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  • Physics  (1,092)
  • 1980-1984  (1,092)
  • 1984  (554)
  • 1983  (538)
  • 101
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2067-2083 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Reversible and irreversible spectral changes are observed on heating of solvent-cast films of poly(ethylene terephthalate) (PET) between 30 and 230°C. The irreversible changes are due to the gauche-trans isomerization of the ethylene glycol segments and the corresponding changes in the symmetry and resonance characteristics of the aromatic rings. On the other hand, there are thermally reversible spectral changes. These reversible effects are primarily observed for the modes of the aromatic ring and the trans ethylene glycol segment. These reversible spectral changes include intensity variations and frequency shifts and are found to be linearly dependent on the measurement temperature. These reversible changes arise from changes in intermolecular and intramolecular forces as the temperature changes.
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  • 102
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2097-2108 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The theoretical stress relaxation of polymer melts is derived from a new solution of the response of Doi's slip-link model in the plateau zone of the rubberlike part of the spectrum. The results of this treatment, based on the application of the statistical theory of elasticity to a virtual transient network of monodisperse entangled chains, are applied to the calculation of stress-strain relations for uniaxial extension performed at constant strain rate and to that of stress relaxation after such an elongation.
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  • 103
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2123-2134 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A unique retainer/transparent quartz die assembly was designed and fabricated to fit on a melt extruder. It permitted visualization of polymer flow behavior during melt spinning. Tracer particles were mixed with polymer chips prior to extrusion. A laser beam was directed through a lens system and used to illuminate the tracer particles in the melt only in a thin, vertical cross section of the transparent quartz die. Streak photography was used to determine the cross-sectional velocity distribution of the melt as it passed through the die.
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  • 104
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2135-2157 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effect of low-molecular-weight miscible additives on the sub-Tg (β) relaxation process in bisphenol-A polycarbonate (BPAPC) was studied using high-resolution carbon-13 solid-state NMR. The trend of the spin-lattice relaxation times T1 at 50 MHz suggests that strong intermolecular interactions occur upon mixing when BPAPC is physically stiffened by the antiplasticizing diluent, diphenylphthalate. The values of 13C T1 at 15 MHz in d-chloroform solutions for similar BPAPC-diluent mixtures suggest that diluent effects on the megahertz mobility of the polymer occur exclusively in the solid state. These results are explained using equilibrium thermodynamics, in the Ehrenfest sense, at the second-order glass transition temperature Tg. Theory predicts that the temperature dependence of the Flory-Huggins interaction parameter ∂χ/∂T changes abruptly as the polymer-diluent blends are cooled below Tg from the molten state. The difference between ∂χ/∂T in the liquid and glassy states is the major factor which determines the diluent concentration dependence of Tg. A method is developed to estimate the relative magnitudes of χ for polymerdiluent blends in the glassy state.
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  • 105
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2109-2121 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Stress measurements have been performed at constant-strain-rate stretching of narrow distribution polystyrenes with various molecular weights elongated up to 300% at about 30°C above the glass transition temperature. The experimental stress-strain curves are compared with those calculated on the basis of a new treatment of Doi's molecular model (Part I). Satisfactory agreement is obtained, leading to a rather precise estimate of the equilibration time. The latter has a theoretical dependence on the square of molecular weight.
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  • 106
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2201-2201 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 107
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2169-2180 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Wide-angle x-ray line broadening methods have been used to determine the crystallite size and degree of distortion for the crystalline hard domains in MDI/diol polyurethane elastomers. Crystallite widths have been determined from the integral breadths of the 00l reflections following correction for distortions of the second kind according to the method Hosemann for polymers prepared using ethylene glycol, propandiol, butandiol, and hexandiol as the chain extender. These data relate to the width of the crystallites along the chain axis and thus can be interpreted in terms of the morphology of the hard domains. The crystallite sizes increase and the distortions decrease with increasing elongation and annealing time, and the sizes tend toward asymptotic values which correspond approximately to the average lengths of the hard-segment chains. These results rule out any appreciable folding of the hard-segment chains and point to a model for the hard domains formed by lateral aggregation of extended hard segments.
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  • 108
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2159-2167 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A novel method of following polymerization kinetics in dilute solutions of ionic monomers is described. The method, based on conductimetry, is very well adapted to follow polymerization of ionic species in very dilute solutions, in micellar solutions, or at interfaces, i.e., in all systems in which the polymerization process involves a shift in ionic equilibria. The method is applied to matrix polymerization of p-styrene sulfonate-(2,2,2)4-ionene complex and yields results in full agreement with the standard spectroscopic method frequently used in such systems. The conversion curves obtained by conductimetry are satisfactorily explained by Manning's ion condensation model and are in agreement with a previously proposed mechanism, based on ion condensation theory, for matrix polymerization of ionized monomers on polyelectrolytes.
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  • 109
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2181-2200 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The diffuse phase boundary thicknesses of two segmented polyurethane block copolymers have been determined by small-angle x-ray scattering analyses of deviations from Porod's law. A self-consistency test of these measurements is performed by comparing results of experiments carried out under a variety of collimation geometries, and using a number of different analytical procedures. Self-consistent values of the diffuse phase boundary thickness are obtained for both of the materials examined. The discrepancies between these values and previous literature values are discussed and possible origins of these differences are presented.
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  • 110
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2205-2217 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Ba, Ca, Mg, and Zn short-length carboxylato-telechelic polybutadienes (M̄n = 4,600) exhibit thermorheological simplicity. A secondary relaxation characteristic of ionic aggregates obeys an Arrhenius type of activation, the energy of which is in inverse proportion to the ionic radius of the cation, whereas the mean size of the ionic aggregates is proportional to it. The glass transition of the carboxy-telechelic polybutadiene is quite independent of the degree of neutralization and of the subsequent phase separation by the metal cations. The increase in cation size favors the growth of the multiplets into layered structures. Two sets of relaxation times are reported for the smallest alkaline-earth cation (Be). They suggest the existence of small multiplets unable to grow except into clusters.
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  • 111
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2219-2242 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Streak-photographic and stress birefringence techniques were used to analyze the flow of poly(ethylene terephthalate) through potential chain-ordering die geometries. The streak photographs were used to determine velocity distributions and streamlines in various convergent dies. The different contours were seen to have a significant effect on the polymer streamlines and velocity distributions. The measured velocities were used to develop empirical equations, specific for each geometry, which relate velocity to position within the die and to throughput rate. Flow birefringence was used to determine the extent of molecular ordering. The optimum chain-ordering die geometry was determined to be one which included a rapid initial decrease in cross-sectional area. Birefringence was also used to monitor polymer flow instability. An unusual mechanism for instability was observed at intermediate throughput rates.
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  • 112
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2263-2274 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Fourier-transform infrared spectroscopy has been used for the detection of conformational changes induced by plasticization in atactic poly(vinyl chloride) (PVC). The amount of short trans syndiotactic sequences decrease upon plasticization. This change depends on the amount and kind of plasticizer. Difference spectra emphasize changes in the distribution of gauche defects in the chains as a function of temperature in plasticized PVC films.
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  • 113
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2243-2262 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Wide-angle x-ray diffraction studies are reported on polyacrylonitrile (PAN) (homopolymer powder and fiber samples) and its random copolymers with methyl methacrylate (MMA) and methacrylonitrile (MAN). A new method of determination of degree of order which involves resolution of the individual maxima in the diffraction pattern is described and compared with the methods used in the literature. Comparison of the results on untreated fibers with those on untreated homopolymer powder samples, and the effect of heat treatment, suggest the molecular rod conformation of the PAN molecules in the amorphous phase. Heat treatment or the orientation induces a parallel alignment of the molecular rods in the amorphous phase, similar to the cyrstalline structure of PAN. Copolymerization with both the comonomers MMA and MAN produces qualitatively similar effect on the structure of PAN, which depends on the comonomer content. Below a critical comonomer content c* (c* = 12 mol % for MMA and 25 mol % for MAN comonomer), the crystalline lattice remains that characteristic of PAN, whereas above the critical comonomer content some modification in the crystalline lattice is apparent.
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  • 114
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2287-2298 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The rheological properties of narrow-molecular-weight-distribution linear and star-branched polyisoprenes have been determined using both shearing and stretching deformations. At all strain rates studied the tensile stress measured under transient and steady-state conditions did not increase above the linear viscoelastic value. The absence of an enhanced tensile stress for the branched polymer is in contrast to what is observed for branched low-density polyethylene. An explanation for the difference is proposed. Additional remarks are made about the broad distribution of relaxation times observed for star-branched polyisoprenes and about the approach to steady state in constant-strain-rate and constant-stress tests.
