in separate experiments to investigate the increase in the relaxation time with the number of covalent bonds. A comparison with the corresponding study of triepoxide-aniline and triepoxide-3-chloroaniline mixtures shows that steric hindrance of the amine group by chlorine slows the molecular dynamics and the relaxation time of the state containing a fixed number of bonds. The polymerization kinetics measured during ramp heating does not yield a reliable activation energy. A recent empirical relation between the relaxation time and the extent of polymerization, and the condition for the onset of diffusion-control kinetics have been examined using the data for these three polymerizing mixtures. The results show substantial deviations from the empirical relation and appear to conflict with our basic understanding of the polymerization process. It is shown mathematically that features attributed to the onset of diffusion-controlled kinetics can arise from thermochemical behavior alone, without reference to the molecular dynamics. An earlier theory for the change in the kinetics of an addition reaction from mass control to diffusion control has been considered, and is seen as relevant to the polymerization reactions. It is argued that the dielectric relaxation rate does not directly indicate the chemical reaction rate because the reorientational motion of the dipolar entities may not be coupled to the rotational and translational diffusion that brings the sterically hindered chemically reacting sites together. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2703-2716, 1998
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    Communications in Numerical Methods in Engineering 14 (1998), S. 229-240 
    ISSN: 1069-8299
    Keywords: filling of thin section ; finite element method ; surface tension ; interface element ; Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: An interface element to model the pressure discontinuity due to surface tension when applied to the filling of a thin section cavity is presented. The equations used to form the element matrix for the interface element are the line integral form of the continuity and momentum equations. During the development of the finite element model, the pressure difference across the free surface due to surface tension is treated as an additional traction and is applied to all element sides which form the free surface. Simple numerical examples are then presented to illustrate the technique on the filling of a rectangular thin section cavity. © 1998 John Wiley & Sons, Ltd.
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    Communications in Numerical Methods in Engineering 14 (1998), S. 253-269 
    ISSN: 1069-8299
    Keywords: potential flow ; optimization approach ; sensitivity analysis ; adjoint variable method ; finite elements ; Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: Potential flow problems around immersed bodies have been treated by an optimization approach. When the stream function is used as the field variable, the boundary values may not be known a priori and may be taken as the decision parameters to minimize integral objective functionals. The circulation integrals around the immersed bodies or the Kutta condition at the trailing edges of the bodies may be used to construct the objective function of optimization. The sensitivity analysis needed for the minimization process is performed by the adjoint variable method, while the numerical solutions of the primary (flow) and adjoint equations have been obtained by the finite element method. Having checked the present method with exact solutions and the classical superposition method, several flow problems involving one or more immersed bodies with or without circulation are investigated numerically. © 1998 John Wiley & Sons, Ltd.
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  • 162
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    Communications in Numerical Methods in Engineering 14 (1998), S. 289-304 
    ISSN: 1069-8299
    Keywords: stress intensity factors (SIF) ; finite element method (FEM) ; reciprocal work contour integral (RWCI) ; path-independent integrals (PII) ; displacement correlation technique (DCT) ; quarter-point displacement technique (QPDT) ; Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: A new method for improving the approximations of stress intensity factors computed from path-independent integrals is developed. The method uses Richardson's extrapolation. Numerical results are given to show the efficiency and the stability of the present method. © 1998 John Wiley & Sons, Ltd.
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  • 163
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    Communications in Numerical Methods in Engineering 14 (1998), S. 321-333 
    ISSN: 1069-8299
    Keywords: eigenvalue analysis ; sensitivity evaluation ; large-scale systems ; Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: This paper presents a general rank-1 matrix formula which allows for proper rearrangement of individual terms in multiproduct forms involving vectors and matrices. A far-reaching application of the new matrix formula to eigenvalue sensitivity evaluation is presented in the paper. Such an application reduces the sensitivity expressions to elegant, very fast and recursive forms with substantial savings in computer resources. The formula is applicable to rank-1 matrices of special structures which may constitute derivatives of the system state matrix, which is widely used in control system applications, with respect to various parameters of interest. In such cases, the use of the rank-1 formula yields exact non-approximate solutions which are identical to those obtained by other conventional formulas. The applicability of the rank-1 formula is believed to cover a wide variety of practical engineering systems pertaining to control and stability. © 1998 John Wiley & Sons, Ltd.
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  • 164
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    Communications in Numerical Methods in Engineering 14 (1998), S. 719-730 
    ISSN: 1069-8299
    Keywords: phase-change problems ; conduction-advection equation ; upwind weight function ; Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: A finite element formulation for solving transient multidimensional phase-change problems considering advective effects is presented. This temperature-based formulation includes the definition of a phase-change function able to deal with classical isothermal and non-isothermal phase-change cases. Moreover, a new upwind weight function is defined in order to avoid numerical oscillations in problems with dominant advective effects. Further, some important aspects related to its numerical implementation are also addressed. The ability of this methodology is illustrated, firstly, in the solution of a one-dimensional test example. Finally, the numerical simulation of a direct-chill continuous casting process is performed. © 1998 John Wiley & Sons, Ltd.
