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  • Physics  (568)
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  • 11
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 2297-2307 
    ISSN: 0887-6266
    Keywords: crosslinked polymers ; photopolymerizations ; living radical polymerizations ; mechanical properties ; dynamic mechanical analysis ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Crosslinked polymer networks are used in a wide variety of applications. To use these materials effectively, a fundamental understanding of their structural evolution and the relationship between material properties and structure is essential. In this article, a novel technique employing “iniferters,” i.e., living radical polymerizations, to photopolymerize these networks is utilized to study the property and structural evolution of these highly desirable materials. Living radical polymerizations are used in this work since this technique avoids the problem of carbon radical trapping encountered while using conventional initiators. Dynamic mechanical measurements are performed on highly crosslinked methacrylate networks to glean information regarding their structural heterogeneity. By performing these measurements on homopolymerized samples at various stages of the reaction and on copolymerized samples of multifunctional methacrylates, the mechanical properties are characterized as a function of double bond conversion and comonomer composition. From such analyses, with respect to both temperature and frequency, quantitative conclusions regarding the structure of the networks are drawn. This effort is aimed at exploiting the living radical polymerizations initiated by p-xylylene bis(N,N-diethyl dithiocarbamate) (XDT), to study the mechanical property evolution and structural heterogeneity of crosslinked polymers which is nearly impossible otherwise. Polymers examined in this study include networks formed by homopolymerization of diethylene glycol dimethacrylate (DEGDMA) and polyethylene glycol 600 dimethacrylate (PEG600DMA) as well as copolymers of DEGDMA and PEG600DMA. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2297-2307, 1997
    Additional Material: 8 Ill.
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  • 12
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 771-776 
    ISSN: 0887-6266
    Keywords: Nafion ; positron annihilation ; free volume ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We report a new result on positron annihilation studies in acid- and cation-neutralized (Li+, Na+, K+, Rb+, Cs+, UO22+, Ni2+) Nafion membranes using positron lifetime and Doppler-broadened annihilation radiation (DBAR) measurements. The free-volume structure is characterized using a simple quantum mechanical model of positronium (Ps) in a spherical well. Our studies indicate that formation and expansion of clusters is always associated with a change in free-volume structure resulting in smaller free-volume holes. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 771-776, 1997
    Additional Material: 1 Ill.
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  • 13
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 749-761 
    ISSN: 0887-6266
    Keywords: polycarbonate ; polyglutanimide ; polymer blends ; copolymer ; compatibilization ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Imide units copolymerized with MMA units have been selected in order to improve compatibility between PC and acrylics through specific interaction or internal repulsion. Good dispersion of acrylic inside a PC matrix has been observed upon melt mixing, which can be partially explained by the good rheological agreement between these two polymers. Transmission electron microscopy has shown that the system remains phase separated from 5 to 95 wt % of PC. Phase diagrams for three different imide concentrations have been drawn. Results obtained by DSC (conventional and with enthalpy relaxation) are similar to those obtained by optical cloud point detection. The phase diagrams show the raise of the PC/PMMA demixtion curve (LCST type) when percentage of imide increases in the acrylic phase. Theoretical calculations on binary interaction energy density show a slight improvement of the interaction between acrylic and PC when imide percentage increases. Cloud point measurements on 50/50 PC/acrylic blends varying the imide concentration show that the improvement of compatibility deduced from the raise of the demixtion curve (LCST type) is more related to a kinetic effect (the high Tg of imidized samples is reducing macromolecule mobility) than specific interactions. The calculated favorable interactions are probably too weak to be detected with cloud point measurements. The microstructures obtained after crystallization of the PC phase under solvent vapors in phase separated PC/acrylics blends can also be explained by Tg effects. Moreover, solvent vapor exposure could be a powerful tool to determine the real thermodynamic behavior of the blends at room temperature. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 749-761, 1997
    Additional Material: 19 Ill.