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  • 115
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2275-2285 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(∊-caprolactone) and low-molecular-weight esters (methyl acetate and propyl propionate) were dissolved in binary solvent mixtures. The relative ability of the two solvents to associate with the ester group was then determined by examining the equilibrium between the two solvation states of the ester using infrared and nuclear magnetic resonance spectroscopies. The ability of the solvents to associate with the chosen esters was found to be in the sequence α-hydrogenated chlorocarbons 〉 β-hydrogenated chlorocarbon 〉 carbon tetrachloride ≈ aliphatic hydrocarbons. The association-state equilibrium was also shown to be concentration dependent and the polyester was shown to become involved in specific interactions to a lesser degree than the model esters. The relevance of these results to the nature of the specific interactions in polyester/halogenated polymer blends is discussed.
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  • 116
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2299-2309 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Proton spin-spin relaxation times have been measured as a function of temperature for ultradrawn polypropylene with draw ratios λ up to 24. The three relaxation times T2a (the longest), T2i (intermediate), and T2c (the shortest), observed for all the samples, have been ascribed to the relaxations of the amorphous, constrained amorphous, and crystalline components, respectively. T2i and T2a, which reflect the changes in structure and mobility in the noncrystalline regions, decrease with increasing λ; T2i becomes saturated at λ 〉 9, whereas T2a shows a substantial decrease up to λ = 24. The continued decrease in T2a indicates that the constraint on the amorphous segments keeps increasing up to the highest λ. The associated mass fractions Fa, Fi, and Fc also change with λ. At λ 〈 9, the increasc in Fi with increasing λ is accompanied by a decrease in Fa, with Fc remaining unchanged. At higher λ, however, Fa is almost constant, and stepwise rises in Fc at about λ = 12 and 24 are accompanied by corresponding drops in Fi. It seems that, in this high draw ratio range, some of the taut molecules are fully extended and are in sufficiently good lateral register to transform into crystalline bridges. This conjecture is supported by the similarity in the λ dependence of Fc and the mass-fraction crystallinity obtained from the heat of fusion.
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  • 117
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Concentration-dependence coefficients kDφ of the mutual diffusion coefficient of poly(2-vinyl pyridine) in tetrahydrofuran in the temperature range 15-55°C are compared with predictions of recent theories of macromolecular diffusion. In this temperature range a change in local conformation of the polymer occurs. The accompanying changes in chain solvation and coil hydrodynamics result in a sizable decrease in the hydrodynamic interaction parameter X defined by Akcasu. The formulation of theory appropriate for comparison with frame-indifferent experimental diffusivities is discussed. We find that current theories predict qualitatively, but not quantitatively, the change in temperature dependence of kDφ that occurs at the conformational transition. The discrepancies closely parallel those reported in recent independent comparisons of theoretical kDφ versus experimental data for flexible-coil molecules. No theory can adequately predict kDφ over a wide range of X.
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  • 118
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2319-2335 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The carbon-13 spin-lattice relaxation times T1 of the crystalline portion of a set of polyethylenes have been studied. Chain structure and crystallization conditions have been varied over the widest possible extremes so that large differences are developed in the level of crystallinity, the supermolecular structure, and the crystallite thickness. Concomitantly, the observed crystalline T1 values cover the extraordinarily wide range of about 40-4500 s. They bear a one-to-one relation with the crystallite thickness, which is found to be the key structural variable determining this property. A correlation with the temperature for the α-transition can be established, which implies a similar type of segmental motions for the two phenomena. Major changes in the interfacial structure can also have a drastic influence on the value for the crystalline T1. Analysis of the magnetization decay curve also allows for a quantitative determination of the degree of crystallinity, which is found to be in excellent agreement with the corresponding value found from Raman spectroscopy.
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  • 119
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2337-2347 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A model is presented for the adsorption of water by ions in a deformable matrix. Only two opposing “effects” are included. The first is the mechanical resistance of the matrix to deformation which is treated within the framework of linear elasticity extended to the case of large deformations. The other effect is of electrical origin which is shown to be much more important than the purely entropic osmotic pressure. In the model only one immobile ion located at the center of a spherical droplet of water is considered. It is shown that the result does not significantly depend upon the dielectric constant of water, provided it is much larger than that of the matrix. The thermodynamic relations reveal that in fact most of the properties of the system depend mostly on the dielectric and elastic coefficients of the matrix. This simplified model should be considered as a guide for the understanding of the behavior of such systems rather than as a precise description of real materials. Some quantitative comparisons are made with a few experimental results.
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  • 120
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2349-2363 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The crystal structure of oriented poly[di-(3,4-dimethylphenoxy) phosphazene] (PDMP) was determined by x-ray diffraction. Unit-cell parameters were found to be a = 15.85, b = 19.43, and c = 9.85 Å. The unit cell is metrically orthorhombic with monoclinic space group P21. There were 48 refinable diffraction spots in the observed reciprocal lattice region, of which 28 were observed and 20 were unobserved. A refined model yielded the following residuals: R(obs) = 0.162 and 0.138. It was shown that a two-chain unit cell with a [T3C]2 (trans, trans, trans, cis, trans, trans, trans, cis) backbone conformation was the correct structure. The dimethylphenoxy side groups were arranged in nearly parallel planes, slightly off-normal to the fiber c axis. The polymer chains are extremely tightly packed and contain close but reasonable steric contacts.
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  • 121
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2365-2378 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A series of kinetic measurements using FT-IR have been carried out in order to clarify the mechanism of the gauche-trans isomerization process and the time-temperature-transformation relationships in poly(ethylene terephthalate). Two-stage isomerization isotherms are distinguished on the logarithmic scale of annealing time: a primary transformation stage with an activation energy of 40 kcal/mol characterized by a sigmoidal curve, followed by a linear secondary process. The activation energies of the secondary transformation obey an equation of the Arrhenius type InaT = B(1/T - 1/Tm) where 160 〈 T 〈 260°C ≈ Tm and can be used to describe the effects of annealing time and temperature on the isomerization process of PET in the secondary transformation region. On the basis of these analyses, the morphology and microstructure of PET in these temperature regimes of the isomerization process are proposed.
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  • 122
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2379-2387 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Computer models of a series of liquid n-alkanes were generated, allowing for continuous variation of torsion angles and of atomic positions. Torsional and intramolecular and intermolecular non-bonded potentials were introduced. Calculated fractions of gauche bonds are slightly higher than those calculated from a rotational isomeric state model. Calculated radial distribution functions exhibit peaks in good agreement with experimental data. No directional correlation between chains is found, except at very short distances. Calculated end-to-end distances and radii of gyration indicate random coil conformations. These results are unaffected by extension of the range of interaction to the attractive region and by variations of temperature and density.
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  • 123
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2419-2424 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 124
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2389-2402 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Methyl acrylate polymer colloids can be hydrolyzed self-catalytically by bound strong acid surface groups derived from the polymerization initiator. The kinetics of hydrolysis were earlier shown to be apparently pseudo-zeroth-order for any given latex, and first order with respect to surface strong acid concentration. A surface reaction zone model was proposed to explain the kinetics. This model leads to the prediction that the polymer particles will possess a core-shell morphology after some hydrolysis has occurred. This study employs 13C NMR spectroscopy to investigate the particle morphology in the wet latex, a new application for this method. The temperature dependence of the 13C NMR integrated intensities at various levels of hydrolysis provides strong evidence that the particles do possess core-shell morphology, and that the shell is composed of PAA/PMA copolymer. This shell is swollen and plasticized by water, resulting in greatly enhanced segmental mobility of the polymer chains as evidenced by marked narrowing of the NMR lines. Thermal measurements alone cannot distinguish particle morphology because PMA appears to be somewhat compatible with its partially hydrolyzed analog at the temperatures of measurement.
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  • 125
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2425-2426 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 126
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The strength of interaction of infrared radiation with relatively thick polymer films was systematically studied by internal reflection spectroscopy. The so-called “effective thickness” was used as a measure of the strength of interaction. The experimental and theoretical effective thickness were compared, and it was found that the theoretically predicted effective thickness can be approached or achieved experimentally with film samples routinely encountered in the polymer industry when moderate attention is paid to surface preparation and clamping force on the film in the internal reflection sample holder. A series of curves for various types of film samples was developed and found to be useful in predicting the spectral contrast for KRS-5 and germanium internal reflection elements. These data were collected for infrared radiation polarized parallel and perpendicular to the plane of incidence and for unpolarized radiation. The data for unpolarized radiation was checked for the effects of the inherent polarization of the Fourier-Transform Infrared Spectrometer used by comparing it to the arithmetic mean of the data for parallel and perpendicular polarization. These data were in good agreement and this indicated that the inherent polarization of the instrument introduced only minor errors into the data collected with unpolarized radiation. The concept of the “sampling depth” was established where the sampling depth ds was defined as the depth normal to the surface sampled. The sampling depth was found to be on the order of three times the value of dp, the depth of penetration, at 45° for polypropylene and polystyrene on KRS-5 and was observed to exceed the effective thickness values at the same conditions. The value of the electric field amplitude was observed to fall to 5% of its value at the surface at ds.