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  • 165
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    Communications in Numerical Methods in Engineering 14 (1998), S. 763-772 
    ISSN: 1069-8299
    Keywords: coupled vibrations ; Timoshenko beam ; boundary integral equation method ; symbolic computation ; Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: Symbolic computer algebra systems relieve one from the tedious task of different mathematical operations which are essential to obtain solutions. Due to their highly advanced features they have come to be used widely in computational mechanics. This paper describes an application of the modern computer algebra system Mathematica to the derivation of fundamental solutions necessary for the application of the boundary integral equation method. The problem treated is an asymmetric cross-section Timoshenko beam in free vibration. For this problem, the derivation of fundamental solutions involves lengthy mathematical operations which are very tedious if performed explicitly by hand. Therefore, using Mathematica we derive the fundamental solutions and generate the influence matrices from which the natural frequencies can be found. © 1998 John Wiley & Sons, Ltd.
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  • 166
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    Communications in Numerical Methods in Engineering 14 (1998), S. 751-761 
    ISSN: 1069-8299
    Keywords: acoustic ; electromagnetic ; integral equations ; scattering ; time domain ; radar cross-section ; Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: Analysis of high frequency scattering using pulsed illumination generates surface fields which are small over most of the scatterer most of the time. A reformulation of the usual integral equation time domain approach which exploits this is presented. It is shown that cost scaling can be reduced, with costs reduced by an order of magnitude for the examples presented, with negligible accuracy loss. © 1998 John Wiley & Sons, Ltd.
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  • 167
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    Communications in Numerical Methods in Engineering 14 (1998), S. 797-808 
    ISSN: 1069-8299
    Keywords: mesh equidistribution ; area preserving map ; singular BVP ; Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: In this paper, an adaptive mesh method is employed to solve a class of singular boundary value problems. The approach is based on an area-preserving map and some mesh shape control in two-dimensional space. Two benchmark problems, which both involve singularities in physical domains, are tested. © 1998 John Wiley & Sons, Ltd.
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  • 168
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    Communications in Numerical Methods in Engineering 14 (1998), S. 195-208 
    ISSN: 1069-8299
    Keywords: differential quadrature method ; elastic torsion ; numerical solution ; Poisson equation ; Laplace equation ; geometric mapping ; Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: The governing equation of an elastic prismatic shaft is the two-dimensional Poisson equation defined on the cross-sectional area of the shaft. In this paper, the differential quadrature method (DQM) is employed to solve the Poisson equation on some non-rectangular domains. Singularities, which may appear in the expression of stress components or boundary conditions at a degenerated point of the grid, are removed by means of the Taylor expansion. The results of three examples are compared with the exact solutions. It is shown that accurate results can be achieved by the DQM. In addition, three geometric transformations are conducted in the third example so that the effect of mapping on the convergence and accuracy of results is investigated. It is found that rapid convergence can be fulfilled if the degenerated point of the mesh falls on a Dirichlet boundary. The approach addressed in the paper can be extended to other potential problems governed by either the Poisson equation or the Laplace equation. © 1998 John Wiley & Sons, Ltd.
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  • 169
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    Communications in Numerical Methods in Engineering 14 (1998), S. 209-218 
    ISSN: 1069-8299
    Keywords: three-dimensional convection-diffusion equation ; fourth-order compact scheme ; iterative methods ; Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: We present an explicit fourth-order compact finite difference scheme for approximating the three-dimensional convection-diffusion equation with variable coefficients. This 19-point formula is defined on a uniform cubic grid. We compare the advantages and implementation costs of the new scheme with the standard 7-point scheme in the context of basic iterative methods. Numerical examples are used to verify the fourth-order convergence rate of the scheme and to show that the Gauss-Seidel iterative method converges for large values of the convection coefficients. Some algebraic properties of the coefficient matrices arising from different discretization schemes are compared. We also comment on the potential use of the fourth-order compact scheme with multilevel iterative methods. © 1998 John Wiley & Sons, Ltd.
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  • 170
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    Communications in Numerical Methods in Engineering 14 (1998), S. 241-251 
    ISSN: 1069-8299
    Keywords: finite elements ; pollutant ; saturated porous medium ; semi-implicit method ; velocity correction ; mass transfer ; Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: A practical problem of pollutant migration has been studied for different concentration differences and mass diffusivities using the finite element method. The results indicate that the pollutant takes years to travel 10 m into the water-saturated soil when the mass diffusivity and concentration differences are less. © 1998 John Wiley & Sons, Ltd.