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  • 14
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 777-788 
    ISSN: 0887-6266
    Keywords: PMDA-ODA polyimide ; intrinsic molecular properties ; sheet mapping ; fabrication processes ; three-dimensional orientation functions ; anisotropic coefficient of thermal expansion (CTE) ; anisotropic mechanical moduli ; anisotropic compliances ; anisotropic dielectric constants ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A practical methodology for the correlation and prediction of the process-property performance of advanced materials is developed. The model polymer studied is PMDA-ODA polyimide. The connecting link between the process and the properties is the structural state of the polymer. An essential ingredient for a quantitative characterization of the system is a knowledge of its phase state and intrinsic molecular properties. The intrinsic molecular properties define the limiting performance properties available to the polymer. Anisotropic films and sheets produced by five different fabrication processes are examined. Maps of the molecular symmetry axis, the orientation function, and the thickness distributions of two 50-in.-wide sheets fabricated differently are measured nondestructively for process comparison. Four other film fabrication processes are examined and their three-dimensional orientation states determined and correlated. A three-dimensional orientation function triangular plot permits simultaneous representation of the different fabrication processes on the same figure and allows the investigator to choose the most economic and efficient fabrication route. The structure-property study includes the structural correlation and intrinsic molecular property determination of the anisotropic coefficient of thermal expansion (CTE), the anisotropic mechanical moduli and compliances, and the anisotropic dielectric constants. 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 777-788, 1997
    Additional Material: 17 Ill.
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  • 15
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 831-839 
    ISSN: 0887-6266
    Keywords: polymer blends ; analog calorimetry ; heat of mixing ; mean-field binary interaction model ; polystyrene ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Analog calorimetry is used to study the interaction between styrene and acrylonitrile repeat units. Electrostatic charge calculations were used as a guide to divide the polymer repeat units and analogs into groups. A mean-field binary interaction model was used to evaluate group interaction energies. The enthalpic interaction energy for the styrene-acrylonitrile pair from this study is 7.63 ± 0.12 cal/cm3 which is consistent with values obtained from phase behavior studies of poly(styrene-co-acrylonitrile) blends. The cyano group, C(TRIPLE BOND)N, of the acrylonitrile repeat unit has a permanent dipole. The results of this study suggest that the orientation of this dipole with respect to the backbone of the acrylonitrile unit strongly affects its interaction with styrene repeat unit. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 831-839, 1997
    Additional Material: 11 Ill.
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  • 16
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 849-864 
    ISSN: 0887-6266
    Keywords: ABC block copolymers ; self-assembly ; microphases ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The random phase approximation has been used to extend the Leibler theory for the stability limit of a homogeneous melt of A-B diblock copolymers to examine the onset of microphase and macrophase separation in a variety of ABC block copolymer systems. The stability limit is located by the divergence of the collective structure factor of the melt. We introduce and analyze three models for ABC block copolymers: linear triblocks, random comb copolymers where a fixed number of A and B teeth are placed randomly along a C backbone, and statistical comb copolymers, with A or B teeth spaced regularly, but with sequences constructed using a two parameter Markov process. We compute order-disorder stability boundaries for the segregation strength parameter χABN at threshold as a function of χACN, χBCN, composition, and other model parameters, and compare the results for the three different architectural models. An interesting “reentrant order-disorder transition” is located in several model phase diagrams, and is associated with a peculiar situation in which more incompatibility causes less segregation. In the case of statistical combs, macrophase separation into two liquid phases can be favored over microphase separation. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 849-864, 1997
    Additional Material: 13 Ill.