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  • 127
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2427-2444 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A theory for the relaxation of large strains in polymer melts is outlined. It is based on the Doi-Edwards slip-link model and the new concept of tube relaxation. Self-consistency makes this concept necessary when polymer melts are concerned. The discrepancy with previous non-self-consistent theories is not negligible and should be easy to observe experimentally. Special attention is given to the overall size and to the mean orientation of a labeled N-chain in a step-strained melt of P-chains. Using semiquantitative arguments, we predict different regimes depending on the respective values of N and P, and propose approximate evolution equations for each case. These equations may be used to design and interpret a variety of fluorescence, infrared, or NMR polarization measurements, as well as small-angle neutron scattering experiments.
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  • 128
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2445-2451 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effect of the α-methyl group on the mobility of the main and side chains of methacrylateacrylate copolymers has been investigated. Poly(ethyl acrylate) shows a small secondary loss maximum (attributed to the rotation of —COOR side chains) at 145 K, while in the case of poly(n-butyl acrylate) this relaxation process is smeared out or possibly absent. On the contrary, poly(n-butyl methacrylate) and poly(2-hydroxyethyl methacrylate) exhibit secondary relaxations at about 278 and 301 K, respectively. From the dynamic mechanical response spectra of methacrylate-acrylate copolymers one can see that the removal of the α-methyl group causes a qualitative change in the molecular mechanism of the secondary relaxation, presumably as a consequence of the different participation of the main chains. The existing data, however, are insufficient to quantify these differences. The low-temperature relaxation attributed to internal motion within the side groups is not distinctly affected by the presence of α-methyl groups. If both components of the copolymer display the low-temperature relaxation (above 77 K), the loss maxima preserve their identity to a large extent. The effect of copolymer composition on the main (glass) transition temperature has been described by means of a one-parameter equation.
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2453-2463 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Difficulty in controlling and determining the structural parameters of polymer networks has hindered experimental studies on the glass transition in crosslinked polymers. A series of wellcharacterized networks of poly(propylene glycol) having narrow network chain-length distributions and average molecular weight between crosslinks Mc in the range of 425-3000 has been prepared. The glass transition temperatures Tg of these networks were found to vary linearly with Mc-1, consistent with several theoretical treatments. Both the physical crosslinking and the incorporation of crosslinking agent into the system (a “copolymer” effect) are shown to be responsible for increase in Tg upon crosslinking in this system.Varying the network chain-length distribution without changing Mc did not affect the Tg of the system. The chemical nature of the crosslinking agent, however, does affect the Tg of the network, particularly at high crosslink densities.
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  • 130
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2465-2471 
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    Keywords: Physics ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Changes in the light-scattering components (λ = 0.53 μm) induced by a strong picosecond optical field (λ = 1.06 μm) applied to macromolecular transfer ribonucleic acid (tRNA) solutions were studied. Two beams were polarized vertically, and the intensity of the vertical and horizontal components of the light (λ = 0.53 μm) scattered at an angle of 90° were measured. The electric field of the strong 30-ps laser pulse was 5.0 × 103 esu cgs. The experimentally determined changes allowed for calculation of the mean third-order optical polarizability c, and its anisotropy δc. The measurements were performed in three different solutions: salt free, with magnesium ions, and without magnesium ions. Changes in tRNA structure reflected in changes of nonlinear light scattering, third-order optical polarizability, and its anisotropy were observed.
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  • 131
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2473-2482 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A series of polymer networks were prepared by trifunctionally endlinking poly(diethylene glycol terephthalate). The elastomeric properties of these materials were studied at constant temperature using experiments that involve both the elastic force and birefringence. Whereas the stress-strain isotherms show an anomalous increase in the modulus at very high elongation ratios, a downturn appears in the birefringence-strain isotherms at the same extensibilities. These results suggest that the upturn that appears in the force should be attributed to maximum chain extensibility rather than to strain-induced crystallization. A variety of additional thermoelastic experiments were carried out on these networks, to elucidate the dependence of the glass transition temperature on strain. It was found that for the elongation ratios at which the networks exhibit Gaussian behavior, the free-volume effects on the glass transition temperature Tg (decreasing Tg with increasing free volume) offset the conformational effects (increasing Tg with decreasing entropy). However, the contrary occurs in the region where the stress increases anomalously with increasing strain.
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2483-2494 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Resonance Raman spectroscopy has been used to measure the frequencies of the vibrational modes of the polymer backbone of fully and partially polymerized crystals of an ethyl urethane diacetylene. The data have assisted in the assignment of crystallographic structures to the different modifications of the crystals. Effective interatomic force constants have been derived and used to estimate the Young's modulus. For fully polymerized crystals a value of approximately 76 GPa was found. The dependence of the frequencies on elastic tensile strain parallel to the polymer chain direction was determined. By comparing the strain dependence of frequencies of partially polymerized singlecrystal fibers with those expected for model composites, it was concluded that the polymer chains in thermally polymerized crystals are considerably longer than in those polymerized using γ rays.
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2511-2524 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A moment analysis of dipolar-decoupled 19F NMR spectra of deformed polytetrafluoroethylene leads to an expansion which approximates the crystallite orientation distribution function. The resulting distributions are then interpreted in terms of this polymer's known mechanical properties, and an attempt is made to model these functions.
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2495-2509 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Epitaxial crystallization of polyethylene, n-paraffins, aliphatic polyesters, and various polyamides has been achieved on benzoic acid crystal substrates, specifically on their (001) crystals faces, which are made up of the aromatic rings. The epitaxial relationship is very similar for all polymers investigated: it is characterized by a unique chain orientation (parallel to the b axis of the substrate) and a plane of contact which is either the b-c, plane of polyethylene, or crystallographically similar ones for polyesters, or the plane of the hydrogen-bonded sheet for polyamides. Since benzoic acid is structurally similar to its alkali-metal salts, it is inferred that the nucleating efficiency of the latter toward chemically different but structurally similar polymers may well rest on an epitaxial relationship. Finally, the highly oriented morphology made it possible, for some polyesters with a monoclinic cell, to determine the angle between the chain axis and the Z axis of the optical indicatrix, a quantity not measured so far in polymers.
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  • 135
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2525-2541 
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    Keywords: Physics ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Highly oriented poly(vinylidene fluoride) rods have been produced by drawing isotropic polymer through a conical die. A range of oriented products was obtained, depending on the drawing temperature and the deformation ratio achieved. At low draw temperatures the draw ratio and final modulus are comparatively low, but a high Form I crystal content is obtained. At high draw temperatures the Form I content varies greatly with draw ratio, reaching high values at large draw ratios, where the highest-modulus samples were obtained.
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2551-2559 
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    Keywords: Physics ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Physics
    Notes: The effects of magic-angle sample spinning (MAS), high-power decoupling, and resonance frequency on the 13C NMR linewidths of bulk polyisobutylene and bulk trans-polybutadiene are examined. The 13C linewidths increase with resonance frequency, are unaffected by high-power decoupling, and are reduced to different extents by MAS. The dominant contribution of the natural linewidth of the polyisobutylene lines is confirmed. The two carbons of trans-polybutadiene have approximately equal linewidths under all conditions, a result that eliminates residual chemical shift anisotropy as a major contributor to the linewidths. The large reduction of the trans-polybutadiene linewidths with MAS, coupled with the above result, suggests that microscopic variation of magnetic susceptibility is the major factor for this semicrystalline polymer. Cross-polarized 13C spectra of trans-polybutadiene were obtained with and without MAS. With MAS, resonances due to the crystalline and amorphous components were resolved. The principal components of the chemical shift tensor of the vinylene carbons were obtained from the spectrum without MAS.
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2543-2549 
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    Keywords: Physics ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Physics
    Notes: The extended Hückel method was employed to calculate electronic band structures in trans-poly(p-phenylene benzobisthiazole) (trans-PBT) in an attempt to elucidate the packing and electronic properties of these chains in the crystalline state. The unit-cell energies thus calculated indicate that the most stable arrangement for trans-PBT corresponds to the chains in planar configurations, at an interplanar spacing of 3.5 Å, and shifted axially by 3.0 Å relative to one another. These calculated results are in good agreement with experimental results obtained on the polymer and on relevant model compounds. No discernible dispersion of the energy bands perpendicular to the planes is observed, indicating that the neighboring chains are electronically noninteractive, as was found earlier for trans-polyacetylene and polyethylene. Similarly, the band gap of 1.69 eV in the axial direction for one of a pair of chains was nearly the same as that, 1.73 eV, calculated previously for an isolated trans-PBT chain. These values are in the range 1.4-1.9 eV reported for trans-polyacetylene, which has been extensively studied because of its promise as a semiconductor.