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  • 171
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    Communications in Numerical Methods in Engineering 14 (1998), S. 277-285 
    ISSN: 1069-8299
    Keywords: numerical simulation ; steel ; quenching ; finite volume method ; Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: On the basis of the control volume method the algorithm and computer program for prediction of the hardness distribution in quenched steel specimens with complex geometries have been developed. The algorithm and computer program are designed to solve 2D situation problems such as the quenching of complex cylinders, cones, spheres, etc. The computer program consists of three parts: automatic computation of domain and grid generation, computation of cooling curve in grid-points, and computation of hardness in grid-points. The mathematical model has been tested experimentally. The test showed that the model describes the hardness distribution in a quenched steel specimen of a complex form, with quite satisfactory accuracy. © 1998 John Wiley & Sons, Ltd.
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  • 172
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    Communications in Numerical Methods in Engineering 14 (1998), S. 271-275 
    ISSN: 1069-8299
    Keywords: basis transformation ; interpolations ; finite elements ; thin plates ; Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: The 9 df thin plate element of Mohr and Mohr uses cubic interpolation to obtain values of w at the third points of the element sides, in turn interpolating from these and the vertex values within the element. Recently this element has been modified and successfully applied to ‘potential’ problems. Subsequently it was found that the interpolations of the element of Bazeley et al. (1965, 1968) gave identical results for potential problems. In the present paper it is shown that this is because the interpolations of the two elements are exactly equivalent. © 1998 John Wiley & Sons, Ltd.
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  • 173
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    Communications in Numerical Methods in Engineering 14 (1998), S. 313-319 
    ISSN: 1069-8299
    Keywords: fluid mechanics ; vortex dynamics ; viscous flow ; Navier-Stokes equation ; vortex methods ; splitting procedure ; Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: A numerical scheme has been obtained rigorously from the initial-boundary value problem for the Navier-Stokes (NS) equations in the context of the vortex method. The technique is based on a transformation of the NS equation into a parabolic equation which has an exact solution. The numerical scheme is derived by expanding the exact solution in Taylor series in powers of a small time interval. Numerical implementation is developed with use of vortex particles to represent the vortex flow domain. The method is used to solve practical engineering problems. The technique can also incorporate turbulence modelling. © 1998 John Wiley & Sons, Ltd.
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  • 174
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    Communications in Numerical Methods in Engineering 14 (1998), S. 347-354 
    ISSN: 1069-8299
    Keywords: thin wire loop antenna ; integro-differential equation ; frequency domain ; current distribution ; the weak formulation ; finite element technique ; Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: The circular loop antenna is analysed by using the electric field integro-differential equation in the frequency domain. The weak form of the integro-differential is derived and then the current distribution along the circular loop antenna is calculated by solving the resulting equation via the finite element technique. Accurate results are obtained using the linear shape and test functions. © 1998 John Wiley & Sons, Ltd.
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  • 175
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    Communications in Numerical Methods in Engineering 14 (1998), S. 355-365 
    ISSN: 1069-8299
    Keywords: transient dynamics ; interaction of the crack sides ; crack propagation ; time domain formulation ; boundary element method ; Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: For two-dimensional solids the multiregion concept and the time-domain approach in the boundary element method are employed to model cracks in transient dynamics. The propagation of cracks and the closing and opening of crack sides are simulated by disconnecting and connecting degrees of freedom of a stationary mesh, as was also demonstrated recently in statics by Beer. An iterative technique is developed to determine the changes of the extent of the area where there is connection, contact or no contact at the interface between dynamically loaded regions. © 1998 John Wiley & Sons, Ltd.
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  • 176
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    Communications in Numerical Methods in Engineering 14 (1998), S. 941-957 
    ISSN: 1069-8299
    Keywords: geometrical non-linear ; UL formulation ; drilling degrees of freedom ; generalized conforming ; arc-length method ; Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: An updated Lagrangian formulation of the generalized conforming flat shell element with drilling degrees of freedom is derived based on the incremental equation of virtual work of a three-dimensional (3D) continuum for a purely geometric non-linear analysis of the space structure. While solving the non-linear equations, the Euler-Newton method and modified Euler-Newton method are used in static analyses, and the modified arc-length method and Newton arc-length method for post-buckling problems. A number of numerical examples are given to demonstrate the effectiveness of the proposed approach and programs. © 1998 John Wiley & Sons, Ltd.
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  • 177
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    Communications in Numerical Methods in Engineering 14 (1998), S. 473-491 
    ISSN: 1069-8299
    Keywords: temporal acceleration ; viscoelastic ; recovery ; Taylor-Galerkin ; finite elements ; Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: This paper presents a finite element study based on a technique associated with time extrapolation to accelerate the convergence rate to the steady state for viscoelastic flows. The approach adopted is a local extrapolation method attributed to Neville. Temporal extrapolation is embedded within a time-marching Taylor-Galerkin/pressure-correction scheme as applied to the solution of model channel flow, 4:1 plane contraction flow and flow past a circular cylinder. In particular, consideration is given to obtaining steady-state solutions for an Oldroyd-B model. When extrapolation is performed for stress and velocity or pressure, then stress and velocity overshoot, which consequently leads to divergence. In contrast, a stable numerical scheme emerges when only the stress is extrapolated. © 1998 John Wiley & Sons, Ltd.