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  • 17
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 1373-1381 
    ISSN: 0887-6266
    Keywords: PDLC ; LC droplet ; LC configuration ; electro-optical response ; conductance ; dielectric constant ; dielectric loss ; switching voltage ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polymer dispersed liquid crystal (PDLC) films (5CB/PMMA, 60/40) of different droplet size were prepared by a solvent-induced phase separation method under different N2 flow speeds. The effects of droplet size on the thermal transitions of the LC and various dielectric properties such as dielectric constant, conductance, dielectric loss, and the electric field induced in a droplet were examined. The configuration of the LC in the film with smaller droplets can be identified by comparing the dielectric constant of the film with the one predicted by Boettcher's mixture formula. In addition, the effect of droplet size on the electro-optical response of the PDLC film was investigated. Variations of the conductance and the dielectric constant of the film were analyzed under various AC frequencies, with the purpose of elucidating the polarization mechanism of the LC molecules in the droplet. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1373-1381, 1997
    Additional Material: 6 Ill.
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  • 18
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 1415-1421 
    ISSN: 0887-6266
    Keywords: epitaxy ; recrystallization ; high-density polyethylene ; isotactic polypropylene ; morphology ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The recrystallization behavior of high-density polyethylene (HDPE) on the highly oriented isotactic polypropylene (iPP) substrates at temperatures below the melting temperature of HDPE has been investigated by means of transmission electron microscopy. The results obtained by the bright-field observation and the electron diffraction show that upon annealing the HDPE-quenched films on the oriented iPP substrates at temperatures below 125°C, only a small amount of HDPE recrystallizes on the iPP substrate with [001]HDPE//[001]iPP, while annealing the HDPE-quenched films at temperatures above 125°C, all of the HDPE crystallites recrystallize epitaxially on the iPP substrate with [001]HDPE//[101]iPP. © 1997 John Wiley & Sons, Inc. J Polym Sci B: 35: 1415-1421, 1997
    Additional Material: 9 Ill.
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  • 19
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 1433-1438 
    ISSN: 0887-6266
    Keywords: polyelectrolyte gel ; reduced viscosity ; dipole-dipole attraction ; medium polarity ; copolymerization ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Copolymerization of 2-acrylamido-2-methylpropane sulfonic acid (AMPS, monomer 1) with 2-hydropropyl methacrylate (HPM, monomer 2) was conducted in ethylene glycol/water (1 : 1 in weight) at 70°C. The reactivity ratios estimated from the copolymer composition at low conversion are r1 = 2.31 ± 0.25 and r2 = 11.70 ± 1.05. The azeotropic composition was found at the monomer mole ratio AMPS/HPM equal to 8/2. Viscosity of these copolymers was measured in dimethyl sulfoxide (DMSO) and DMSO/tetrahydrofuran (THF) mixed solvent at 25 ± 0.05°C. Polyelectrolyte behavior was observed for all the copolymers, even in the mixed solvent containing 65 wt % of THF. The reduced viscosity at constant polymer concentration decreased with increasing THF content in the mixed solvent. The copolymers having AMPS repeat units more than 42 mol % precipitated in the mixed solvent when the THF was beyond 68 wt %. The viscosity reduction and precipitation in the copolymer solutions with increasing THF can be attributed to the dipole-dipole attraction between ion-pairs formed in less-polar medium. This is helpful in understanding the volume phase transition in highly charged hydrogels caused by mixing solvents. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1433-1438, 1997
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  • 20
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 1261-1267 
    ISSN: 0887-6266
    Keywords: FTIR-ATR spectroscopy ; gravimetric sorption ; diffusion ; polymer ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In this study, vapor sorption FTIR-ATR (Fourier Transform Infrared Attenuated Total Reflectance) spectroscopy was combined with a conventional gravimetric sorption balance to examine diffusion in polymers. Mutual diffusion coefficients of methyl ethyl ketone in polyisobutylene were measured using both methods at various penetrant activities and temperatures in the range 40-60°C. Actual penetrant concentrations were determined from the sorption balance. The diffusion coefficients from the two techniques agree very well with each other. In addition, the diffusivity data from both techniques could be correlated successfully as a function of temperature and concentration with the Vrentas and Duda free-volume model. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1261-1267, 1997
    Additional Material: 7 Ill.
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