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    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 1-19 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A unique capillary die was designed which made possible the measurement of extrusion pressure at various locations along the capillary length. Entrance pressure drops, exit pressures, and other rheological characteristics were determined for the flow of poly(ethylene terephthalate) through this extrusion apparatus. The effect of die entrance angle, extrusion temperature, throughput rate and polymer molecular weight were considered. Two samples differing in molecular weight exhibited power-law behavior at shear rates below 1000s-1. The entrance pressure drops and exit pressures were observed to increase with increasing molecular weight; furthermore, at a specific temperature, both-increased with increasing shear rate. The values for entrance pressure drop obtained using Bagley analysis were consistently higher than those obtained from direct measurements.
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    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 21-32 
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    Topics: Chemistry and Pharmacology , Physics
    Notes: The determination of charge storage and charge decay processes in polyethylene electrets by means of TSD techniques alone seems to be limited by deficiencies in resolving power and reproducibility. Therefore, in the present work, we describe a new differential technique which cancels the effects of parasitic currents and improves the reproducibility of the measurements. The dependence of the shape of thermograms on experimental poling conditions has been studied. The comparison of discharge currents from the differential technique and from the usual one has also been found to be an interesting means of investigating the charge decay processes.
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    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 33-39 
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Polythiophene and substituted polythiophene can be electrochemically generated as very adhesive thin films or as thick powdery deposits. The homogeneity of the thin films is very high, but it decreases when the film thickness is increased. Scanning electron microscopy shows that the nature of the dopant strongly influences the film morphology. Transmission electron microscopy reveals mainly a fibrillar structure, with a fibril diameter of 200 Å in the undoped state, and 800 Å in the doped conducting state.
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    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 41-47 
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    Topics: Chemistry and Pharmacology , Physics
    Notes: X-ray studies on polymers with phenyl benzoate side groups separated from the main chain by spacer groups of various lengths have been performed. It was found that the dimensions of liquid-crystalline regions are 15-20 nm, and they contain four to six close-packed layers. Thermal changes in x-ray scattering are associated with the variation of sizes and concentration of liquid-crystalline regions determined by the mobility of the main chain.
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    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 49-55 
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Results of Krik, Bidstrup, Merrill, and Meyers on polydimethylsiloxane networks of high functionality φ yield values of the reduced force [f*] in the high-extension limit that are directly proportional to (vs/V) (1 - 2/φ) where vs/V is the number of effective chains in volume V. The contention that trapped entanglements contribute significantly to the modulus is refuted by adherence of the results to this proportionality down to the lowest degrees of interlinking. Features of the relationship of stress to strain that appear to be in conflict with current theory are attributable to crowding of chains about the junctions of high functionality and of large linear dimension in the networks investigated by these authors.
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    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 67-77 
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    Topics: Chemistry and Pharmacology , Physics
    Notes: The far-infrared spectra of poly(styrene sulfonic acid) (PSSA) ionomer films containing alkaline and alkaline earth ions have been studied, and strong, broad bands, whose frequencies are cation dependent, have been observed and assigned to cation motion. The force field elements for cations vibrating at sulfonate-containing sites have been obtained for different models of the cation-motion vibration. The effects of hydration, dehydration, and thermal annealing are discussed in light of ion clustering in these materials.
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    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 57-66 
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    Topics: Chemistry and Pharmacology , Physics
    Notes: The changes in the structure and morphology of a random copolymer containing 92 mol % glycolide units and 8 mol % lactide units as a function of in vitro hydrolysis have been studied. A number of techniques, such as wide-angle x-ray diffraction, small-angle x-ray scattering, density measurements, infrared spectroscopy, and viscometry were employed in this study. The results showed that the hydrolytic attack was initiated in the amorphous areas of the polymer. After 28 days in the in vitro medium most of the amorphous areas had been chemically converted to lower-molecular-weight species such as oligomers of poly(glycolide-co-lactide). These low-molecular-weight species become water solble and are removed rapidly after day 28. Thus the fiber takes on a Swiss cheese character as the amorphous matter is hydrolyzed and eventually dissolved. As hydrolysis proceeds further, the crystalline areas of the polymer are attacked and eventually removed from the fiber by solubilization. The resulting voids in the fiber are eventually filled by a “collapse” of the structure. The role of the amorphous areas of the polymer in controlling the tensile strength of the suture is discussed.
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    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 79-93 
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    Topics: Chemistry and Pharmacology , Physics
    Notes: It has been found that flow-induced coalescence occurs at a very rapid rate during the mixing of polymeric fluids. Furthermore, the rheological properties of the dispersed and continuous phases, as well as the nature of the flow field used in their blending, can greatly influence this coalescence. The significance of these findings is that in the development of a mixing scheme to obtain a desired morphology with minimum expenditure of time or energy, attention is usually focused only on the particle breakup aspects of the blending process. The competing coalescence can, however, be accelerated by the same conditions often employed to facilitate particle breakup (e.g., higher shear rates, reduced dispersed-phase viscosity).A better understanding of the mechanism for coalescence of viscoelastic fluids is clearly required. In this manner optimal blending of immiscible polymers can be achieved with respect to both the nature of the final material and the ease with which it is obtained.
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    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 95-99 
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Broad-line NMR measurements have been carried out on solid amylose, pullulan, and dextran in order to shed light upon the relations between different modes of linkage of glucose residues and physical properties. Rotation of the methylol group attached to the C5 atom around the C5—C6 linkage and the libration of glucose residues around the α-1,6 linkage are suggested as the origins of the observed decrease of the second moment with increasing temperature.
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    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 107-115 
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Fourier-transform infrared (FTIR) studies of polystyrene (PS)/poly(vinyl methyl ether) (PVME) blends are presented. Both compatible (one-phase) and phase-separated blends were studied. In the case of compatible PS/PVME blends, there is strong evidence for molecular interactions. The interaction spectrum was obtained by digital subtraction techniques. In contrast, no interaction is detected for the phase-separated blends. In view of these results, molecular interactions must play a role in the compatibility of the two polymers. The merits of factor analysis and least-squares fit methods, as pertaining to our data, are also discussed.
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    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 101-106 
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(ethylene terephthalate) (PET) (intrinsic viscosity 0.59) and cellulose (Whatman) are compatible in up to 7.5% (w/v) solutions in trifluoroacetic acid and in mixtures of trifluoroacetic acid and methylene chloride. Evaporation of the solutions yielded films that did not contain cellulose per se, but rather partial esters of cellulose and trifluoroacetic acid. Clear films were cast from these solutions with compositions of 100/0, 75/25, 50/50, 25/75, and 0/100 PET. cellulose (w/w). Infrared spectra and DSC measurements indicate specific polymer-polymer interaction although two Tg were observed. Hydrolysis of the trifluoroacetate films to blends of PET and regenerated cellulose was accomplished by suspending the films in water at the boil. Infrared spectra indicate no interaction between the two polymers, although the films of the 50/50 and 25/75 PET. cellulose compositions were clear. The 25/75 composition, from its Tg and melting-point behavior appears to be a dispersion of very small-particle PET in a cellulose matrix. The 75/25 composition became opalescent during the hydrolysis and may be a dispersion of large-particle cellulose in a PET matrix. The regenerated cellulose appears to be a mixture of cellulose II and IV polymorphs.
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    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 117-127 
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    Keywords: Physics ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Wide-line NMR has been used in an investigation of noncrystalline (amorphous) regions in oriented semicrystalline polymers. Nylon 6 was chosen as a model material. The tie-chain length distribution function, the fraction of tie chains in the total number of chains in the crystallite cross section, and the relative number of taut tie chains have been determined. The data on the tie-chain length distribution are used in discussing specific features of vitrification of the amorphous regions in oriented polymers and in prediction macroscopic mechanical properties.
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    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 129-131 
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    Topics: Chemistry and Pharmacology , Physics
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    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 133-138 
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    Topics: Chemistry and Pharmacology , Physics
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    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 139-142 
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    Topics: Chemistry and Pharmacology , Physics
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    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 143-161 
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    Topics: Chemistry and Pharmacology , Physics
    Notes: The crystallization of highly oriented homopolymer melts (or glasses) is modeled. It is shown that in such cases heat flow controls the kinetics and microstructure of the transforming material. The situation is modeled similarly to the growth of a thermal dendrite, with the inclusion of large and variable concentrations of defects in the fibrillar crystals. Expressions relating the undercooling, growth velocity, filament tip radius, and defect concentration to a normalized tensile force are derived. Example predictions for the case of isotactic polystyrene are given.
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    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 175-182 
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Phase diagrams of low-molecular-weight polyethylene (M = 1000, 2000, 6500, 16,000) and polyethylene (M ≈ 1,000) after fuming nitric acid treatment have been determined from 20 to 300°C up to pressures of about 10 kbar. The fractions with molecular weights 1000 and 2000 do not exhibit the hexagonal phase, but the others do. Effects of molecular weight and fuming nitric acid treatment on the phase diagrams are discussed in terms of the entropy of the melt.