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  • 178
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    Communications in Numerical Methods in Engineering 14 (1998), S. 505-517 
    ISSN: 1069-8299
    Keywords: hypersingular integral equation ; continuous elements ; stress analysis ; Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: In this paper, a method for the evaluation of boundary stresses directly from the BEM solution of elastostatic problems using the static boundary integral equation is presented. The technique is valid for corners and edges as well as smooth points on the boundary, and involves defining a new interpolation function for continuous elements which incorporate certain continuity conditions arising from the hypersingular nature of the integrals involved. An integration technique based on the singularity subtraction method using series expansions is adopted for the hypersingular intergrals. Results are shown to be more accurate than those obtained with conventional techniques. © 1998 John Wiley & Sons, Ltd.
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  • 179
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    Communications in Numerical Methods in Engineering 14 (1998), S. 539-547 
    ISSN: 1069-8299
    Keywords: boundary-only element analysis ; thermal cracking ; crack trajectory ; singular elements ; traction formula ; Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: A boundary element procedure is developed concerning the prediction of the quasistatic crack growth in uniformly heated bimaterials. This procedure assumes the existence of an initial small crack in one of the two phases, and further cracking progress from this point due to thermal loading. The resulting mixed boundary value problem is solved by applying an incremental boundary-only method in conjunction with the multidomain technique. Fracture characterizing parameters are evaluated utilizing special crack tip singular elements and appropriate formulas. The crack path is predicted using the strain energy release rate criterion, and the mesh is updated at the end of each increment. The presented results are in good agreement with previously reported experimental results and those obtained by the finite element method. Various numerical studies were conducted and interpreted concerning crack-path dependence on individual material property mismatch. © 1998 John Wiley & Sons, Ltd.
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  • 180
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    Communications in Numerical Methods in Engineering 14 (1998), S. 559-567 
    ISSN: 1069-8299
    Keywords: gust ; buffet ; random ; vibration ; Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: A convenient and effective finite-element-based method for buffeting analysis of complex structures is presented. This method is very efficient for structures with the natural frequencies closely spaced because their corresponding modes and the cross-correlation terms between them should be included in the mode-superposition analysis. The imperfect correlation between gust excitations can also be dealt with conveniently. A numerical example is given which shows that by using this method the buffeting analysis of complex structures with thousands of degrees of freedom, dozens of imperfectly related excitations and a number of participating modes can be executed quite easily on an ordinary IBM/486 (or 586) personal computer. © 1998 John Wiley & Sons, Ltd.
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  • 181
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    Communications in Numerical Methods in Engineering 14 (1998), S. 519-527 
    ISSN: 1069-8299
    Keywords: shell element ; large strain ; sheet metal stamping ; Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: The paper presents a general method of large strain determination over the deformed surface of a sheet metal stamping. It is demonstrated that the conventional degenerated shell element with two normal rotation degrees of freedom is not suitable for large deformation, especially when large element rotation is present. This inaccuracy is primarily caused by the fact that the displacement field description used in the degenerated shell element is only a first-order approximation with respect to the two rotation degrees of freedom, and is therefore suitable only for small rotation angles. The new method presented in this paper replaces the two rotation DOFs with three new degrees of freedom to describe the rotation of the surface normal so that the element deformation can be accurately described with no limitation on the amount of deformation and rotation involved. The advantages of this new method are: (i) a linear and accurate expression of the displacement field in terms of nodal DOFs is obtained; (ii) the formulation is easily incorporated into any existing degenerated shell elements; (iii) the strain calculation is accurate for any amount of element rigid body rotation; (iv) if the method is used in surface grid analysis, the algorithm will not only provide correct surface strains, but also their variation through the thickness direction, i.e. the bending deformation. © 1998 John Wiley & Sons, Ltd.
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  • 182
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    Communications in Numerical Methods in Engineering 14 (1998), S. 597-608 
    ISSN: 1069-8299
    Keywords: inverse problems ; dual systems ; vibrating rod ; Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: The discretization of the differential equation governing the axial vibration of a rod with varying cross-section leads to a specially structured matrix pencil. This paper deals with the reconstruction of this pencil from its spectrum. An iterative algorithm for this problem and an analytic characterization of complementary solutions are given. The method is demonstrated on some examples. © 1998 John Wiley & Sons, Ltd.