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  • 155
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    Notes: Single-crystal x-ray diffraction analysis is performed on a model compound (bisurethane of diphenylmethane-4-monoisocyanate and butanediol-1,4) for the thermoplastic polyurethane (TPU) hard segment formed from diphenylmethane-4,4′-diisocyanate and butanediol-1,4. The resulting structure is compared to structure models of corresponding TPU hard segments, especially to the structure proposed by Blackwell and Ross. Our results confirm this structure model showing a planar zigzag of the (CH2)4 group and planar hydrogen bonding between the urethane groups of adjacent molecules. X-ray diffraction analyses of polymeric TPU hard segments and of TPU elastomers with noncrystallizing soft segments lead to a revision of the dimensions of the proposed lattice cell, resulting in a more plausible value of 1.3226g/cm3 for the crystal density.
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    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 183-189 
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Attention is called to an early observation of Case II diffusion kinetics during penetration of a liquid into a uniaxially prestretched polymer film along the axis of stretching. Application of a previously developed transverse differential swelling stress model to these experimental conditions is described. It is shown that the model can predict Case II diffusion kinetics in a physically meaningful manner and will also explain the transition of the kinetics of the above system into normal or hindered diffusion regimes as either the degree of stretching or its direction relative to that of penetration is changed.
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    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 191-209 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The temperature, strain-rate, and pressure dependences of the yield stress have been determined for two polyethylene homopolymers of differing molecular weights and for a polyethylene copolymer. Samples were prepared by slowly cooling from the melt, and also by quenching in order to assess the effects of morphology on the yield behavior. The data have been analyzed on the basis of two Eyring processes acting in parallel. Comparison of all data sets reveals the existence in general of three distinct activated processes each with its own temperature, strain-rate, and pressure dependences. The relative contribution of each process is dependent on the molecular weight, morphology, etc. Also discussed is the relation of these three yield processes to the well-known loss processes of linear viscoelasticity.
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  • 158
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    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 211-221 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effect of diluents and temperature on segmental motion in poly(vinyl acetate) was investigated by both NMR and ESR spectroscopy. Three classes of diluents were studied: chloroform, a thermodynamically good solvent; water, a poor solvent which slightly swells the polymer and lowers its glass transition temperature; and decane, a nonsolvent so poor it does not appear to swell the polymer nor lower the calorimetric glass transition temperature. At all temperatures investigated each type of diluent increased the segmental motion of the polymer over that of the bulk sample. Under the conditions studied, 13C and 2H NMR and nitroxide spin-label ESR data gave similar views of segmental motion of the polymer, indicating that in this amorphous polymer the segmental motion of the polymer may be safely inferred from spin-label data.
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  • 159
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    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 223-236 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(tetramethyl-p-silphenylene siloxane) crystal mats initially prepared from benzene/methanol (2:1 v/v), when annealed in small amounts of solvent undergo considerable thickening in the chain direction. When the crystals are annealed above their formation temperature, their physical properties change rapidly at first before reaching an asymptotic limit commensurate with annealing time and type of solvent. Changes in melting temperature, heat of fusion, small-angle x-ray spacing, and wide-angle x-ray scattering patterns have been monitored for three solvents of varying solvent power, ranging from very good to extremely poor. Upon solution annealing, the original crystals mats equilibrate to more stable dimensions compatible with their environment. The activation energy of crystal thickening in contact with a liquid is estimated to be about an order of magnitude lower than that deduced from dry annealing data. It appears that the crystal surface and the crystalline core of the crystals comprising the mats must participate in the measured severalfold increase in long period noted after annealing. The lower surface (or interfacial) energy of the liquid annealed mats compared to isothermally melt-crystallized polymer of similar molecular weight has a direct bearing on the polymer morphology and crystallinity.
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  • 160
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    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 237-243 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Previous interpretations of gas transport data in crosslinked networks have been hindered by an inability to accurately control and evaluate the network parameters. We have recently prepared a series of model networks by reacting poly(propylene glycol) with a triisocyanate crosslinking agent. The poly(propylene glycol)s had narrow molecular weight distributions and average molecular weights between 425 and 3000, so the resulting networks had uniform average molecular weights between crosslinks. Hydrogen and carbon monoxide permeabilities in membranes formed from these networks increase with decreasing crosslink density. These results indicate increased cooperative molecular motions in the networks with longer average chain lengths between crosslinks. Increasing the average molecular weight between crosslinks also reduces the discrimination between these two gases so that the separation factors decrease. For networks prepared from mixtures of poly(propylene glycol)s with different molecular weights the gas permeabilities (but not the separation factors) depend on the molecular weight distribution.
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  • 161
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    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 245-254 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effects of poling temperature on piezoelectricity and its thermal stability were investigated on the basis of the thermal molecular motion associated with the crystalline region. This was done by using a film of highly oriented poly(vinylidene fluoride) containing form-I crystals. The film was prepared by a zone-drawing apparatus of the forced-quenching type. The piezoelectric stress constant e31 is a monotonically increasing function of the poling temperature which becomes steeper above ca. 320 K and again at ca. 400 K. The degree of orientation of the crystal b axis generated by poling also increases more steeply with poling temperature above ca. 320 K and again at 400 K. These temperatures correspond, respectively, to the crystalline dispersion temperature at 11 Hz, designated as αc, and the initiation temperature Tpm of large-scale molecular motion corresponding to premelting of form-I crystals. Thus the effect of poling temperature on piezoelectricity closely reflects the moleculer motion in form-I crystals. The annealing temperature T'a at which e31 decreases to 70% of that of unannealed sample by annealing a poled sample increases with the poling temperature and again this increase is steeper above poling temperatures of ca. 320 K and ca. 400 K. Thus the decay of piezoelectricity depends on both the αc temperature and Tpm.
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  • 162
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    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 279-284 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The probability W(t) that a given number t of segments of an infinite chain lie within a given sphere can be expressed in terms of the single-pass length probability and the probability of reentrance into the sphere. The problem of calculating these two probabilities is equivalent to that of a diffusing particle exiting or entering the sphere after a given time, when the surface of the sphere is an absorbing wall. It is shown that the boundary condition, c = 0, usually applied to an absorbing surface cannot be used for the present purpose. The boundary condition used instead is the so-called radiation condition ∂c/∂z = kc; it is shown that when k approaches infinity the final answer for W(t), which is given in the form of an infinite series, approaches the correct limit. In this same limit the ratio 〈t〉2/〈t〉2 has the value 2.4
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  • 163
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    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 255-263 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A new chlorination mechanism has been suggested for polyethylene crystals. Based on electron microsocopy and infrared spectroscopy of chlorinated high-density polyethylene single crystals, it is proposed that beyond the initial chlorination of the lamellae surfaces, which accounts for only 2-3% chlorine uptake, the reaction proceeds through the lamellar side faces from the periphery inward. Thus at intermediate degrees of chlorination two major phases coexist: the undamaged interior regions of the lamellae and the surrounding chlorinated material. This mechanism differs from that of oxidative degradation, and also from the generally Accepted mechanism of chlorination. Rather than proceeding through the reacted fold surface into the crystalline core, it is proposed that the direction of chemical attack is prependicular to that suggested previously. This mechanism probably describes any chemically nondestructive attack on the crystalline regions of polymers in general.
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  • 164
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    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 285-294 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The ion etching technique has been applied to a morphological study of mechanically blended polypropylene (PP) with high-density polyethylene (HDPE). Samples blended to PP/HDPE compositions of 65/35 and 85/15 by weight were highly drawn and then heat treated for 30 min at selected temperatures up to 163°C. When these samples are carefully ion-etched several features are observed in electron micrographs, namely (i) crosshatched, and (ii) twisted or layered textured inclusions of HDPE crystals within arrays of lamellalike PP crystals situated perpendicular to the direction of drawing. X-ray diffraction measurements of the drawn samples heat treated in the range 145-163°C for 30 min shows that oriented HDPE crystallizes with b-axis orientation along the drawing direction. Supporting evidence is obtained from electron diffraction measurements. The molecular weight of the HDPE component is a major factor in the b-axis-oriented growth of HDPE crystals in PP/HDPE blends.
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  • 165
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    Notes: The mechanical and optical behavior in the dry and swollen states of loosely crosslinked epoxy networks prepared from the diglycidyl ether of bisphenol A, phenylglycidyl ether, and 4,4′-diaminodiphenylmethane was investigated, and the weight fraction of sol in the networks was determined. The crosslinking density was controlled by an excess of diamine and by the fraction of monoepoxide. The reaction proceeded to almost full conversion of epoxy groups. With increasing content of monoepoxide or with increasing excess of diamine, the main transition region is shifted to lower temperatures. The dependence of the viscoelastic modulus on temperature and the optical behavior indicate that the networks are homogeneous. In all cases, the sol fraction is adequately described by the theory of branching processes (cf. Part I). The equilibrium modulus related to the dry state is the same irrespective of whether it is obtained by measurements in the dry or swollen state. The mechanical behavior in the rubbery state can be described by the theory of phantom networks with fully suppressed fluctuations of crosslinking (front factor A = 1) or by the theory of phantom networks with fully released fluctuations of crosslinks (front factor) A = fe-2/fe] and contribution of trapped entanglements of the Langley-Graessley type (cf. Part I). In the analysis of the equilibrium behavior, it is advantegeous to use the plot of superimposed dependences of Ge on the gel fraction, which considerably reduces the effect of experimental inaccuracy in determination of composition and degree of conversion.
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  • 166
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    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 307-310 
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    Keywords: Physics ; Polymer and Materials Science
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  • 167
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    Notes: A simulation has been made of the dielectric relaxation behavior of poly(n-hexylisocyanate) in solution covering the isotropic, biphasic, and anisotropic ranges. The simulation incorporates the Flory-Abe statistical mechanical theory for the phase behavior of rodlike macromolecules in solution and the Warchol, Vaughan, Wang, and Pecora theory for the dynamics of a rodlike molecule in a virtual cone prescribed by the neighboring molecules. It is shown that asymmetric Gaussian, Gaussian, or Poisson distributions of molecular weight do not lead to dielectric behavior of the type observed experimentally by Moscicki, Williams, and Aharoni but addition of a high-molecular-weight “tail” to such distributions and taking account of the dependence of relaxation time on molecular length gives a simulation of the dielectric increment Δε, the loss maximum ε″m, and frequency of maximum loss fm, which vary with polymer concentration in a manner entirely consistent with the experimental data.
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  • 168
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 605-611 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Photon correlation spectroscopy is employed to study the slowly relaxing density and anisotropy fluctuations in bulk atactic polystyrene as a function of temperature from 100 to 160°C and pressure from 1 to 1330 bar. The light-scattering relaxation function is well described by the empirical function φ(t) = exp[-(t/τ)β], where for polystyrene β = 0.34. The average relaxation time is determined at each temperature and pressure according to 〈τ〉 = (τ/β)Γ(1/β) where Γ(x) is the gamma function. The data can be described by the empirical relation 〈τ〉 = 〈τ〉0 exp[(A + BP)/R(T - T0)] where R is the gas constant and T0 is the ideal glass transition temperature. The empirical constant A/R is in good agreement with that determined from the viscosity or the dielectric relaxation data (1934 K). The empirical constant B can be interpreted as the activation volume for the fundamental unit involved in the relaxation and is found to be comparable to one styrene subunit (100 mL/mol). The quantity B appears to be a weak function of temperature. The use of pressure as a tool in the study of light scattering near the glass transition now has been established.
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  • 169
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 625-645 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The most striking feature of the mechanism of thermal annealing of doubly oriented samples of low-density polyethylene (LDPE) and probably of high-density polyethylene (HDPE) is a progressive tilt of lamellar crystals around their crystallographic b axis. Such a rotation does not occur on thermal annealing in doubly oriented nylons. However, this rotation mechanism occurs during the thermal annealing of doubly oriented samples of nylon 11 in contact with a solvent below its dissolution temperature. As for oriented samples of polyethylene (PE), a correlation between the changes of macroscopic dimensions and long spacing obtained from the small-angle x-ray pattern is difficult to establish. In doubly oriented samples of nylon 11, the basal faces of the lamellar crystals are parallel to the a axis of the unit cell. Nevertheless, simple Miller indices cannot be assigned to the basal planes of the lamellae. On thermal annealing in formic acid, the basal planes of the lamellar crystals are, in some cases, parallel to (00l) planes. Annealing in formic acid at room temperature induces a phase transition: the chain c axis remains oriented along the rolling direction and the (00l) planes become parallel to the limiting planes of the lamellar crystals. Bulk doubly oriented samples of nylon 11 annealed in formic acid just below the “dissolution temperature” have the same texture of orientation as filter mats of single crystals grown from dilute solution; moreover, as these bulk specimens remain doubly oriented, they can be used for further physicochemical investigations. The usual interpretation of the small-angle x-ray pattern is also discussed on the basis of the results reported in this paper.
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  • 170
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 647-655 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The optical absorption spectrum of poly(methyl methacrylate) (PMMA) has been obtained in the wavelength range 570-780 nm via laser calorimetry (employing a dye laser source). Because of the low thermal conductivity of PMMA, the complete solution to the heat conduction equation (carried out numerically) was required in the analysis of the data. At the wavelength of minimum absorption (near 647 nm), the absorption coefficient had the value 153 dB/km.
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  • 171
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 657-665 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The thermal expansivities along (α∥) and perpendicular (α⊥) to the draw direction of poly(methyl methacrylate) (PMMA) with extrusion draw ratios 1 ≤ λ ≤ 4 have been measured between 150 and 298 K. As λ was increased from 1 to 4, α∥ decreased 2-3 times, whereas α⊥ increased only 20-35%. The orientation function f calculated from thermal expansivity using the aggregate model is found to change linearly with birefringence, indicating that each property provides a sensitive measure of molecular orientation. For PMMA, however, only thermal expansivity can give an absolute f, with results at 150 K in reasonable agreement with previous studies using other techniques. At higher temperature, i.e., above ambient, PMMA side-group motions are excited, expanding volume, and calculations based on the aggregate model may not be valid.
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  • 172
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1251-1253 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1255-1274 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A group of rodlike polymers soluble only in strong protic acids was studied using light scattering and viscosity techniques. These include poly(1,4-phenylene benzobisoxazole), poly(1,4-phenylene benzobisthiazole) and poly(1,4-phenylene terephthalamide). The solution properties were dependent on the ionic strength of the acid used as solvent. In a low ionic strength acid such as chlorosulfonic acid, the polymer solutions exhibited decreased unpolarized scattering, an extremely small translational diffusion coefficient, and high viscosity. All of these effects could be eliminated by the addition of a salt such as lithium chlorosulfonate, which increased the ionic strength of the solvent. The effects were attributed to a pseudo ordering of the polymer solvent system caused by electrostatic repulsions between protonated polymer chains effective over large distances (ca. 100 Å) in the low ionic strength solvent. This type of ordering is distinct from actual anisotropic phase formation, which occurs at higher concentrations in these systems. Analysis of data at infinite dilution gave a persistence length of at least 45 nm for poly(1,4-phenylene terephthalamide), larger than previous experimental results, but in accord with recent rotational isomeric state calculations and similar to experimental data for poly(p-benzamide).
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  • 174
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1313-1322 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: As in the two-dimensional case, the density change due to crystallization leads to a buildup of internal strain in some regions of a polymer melt occluded by growing spherulites. The occluded parts of the sample are called “weak spots.” Computer simulation of spherulite growth in bulk samples shows that the largest weak spots have the size of an average spherulite. The total volumes of weak spots are 0.47, 0.094, and 0.119% of the sample for athermal, thermal, and mixed primary nucleation, respectively. The weak spots in the bulk material exhibit distance correlation. Within weak spots, internal strain is released (Raman spectroscopy), and holes develop. Polypropylene bulk spherulite samples contain holes distinctly visible under a microscope with infrared optics and illumination. The number of visible holes is in agreement with the computer prediction. The increase of impact strength with decreasing spherulite size is explained in terms of changes in the number and size of weak spots.
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  • 175
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1341-1346 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The longitudinal acoustic elastic modulus of polyethylene has been calculated with the aid of the ab initio crystal orbital method applying corrections also for electronic correlation effects. The basis set and correlation dependence of the elastic modulus have been investigated. The best theoretical value of 305 GPa of this modulus is in reasonable agreement with the published experimental values. At an elongation of ca. 0.1 the deviation from Hooke's law is found to be substantial.
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1381-1388 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A three-component system containing a polymer (2), a good solvent (1) for that polymer, and a second polymer (3) that is compatible with component (2) and isorefractive with the solvent (1) has been studied by static and dynamic light-scattering methods. In concentrated toluene (1) solutions of poly(vinyl methyl ether) (3), where appreciable chain overlap occurs and excluded-volume effects are reduced, polystyrene (2) may be studied in the dilute-solution limit. Consequently, these light-scattering measurements provide an explicit measure of both thermodynamic and hydrodynamic changes that occur as the total polymer concentration is increased from dilute to concentrated solution. Precise numerical coefficients, correct scaling exponents, the radius of gyration, and the effective hydrodynamic radius can be measured directly along with the observation of long-wave single-chain reptation motions and short-range cooperative motions in semidilute and concentrated solutions.
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  • 177
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    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1427-1438 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The linear thermal expansivity of poly(ethylene terephthalate) extruded at 50 and 90°C to extrusion ratios λ of 1-4.8 has been measured between 120 and 300 K. With increasing λ, the expansivity along the extrusion direction (α∥) decreases sharply, while that in the transverse direction (α⊥) shows a slight increase. For λ 〈 3, the large drop in α∥ and the accompanying increase in the axial Young's modulus E∥ can be ascribed to chain alignment in the crystalline regions and to an increase in number and tautness of intercrystalline tie chains. At higher λ, however, the crystalline orientation apparently becomes saturated, so that taut tie molecules are solely responsible for further changes in both α∥ and E∥. On the other hand, α⊥ is mainly determined by crystalline orientation for all λ, thus showing very little increase at large λ. For the highly oriented samples (λ ≥ 3), the Takayanagi model provides a reasonable description of the behavior of α∥ and α⊥.