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  • 183
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    Communications in Numerical Methods in Engineering 14 (1998), S. 621-632 
    ISSN: 1069-8299
    Keywords: segmentation ; finite elements ; adaptive ; image ; Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: The image segmentation problem in computer vision is considered. Given a two-dimensional domain D and a function defined on it (the original image), the problem is to obtain a ‘cartoon’ associated with this function, namely to find a set of inner boundaries which divide D into subdomains (objects) in an optimal way. The optimality criterion used here is given by the Mumford-Shah (MS) and Blake-Zisserman model, which leads to a strongly non-linear problem. Related problems appear in multiphase continuum mechanics. An iterative procedure based on an h-adaptive finite element method is proposed for the solution of this problem. The mesh adaptivity enables an efficient solution technique, with the use of basic coarse discretization and a few local regions of high resolution where needed. © 1998 John Wiley & Sons, Ltd.
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  • 184
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    Communications in Numerical Methods in Engineering 14 (1998), S. 633-645 
    ISSN: 1069-8299
    Keywords: error estimation ; boundary elements ; adaptive mesh ; Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: A posteriori error estimation for the boundary element method is developed. The nodal error is estimated from the difference of two solutions - one from the original BEM solution, and the other from interpolation of the original solution. Based on nodal errors, a matrix analysis is carried out to calculate the corresponding errors at source points. Two formulae for estimating global percentage errors are proposed in the paper. The first formula uses nodal errors directly to estimate element error, and the second uses an integral form to calculate element error to eliminate extremely high mesh concentration near areas with singular solutions. An h-version adaptive mesh refinement is implemented to study the accuracy of the proposed error estimation. Numerical examples show that the error estimator can correctly guide mesh refinement, and a final mesh can be obtained in a few iterations. © 1998 John Wiley & Sons, Ltd.
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  • 185
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    Communications in Numerical Methods in Engineering 14 (1998), S. 647-655 
    ISSN: 1069-8299
    Keywords: finite difference methods ; stability and convergence of numerical methods ; advection schemes ; Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: This paper discusses implementation strategies for second-order finite difference discretizations of advection. Purely explicit and implicit methods both have disadvantages, and we consider semi-implicit schemes in which the flux is split into a primary implicit part and a secondary explicit correction. One-dimensional scalar advection is used as a model problem to analyse the leading order error terms and the stability of the schemes. Some of the splittings turn out to be unconditionally stable, but accuracy or monotonicity may deteriorate for large time steps. © 1998 John Wiley & Sons, Ltd.
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  • 186
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    Communications in Numerical Methods in Engineering 14 (1998), S. 697-708 
    ISSN: 1069-8299
    Keywords: incompressible flow ; generalized streamline operator ; upwinding tensor ; Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: In the present work the backward-facing step problem is analysed in the framework of the finite element method. It is a very well-known benchmark problem for the numerical resolution of the incompressible Navier-Stokes equations. In particular, a generalized streamline operator technique (GSO) is used in the numerical approach to these equations. The results show very good agreement with those reported by other authors using different methodologies. © 1998 John Wiley & Sons, Ltd.
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  • 187
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    Communications in Numerical Methods in Engineering 14 (1998), S. 773-781 
    ISSN: 1069-8299
    Keywords: indirect address lists ; unstructured grids ; shared-memory parallel machines ; Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: A way has been found to form indirect addressing lists in parallel on shared-memory parallel machines. The maximum possible speed-up for typical tetrahedral grids is approximately 1:23. The algorithm requires an additional scratch array to shift from the serial ‘elements surrounding points’ to the parallel ‘elements surrounding processors surrounding points’ paradigm. The algorithm developed is general in nature, i.e. applicable to all indirect addressing lists. All numerical methods requiring the construction of indirect data structures, such as sparse matrix linear algebra procedures, field and particle solvers operating on unstructured grids, and network flow applications should see a benefit from this algorithm when running on shared-memory parallel machines. © 1998 John Wiley & Sons, Ltd.
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  • 188
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    Communications in Numerical Methods in Engineering 14 (1998), S. 783-792 
    ISSN: 1069-8299
    Keywords: substructure ; frontal technique ; heat transfer ; moisture transfer ; displacement ; Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: This paper presents a substructuring-frontal combined algorithm for the analysis of fully coupled heat, moisture and displacement problems in unsaturated soil. The method adopted for solving the assembled matrix equations has a significant bearing on the computer storage requirement and execution time. Numerical examples are given to validate the proposed model. © 1998 John Wiley & Sons, Ltd.
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  • 189
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    Chichester : Wiley-Blackwell
    Communications in Numerical Methods in Engineering 14 (1998), S. 809-819 
    ISSN: 1069-8299
    Keywords: finite element analysis ; diffusion problems ; minimum time step size ; Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: The solution of the equation system of the finite element method for diffusion problems is presented in the format of a sequence. The characteristics of the numerical results can thus be known through an analysis of this ‘theoretical expression’ of the solution. The characteristics of the sequence are analysed to yield expressions for the minimum time step size. © 1998 John Wiley & Sons, Ltd.
    Additional Material: 1 Ill.
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  • 190
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    Chichester : Wiley-Blackwell
    Communications in Numerical Methods in Engineering 14 (1998), S. 849-861 
    ISSN: 1069-8299
    Keywords: outgoing boundary condition ; Berkhoff ; discrete ; non-local ; surface waves ; scattering ; Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics , Technology
    Notes: A discrete non-local (DNL) boundary condition is used to solve the water waves propagation problem over variable depth. This condition is obtained by means of full solution of the discrete Helmholtz operator in a structured network. We consider a simulation of wave propagation around a circular island located on either a paraboloidal shoal or constant depth bathymetry. Such examples confirm the important improvement in accuracy for the DNL method over standard conditions in the near field. © 1998 John Wiley & Sons, Ltd.
    Additional Material: 8 Ill.
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  • 191
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    New York, NY [u.a.] : Wiley-Blackwell
    Numerical Linear Algebra with Applications 5 (1998), S. 147-164 
    ISSN: 1070-5325
    Keywords: eigenvalue problem ; Lanczos method ; power method ; Krylov information ; Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: We study Lanczos and polynomial algorithms with random start for estimating an eigenvector corresponding to the largest eigenvalue of an n × n large symmetric positive definite matrix. We analyze the two error criteria: the randomized error and the randomized residual error. For the randomized error, we prove that it is not possible to get distribution-free bounds, i.e., the bounds must depend on the distribution of eigenvalues of the matrix. We supply such bounds and show that they depend on the ratio of the two largest eigenvalues. For the randomized residual error, distribution-free bounds exist and are provided in the paper. We also provide asymptotic bounds, as well as bounds depending on the ratio of the two largest eigenvalues. The bounds for the Lanczos algorithm may be helpful in a practical implementation and termination of this algorithm. © 1998 John Wiley & Sons, Ltd.
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  • 192
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    New York, NY [u.a.] : Wiley-Blackwell
    Numerical Linear Algebra with Applications 5 (1998), S. 203-217 
    ISSN: 1070-5325
    Keywords: boundary value problem ; boundary element method ; preconditioning ; fast Fourier transform ; Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: The algebraic properties of the matrix arising for the three-dimensional Dirichlet problem for Lamé equations in a rotational domain by the boundary element method are considered. The use of the special basis leads to a matrix having a block structure with sparse blocks. The possible strategies for the efficient solution of the above problem are discussed. © 1998 John Wiley & Sons, Ltd.
    Additional Material: 1 Tab.
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  • 193
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    Numerical Linear Algebra with Applications 5 (1998), S. 299-311 
    ISSN: 1070-5325
    Keywords: iterative methods ; singular linear systems ; index of a matrix ; M-splittings ; multi-splittings ; Q-matrices ; Markov chains ; Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: Given a singular M-matrix of a linear system, convergent conditions under which iterative schemes based on M-multisplittings are studied. Two of those conditions, the index of the iteration matrix and its spectral radius are investigated and related to those of the M-matrix. Furthermore, a parallel multisplitting iteration scheme for solving singular linear systems is suggested which can be applied to practical problems such as Poisson and elasticity problems under certain boundary conditions, the Neumann problem, and in Markov chains. A discussion of that multisplitting scheme, based on Gauss-Seidel type splittings is given for computing the stationary distribution vector of Markov chains. In this case a computational viable algorithm can be constructed, since only the nonsingularity of one weighting matrix of the multisplitting is needed. © 1998 John Wiley & Sons, Ltd.
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  • 194
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    New York, NY [u.a.] : Wiley-Blackwell
    Numerical Linear Algebra with Applications 5 (1998), S. 275-297 
    ISSN: 1070-5325
    Keywords: GMRES method ; Krylov subspace methods ; non-symmetric linear systems ; homotopy curve tracking ; sparse matrix ; Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: GMRES(k) is widely used for solving non-symmetric linear systems. However, it is inadequate either when it converges only for k close to the problem size or when numerical error in the modified Gram-Schmidt process used in the GMRES orthogonalization phase dramatically affects the algorithm performance. An adaptive version of GMRES(k) which tunes the restart value k based on criteria estimating the GMRES convergence rate for the given problem is proposed here. This adaptive GMRES(k) procedure outperforms standard GMRES(k), several other GMRES-like methods, and QMR on actual large scale sparse structural mechanics postbuckling and analog circuit simulation problems. There are some applications, such as homotopy methods for high Reynolds number viscous flows, solid mechanics postbuckling analysis, and analog circuit simulation, where very high accuracy in the linear system solutions is essential. In this context, the modified Gram-Schmidt process in GMRES, can fail causing the entire GMRES iteration to fail. It is shown that the adaptive GMRES(k) with the orthogonalization performed by Householder transformations succeeds whenever GMRES(k) with the orthogonalization performed by the modified Gram-Schmidt process fails, and the extra cost of computing Householder transformations is justified for these applications. © 1998 John Wiley & Sons, Ltd.