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  • 178
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    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 317-344 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An experimental study has been made to specify how the time-temperature superposition and the linear viscoelastic characteristics vary with the degree of crosslinking for a broad class of noncrystalline peroxide-cured EPDM networks. A new, very sensitive method is applied to determine the horizontal and vertical shift functions in an independent way. All uncrosslinked samples are thermoelasticoviscously simple with horizontal shift functions aT of the WLF type and vertical shift functions almost independent of temperature, in agreement with recent theoretical understanding. Upon crosslinking, these materials become thermoviscoelastically complex networks, but superposition can still be accomplished by assuming different temperature dependences for the relaxational strength and the equilibrium modulus. The aT functions can be taken independent of the degree of crosslinking. The vertical shift functions bT for the relaxational strength vary with the degree of crosslinking between theoretical predictions for uncrosslinked and perfectly crosslinked EPDM networks. The equilibrium moduli of the lightly cured networks decreases with increasing temperature, which is ascribed to the presence of interchain associations between ethylene sequences in the trans state. Upon further crosslinking, these effects gradually vanish and eventually the networks can be described as viscoelastically simple with an energy elastic contribution due to the ethylene trans-gauche transitions. The linear viscoelastic characteristics, namely the storage and loss moduli and compliances and phase-angle master curves and the relaxation and retardation spectra are discussed as a function of the degree of crosslinking. A sol/gel analysis and equilibrium swelling measurements complete the experimental characterization of three familes of five EPDM networks each.
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    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 379-405 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polytetrafluoroethylenes of different crystallinity were analyzed between 220 and 700 K by differential scanning calorimetry. A new computer coupling of the standard DSC is described. The measured heat capacity data were combined with all literature data into a recommended set of thermodynamic properties for the crystalline polymer and a preliminary set for the amorphous polymer (heat capacity, enthalpy, entropy, and Gibbs energy; range 0-700 K). The crystal heat capacities have been linked to the vibrational spectrum with a θ3 of 54 K, and θ1 of 250 K, and a full set of group vibrations. Cv to Cp conversion was possible with a Nernst-Lindemann constant of A = 1.6 × 10-3 mol K/J. The glass transition was identified as a broad transition between 160 and 240 K with a ΔCp of 9.4 J/K mol. The room-temperature transitions at 292 and 303 K have a combined heat of transition of 850 J/mol and an entropy of transition of 2.90 J/K mol. The equilibrium melting temperature is 605 K with transition enthalpy and entropy of 4.10 kj/mol and 6.78 J/K mol, respectively. The high-temperature crystal from is shown to be a condis crystal (conformationally disordered), and for the samples discussed, the crystallinity model holds.
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    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 681-698 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Quantitative Fourier-transform infrared (FTIR) measurements of frequency shifts Δν and absorbance profile asymmetry are reported for various polypropylene samples as a function of uniaxial stress σ. Generally, it was found that the frequency shift coefficient αχ, defined by Δν = αχσ, depended on stress rate \documentclass{article}\pagestyle{empty}\begin{document}$\dot \sigma$\end{document}, draw ratio, λ, molecular orientation f, tensile modulus E, and annealing conditions. With annealing, αχ decreased with increasing shrinkage in the case of highly oriented isotactic PP. The αχ values for the “helix bands” were less affected than those for the “liquid bands.” With increasing \documentclass{article}\pagestyle{empty}\begin{document}$\dot \sigma$\end{document}, generally αχ increased to an apparent asymptotic limit. With increasing λ, f, or E, αχ also increased from αχ ≃ 0 for λ = 1 (spherulitic) to maximum values for highly oriented isotactic PP. The observed variations in αχ can be interpreted in terms of the changes in the peak position and shape of the nonuniform molecular stress distribution. Analogous behavior with x-ray diffraction peaks obtained for polymers under stress is discussed.
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    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 707-719 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The sorption and diffusion of toluene vapor at 30°C in polypropylene with draw ratios from 1 to 18 have been studied. Drawing leads to the transformation of the initially spherulitic material into the fibrous structure, with many taut tie molecules lying mainly on the outer boundary of the microfibrils. The free volume and hence the sorption sites are thereby reduced, and the microfibrils become less and permeable as the draw ratio increases. As a result, the equilibrium concentration and the zero-concentration diffusion coefficient drop by factors of 4 and 30, respectively. The diffusion coefficient increases exponentially with toluene concentration but the concentration dependence becomes weaker with increasing draw ratio, indicating that the severely constrained chain segments in the drawn samples have much less freedom to mix with penetrant molecules. Annealing relaxes the tie molecules and thus restores the sorption and diffusion properties to values corresponding to completely relaxed amorphous component, i.e., to values even higher than those of the undrawn but quenched material.
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  • 182
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    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 773-775 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 183
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    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 759-772 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: X-ray analyses of methylene-bis(4)phenyl isocynate(MDI)/diol/poly(tetramethylene adipate) polyurethane elastomers prepared using hexanediol (HDO), butanediol (BDO), and propanediol (PDO) point to the development of a second crystalline structure in the hard segments as a result of thermal elongation and annealing. The HDO polymer crystallizes initially in the fully extended conformation, but a second crystal structure, a contracted form, develops with stretching and annealing at 130°C. In contrast, the BDO and PDO polymers crystallize initially in contracted conformation, but fully extended forms develop as a result of elongation and annealing. Only a contracted conformation has been seen so far in hard segments prepared using ethylene glycol (EDO) as the chain extender. These results correlate very well with DSC data for the same polymers. The development of the new crystal structures is accompanied by the appearance of new hard-segment melting peaks in the DSC traces. For the HDO polymer, the new peak for the contracted form appears at a higher temperature than that for the original extended form; for the BDO and PDO polymers the new peaks for the extended forms appear at lower temperatures than those for the contracted forms. Only a single peak is seen for the EDO polymer, for which only one crystal structure has been detected for the hard segments. These results indicate that the development of polymorphic crystal structures must be taken into account in interpreting the multiple melting phenomena seen for the hard domains in polyurethane elastomers.
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  • 184
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    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 909-910 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
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  • 185
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    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 979-991 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A linear chain model is used to calculate the thermal expansivities of polymer crystals from room temperature down to liquid-helium temperature. Because of restraint by strong covalent forces, vibrations along the chains give a negligible contribution. Vibrations transverse to the chains cause the length projected along the chain direction to decrease. The expansivity along the chain direction, αc∥ is therefore negative, and has temperature dependence characterized by the low Debye temperature of transverse vibrations. These vibrations, through a cubic term in the interchain van der Waals potential, also cause a positive expansivity, αc⊥ perpendicular to the chain direction. The theoretical predictions for αc∥ and αc⊥ agree quite well with experimental data over the wide temperature range under consideration.
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  • 186
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Sorption isotherms for pure CO2 and pure CH4 in Kapton H® polymide films at 60°C are reported for pressures up to 20 atm and are analyzed in terms of the dual-mode sorption model. An experimental scheme for the measurement of steady-state permeabilities of both pure and mixed gas feeds is described. Permeabilities of Kapton to the individual components at 60°C are presented for a mixture comprised of 32.2% CO2 in CH4 as functions of feed pressure up to 590 psi (absolute). The permeabilities for the individual penetrants in the mixed feed are lower than the respective purecomponent values at the corresponding partial pressures. Furthermore, the permeabilities of both penetrants drop as the feed pressure is increased at constant composition. The dual-mobility transport model used to analyze the data postulates that the observed pressure and composition dependence of the permeabilities is due to competition between penetrants for a limited microvoid sorption capacity in the glassy polymer. It is demonstrated that in addition to flux depressions due to dual-mode effects, nonideality of the gas phase must be accounted for to explain the substantial flux depressions observed for the CO2/CH4 mixtured used in this study.
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  • 187
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    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 1105-1117 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The morphology of isotropic films of poly[N,N'-bis(phenoxyphenyl)-pyromellitimide] was investigated by means of small-angle x-ray scattering. A significantly different morphology was found to develop in these films as compared to that in films possessing as in-plane molecular orientation. It was found that morphology could be described by a damped periodic modulation in the electron density characteristic of a chain segment aggregation. An increase in the initial imidization temperature resulted in an overall increase in the lateral packing of the chains and a reduction in the amplitude of the density modulation. Evidence was also found for segmental aggregation in the precursor polyamic acid which contained up to 35% solvent.