    Additional Material: 8 Ill.
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  • 195
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    New York, NY [u.a.] : Wiley-Blackwell
    Numerical Linear Algebra with Applications 5 (1998), S. 347-362 
    ISSN: 1070-5325
    Keywords: almost incompressible elasticity ; finite elements ; semi-coarsening refinement ; algebraic multilevel ; Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: The constant γ in the strengthened Cauchy-Buniakowski-Schwarc (CBS) inequality plays a key role in the convergence analysis of the multilevel iterative methods. We consider in this paper the approximation of the two-dimensional elasticity problem by bilinear rectangle finite elements. Two semi-coarsening refinement procedures are studied. We prove for both cases new estimates of the constant γ, uniformly on the Poisson ratio.As a result of the presented analysis we obtain an optimal order algebraic multiLevel iteration (AMLI) method for the case of balanced semi-coarsening mesh refinement. The total computational complexity of the algorithm is proportional to the size of the discrete problem with a proportionality constant independent of the Poisson ratio, that is, the algorithm is of optimal order for almost incompressible elasticity problems. Copyright © 1999 John Wiley & Sons, Ltd.
    Additional Material: 3 Ill.
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  • 196
    ISSN: 0730-2312
    Keywords: somatostatin ; receptor isotypes ; adenylyl cyclase ; Interleukin-2 (IL-2) ; proliferation ; Jurkat cells ; Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: The neuropeptide somatostatin (SRIF) modulates normal and leukemia T cell proliferation. However, neither molecular isotypes of receptors nor mechanisms involved in these somatostatin actions have been elucidated as yet. Here we show by using RT-PCR approach that mitogen-activated leukemia T cells (Jurkat) express mRNA for a single somatostatin receptor, sst3. This mRNA is apparently translated into protein since specific somatostatin binding sites (KI1 = 78 ± 3 pM) were detected in semipurified plasma membrane preparations by using 125I-Tyr1-SRIF14 as a radioligand. Moreover, somatostatin inhibits adenylyl cyclase activity with similar efficiency (IC50 = 23 ± 4 pM) thus strongly suggesting a functional coupling of sst3 receptor to this transduction pathway. The involvement of sst3 receptor in immuno-modulatory actions of somatostatin was assessed by analysis of neuropeptide effects on IL-2 secretion and on proliferation of mitogen-activated Jurkat cells. Our data show that in the concentrations comprised between 10 pM and 10 nM, somatostatin potentiates IL-2 secretion. This effect is correlated with somatostatin-dependent increase of Jurkat cell proliferation since the EC50 concentrations for both actions were almost identical (EC50 = 22 ± 9 pM and EC50 = 12 ± 1 pM for IL-2 secretion and proliferation, respectively). Altogether, these data strongly suggest that in mitogen-activated Jurkat cells, somatostatin increases cell proliferation through the increase of IL-2 secretion via a functional sst3 receptor negatively coupled to the adenylyl cyclase pathway. J. Cell. Biochem. 68:62-73, 1998. © 1998 Wiley-Liss, Inc.
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  • 197
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    New York, N.Y. : Wiley-Blackwell
    Journal of Cellular Biochemistry 68 (1998), S. 74-82 
    ISSN: 0730-2312
    Keywords: cell culture ; nuclei ; nuclear degradation ; endonucleases ; polycytosine degradation ; differentiation ; cornification ; stratum corneum ; Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: Desquamin is a glycoprotein that we have isolated from the upper granular layer and the stratum corneum of human epidermis; it is not ordinarily expressed in submerged cultures, whose terminal differentiation stops short of formation of these layers. The exogenous addition of desquamin to human cultured keratinocytes extended their maturation, and hematoxylin staining indicated a loss of cell nuclei. For confirmation, cultured cells were lysed in situ, and the nuclei were incubated with desquamin for several days, then stained with hematoxylin. Damage to the nuclei was evident: the nuclear inclusions remained intact, while the surrounding basophilic nuclear matrix was degraded. Desquamin was then tested directly for nuclease activity. Ribonuclease activity was determined by incubating desquamin with human epidermal total RNA and monitoring the dose-dependent disappearance of the 28S and 18S ribosomal RNA bands in an agarose/formaldehyde gel. On RNA-containing zymogels, we confirmed the RNase activity to be specific to desquamin. Using synthetic RNA homopolymers, we found the active RNase domains to be limited to cytosine residues. On the contrary, DNA was not degraded by an analogous procedure, even after strand-separation by denaturation. J. Cell. Biochem. 68:74-82, 1998. © 1998 Wiley-Liss, Inc.
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  • 198
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    New York, N.Y. : Wiley-Blackwell
    Journal of Cellular Biochemistry 68 (1998), S. 100-109 
    ISSN: 0730-2312
    Keywords: carcinogens ; mitochondrial DNA ; nuclear DNA ; LINE ; mobile elements ; cancer ; Huntington's disease ; Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: The nuclear DNA of normal and tumor mouse and rat tissue was examined for mitochondrial-DNA-like inserts by means of the Southern blot technique. The two probes were 32P-labeled cloned mitochondrial DNA. KpnI, which doesn't cut either mitochondrial DNA, was one of the restriction enzymes, while the enzymes that fragment mitochondrial DNA were for mouse and rat PstI and BamHI, respectively. When KpnI alone was used in the procedure a nuclear LINE family whose elements had mitochondrial-DNA-like insertions was selected. Such elements were much more abundant in tumor than in normal tissue. The results with PstI alone and BamHI alone and each combined with KpnI indicated that there were mobile LINE elements with mitochondrial-DNA-like inserts in the nuclear genome of tumor. The mouse tissues were normal liver and a transplantable lymphoid leukemic ascites cell line L1210 that had been carried for 40 years. The rat tissues were normal liver and a hepatoma freshly induced by diethylnitrosoamine in order to minimize the role of 40 years of transplantation. Our unitary hypothesis for carcinogenesis of 1971, which suggested these experiments, has been augmented to include mobile nuclear elements with inserts of mitochondrial-DNA-like sequences. Such elements have been related to diseases of genetic predisposition such as breast cancer and Huntington's disease. J. Cell. Biochem. 68:100-109, 1998. © 1998 Wiley-Liss, Inc.
    Additional Material: 4 Ill.
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  • 199
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    New York, N.Y. : Wiley-Blackwell
    Journal of Cellular Biochemistry 68 (1998), S. 121-127 
    ISSN: 0730-2312
    Keywords: heme oxygenase ; stress protein ; overexpression ; oxidative injury ; endothelial cells ; Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: Heme oxygenase (HO-1) is a stress protein that has been suggested to participate in defense mechanisms against agents that induce oxidative injury such as hemoglobin/heme, hypoxia-ischemia and cytokines. Overexpression of HO-1 in endothelial cells (EC) might, therefore, protect against oxidative stress produced under these pathological conditions, by generation of CO, a vasodilator, and bilirubin, which has antioxidant properties that enhance blood vessel formation to counteract hypoxia-induced injury. A plasmid containing the cytomegalovirus promoter (pCMV) neomycin human HO-1 gene complexed to cationic liposomes, lipofectin, was used to transfect rabbit coronary microvessel EC. Cells transfected with human HO-1 gene demonstrated a twofold increase in HO activity and maintained a similar phenotype as in the nontransfected cells. Cell number in transfected cells with human HO-1 gene increased by about 45%, as compared to nontransfected or those transfected with control pCMV. Transfected and nontransfected EC revealed a similar response to basic fibroblast growth factor (bFGF) in capillary formation. However, transfected cells with the human HO-1 gene exhibited a twofold increase in blood vessel formation. The angiogenic response of EC to overexpression of HO-1 gene provides direct evidence that the inductive form of HO-1 following injury represents an important tissue adaptive mechanism for moderating the severity of cell damage produced in inflammatory reaction sites of hemorrhage, thrombosis and hypoxic-ischemia. Thus, HO-1 may participate in the regulation of EC activation, proliferation and angiogenesis. J. Cell. Biochem. 68:121-127, 1998. © 1998 Wiley-Liss, Inc.
    Additional Material: 3 Ill.
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  • 200
    ISSN: 0730-2312
    Keywords: tyrosine phosphorylation ; insulin signaling ; tyrosine kinase ; confocal microscopy ; Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: The recently identified 53-kDa substrate of the insulin receptor family was further characterized in several retroviral-generated stable cell lines overexpressing the wild type and various mutant forms of the protein. To facilitate the study of its subcellular localization in NIH3T3 cells overexpressing insulin receptor, a myc epitope-tag was added to the carboxy terminus of the 53-kDa protein. Like the endogenous protein in Chinese hamster ovary cells, the expressed myc-tagged 53-kDa protein was found partially in the particulate fraction and was tyrosine phosphorylated in insulin-stimulated cells. Immunofluorescence studies showed for the first time that a fraction of the 53-kDa protein was localized to the plasma membrane. Confocal microscopy of cells double-labeled with antibodies to the insulin receptor and the myc epitope showed the two proteins co-localize at the plasma membrane at the level of light microscopy. Further analyses of the protein sequence of the 53-kDa substrate revealed the presence of a putative SH3 domain and two proline-rich regions, putative binding sites for SH3 and WW domains. Disruption of these three motifs by the introduction of previously characterized point mutations did not affect the membrane localization of the 53-kDa protein, its ability to serve as substrate of the insulin receptor, or its colocalization with the insulin receptor, suggesting these domains are not important in the subcellular targeting of the protein and instead may function in the interaction with subsequent signaling proteins. J. Cell. Biochem. 68:139-150, 1998. © 1998 Wiley-Liss, Inc.
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