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  • 188
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    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 1085-1096 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The newly arisen possibility of crystallizing polyethylene at supercoolings much higher than were achievable previously has enabled the study of crystallization to be extended in several directions. Thus, fold length can be followed down to previously inaccessibly low crystallization temperatures, in the present case with sharp fractions, demonstrating the essential independence of the fold length of molecular weight. In this context the thinnest isolated crystal reported so far was obtained (ca. 6 nm). The faceted nature of crystals grown at such low temperatures and high rates has been noted, and is in line with new conceptions of polymer crystal growth. A previous observation of exceptionally high crystal growth rate (ca. 2 m/s) has been supplemented by measurements over a range of crystallization temperatures and the results found to be in good agreement with the predicated regime III behavior in the least theory of Hoffman. Observations of epitaxy on mica, while broadly in line with those by Lovinger, were revealing in several respects. Among these the observation that the substrate can influence the fold length when the chains are parallel to the substrate plane remains unexplained and puzzling.
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  • 189
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    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 1149-1151 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 190
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    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 1155-1162 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Uniaxial stretching and orientation of some linear flexible-chain polymers have been investigated. A functional relation has been found between the maximum recoverable deformation and the limiting extension of the macromolecules. These deformations are found to increase in direct proportion to the square root of the degree of polymerization and to decrease with increasing stiffness of the polymer chain.
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  • 191
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    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 1119-1148 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Transient and steady-state rheological data are reported for several anionic polystyrene solutions in tritolylphosphate (1. 6 〈 cM/ρMc 〈 7). Here c is the concentration of the solution, M is the molecular weight, ρ the density of the undiluted polymer, and Mc the molecular weight between entanglements as determined from zero-shear viscosity. The polystyrene used had Mw = 410,000 and Mw/Mn 〈 1.06. Data are also given for solutions of polyisobutylene and poly(vinyl acetate) with larger Mw/Mn. The results give a critical strain γ′ ∝ c-1 such that linear viscoelastic behavior was obtained in a simple shear deformation with shear less than γ′. A simplified version of the constitutive equation of Bernstein, Kearsley, and Zapas is used with an empirical strain function F (γ) which contains γ′ as a parameter to discuss transient and steady-state behavior in terms of the distribution of relaxation (or retardation) times determined for linear viscoelastic responce. Features of the dependence of the steady-state viscosity ηk, recoverable compliance Rk, the first-normal stress function Nk(1) on shear rate k are discussed in terms of F (γ) and the distribution of relaxation times to conclude that the latter plays a dominant role in the behavior observed in the range of k usually studied. The results predict that the reduced functions ηk/η0, Rk/R0, and Nk(1)/N0(1) should depend on η0R0k, and that the functional form depends markedly on the distribution of relaxation times, at least in the range η0R0k 〈 102. Comparison with the mechanistic model of Doi and Edwards shows a similar F (γ) but substantial differences in the reduced functions caused by a very narrow distribution of relaxation times in the model.
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  • 192
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    Keywords: Physics ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Physics
    Notes: The major objective of this work was to develop a simple and rapid technique to quantitatively measure the macromolecular chain orientation in polypropylene surfaces. A previously described experimental design employing attenuated total reflection spectroscopy near the critical angle was applied. The infrared dichroism of the 841- and 809-cm-1 bands of polypropylene was used to quantitatively determine a fractional orientation function of the macromolecular chains along the three major film axes (machine direction, transverse direction, and thickness or normal direction). The surface orientation of a set of polypropylene films uniaxially extended from 0 to 500% was determined using this technique. The variation of surface orientation, bulk crystallinity, and thickness with extension of these uniaxially extended films were compared. The surface orientation of an unoriented and several biaxially oriented polypropylene films was compared to the bulk orientation determined by a similar transmission infrared dichroism method. It was found that surface and bulk orientation were generally similar. It was shown that rather small orientations could be measured by the surface orientation method and that it was applicable to multilayer films and very thick samples, where the transmission method fails.
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  • 193
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    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 1331-1342 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Infrared spectra in conjunction with calorimetric measurements have been used to follow the crystallization process and microstructural changes of poly(ethylene oxide) (PEO) in poly(ethylene oxide) and poly(methyl methacrylate) (PMMA) blends. We have given particular attention to compositions containing low PEO concentrations. The crystallization behavior and the resultant microstructures of PEO are strongly perturbed by the presence of PMMA. In addition, we found phase separation and trans sequences of PEO to be present, especially at low PEO concentrations.
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  • 194
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    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 1349-1352 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 195
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    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 1471-1481 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We report polarized photon correlation measurements of bulk poly(phenylmethyl siloxane) (PPMS) with a molecular weight of about 2500 at different pressures from 1 to 1750 bar and temperatures between 269 and 308 K. In the Frequency range accessible by present-day digital correlators, the time correlation function can measure a slow q2-dependent diffusional process due to local concentration fluctuations and a fast α-mode structural relaxation process. The mean characteristic times of the two processes approach each other at low temperatures and high pressures, in contrast to the behavior of the α- and β-relaxation times. We should be cautious in relating the mean characteristic times for the structural relaxation process obtained by different experimental techniques, such as Brillouin scattering and photon correlation spectroscopy, because of the differnces in the probe emphasis and the extremely broad frequency distribution of such relaxation processes.
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  • 196
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    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 1561-1587 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetic network (KN) model discussed previously in the context of monodisperse and bimodal polymer systems is extended to polymers of arbitrary molecular weight distribution. A generalization is proposed for the flow-dependent entanglement loss term in the structure equation, replacing the shear rate \documentclass{article}\pagestyle{empty}\begin{document}$ \dot \gamma $\end{document} by a new variable \documentclass{article}\pagestyle{empty}\begin{document}$ \dot \Gamma $\end{document} which reduces to\documentclass{article}\pagestyle{empty}\begin{document}$ \dot \gamma $\end{document} for simple shear and is more appropriate for elongational and other flows. New data are obtained on shear stress transients of many kinds, using a recently developed parallel-plate rheometer. These data and others on steady and transient flows of well-characterized polydisperse polymers in shear and in elongation are used to demonstrate that the KN model predictions are valid. Comparisons with predictions for monodisperse polymers having the same as Mw polydisperse systems show that transient behavior - especially stress overshoot - is particularly sensitive to details of the molecular weight distribution. Further possible improvements in the theory are suggested, and the relationship of the KN model to other recent network models is discussed. The KN model has greater data fitting capabilities, with fewer parameters, than any other model available at present.
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  • 197
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    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 1615-1621 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The heat of fusion ΔHf of 66 nylon has been determined by use of the Clapeyron equation. Measurements of ΔHf and the unit-cell parameters on molding pellets show that this material contains the α2 crystal phase, which is less dense than the α1 phase obtained by crystallization from solution. The value of ΔHf-45-46 cal/g, is in good agreement with earlier reports.
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  • 198
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    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 1727-1744 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The thermodynamic and structural properties of a series of hydrogenated polybutadienes, crystalized in the bulk and from dilute solution, have been investigated. These polymers are ethyl-branched ethylene copolymers with narrow molecular weight and composition distributions. Despite the fact that for both modes of crystallization these random-sequence copolymers display a lamellar crystalline habit, all of the independent physical chemical measurements are quantitatively consistent in indicating a relatively thin crystallite with a large amorphous disordered overlayer. This is seen to be a very general phenomenon for copolymer crystallization. The core thicknesses, determined from Raman LAM and from small-angle x-ray scattering, are in good agreement. Quantitatively consistent values of the degree of crystallinity are obtained from the density, enthalpy of fusion, Raman internal modes, Raman LAM, and small-angle x-ray scattering. It is significant that independent thermodynamic and structural methods give the same result.
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    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 1753-1771 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Analytical expressions describing the kinetics of photoinitiated free-radical polymerization are derived for a variety of conditions. The effect of the exponential attenuation of intensity of light in the direction of incidence in the system is carefully accounted for in each case. An attempt is made to include the depletion of initiator due to its photolysis in the kinetic scheme. The marked difference between the polymerization kinetics in well-stirred and unstirred systems is shown by comparing them under limiting conditions. The variation of this difference with the optical density of the system is illustrated graphically. The influence of light absorption by components other than the photoinitiator (e.g., solvent, monomer) is examined. The order of the polymerization reaction with respect to initiator as determined by conventional kinetic experiments depends on the amount of light absorbed by components of the system other than the photoinitiator.
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  • 200
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    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 1773-1779 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Fourier transform infrared (FTIR) studies of polystyrene (PS)/poly(vinyl methyl ether) (PVME) miscible blends as a function of temperature are presented. Below the lower critical solution temperature (LCST) little change is observed in the interaction spectrum obtained via digital subtraction techniques. Once above the LCST, the magnitude of the interaction spectrum decreases as a result of the phase separation process. Comparison of the behavior of the ether C—O stretching band in the reference PVME and in the blends has yielded a lower limit estimate for the interaction energy of about 0.15 kcal/mol.
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