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  • Articles  (2,164)
  • Physics  (2,164)
  • 1985-1989  (205)
  • 1980-1984  (977)
  • 1970-1974  (982)
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  • Physics  (2,164)
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  • 1
    Electronic Resource
    Electronic Resource
    Quantum yield for poly(methyl methacrylate) chain scission by 214-229 nm wavelength light (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1749-1758 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The quantum yield for poly(methyl methacrylate)chain scission by ultraviolet light in the 214-229 nm wavelength region was found to be φd = 0.03 scissions per absorbed photon. Samples were 1.65-μm films spun cast on silicon wafers and irradiated under flowing nitrogen by a cadmium vapor lamp. Gel permeation chromatography was used for molecular weight determination. Heating (postbaking) the irradiated films at 150°C for one hour under reduced-pressure flowing nitrogen increased the observed scissions per absorbed photon to 0.04. Glass transition temperatures by DSC are well-represented by Tg (K) = 393.3 - 2.0 × 105/Mn for the postbaked samples (139,000 〉 Mn 〉 6500).
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230902
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  • 2
    Electronic Resource
    Electronic Resource
    The structure of MDI/BDO-based polyurethanes: Diffraction studies on model compounds and oriented thin films (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1915-1932 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polyurethanes based on MDI/BDO are known to crystallize in three distinct forms. Two of these crystal structures, type II and type III, have been characterized by electron and x-ray diffraction experiments on model compounds and oriented thin films of a 77% hard-segment polyurethane elastomer. The model compounds were of the form BDO(MDI/BDO)n with n = 1, 2, 3. Results from the model compounds indicate that the MDI/BDO repeat crystallizes in the type-II structure, which has a contracted conformation with a monomer repeat length of 1.70 nm. MDI/BDO-based polyurethanes also exhibit the type-II structure under quiescent crystallization conditions. Studies of oriented thin films of an MDI/BDO-based polyurethane indicate that a change in crystal form occurs on stretching to the fully extended monomer conformation. This crystal form is termed type III and has a monomer repeat length of 1.92 nm.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230913
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  • 3
    Electronic Resource
    Electronic Resource
    Extraction and sorption studies using linear polymer chains and model networks (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1933-1940 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Model networks have been prepared by tetrafunctionally endlinking linear polydimethylsiloxane (PDMS) chains having molecular weights Mn in the range 2000-15,000 g mole-1. The first series of networks were prepared from mixtures containing known amounts of unreactive linear PDMS chains with molecular weights Md between 1000 and 16,000 g mole-1. Rates of extraction were used to estimate diffusion coefficients; as expected, they were found to increase with increase in molecular weight Mc = Mn between crosslinks, but to decrease with increase in Md. The ease with which all of such a diluent could be removed showed the same dependence on Mc and Md. A second series of networks was prepared from the same reactive PDMS chains without diluents. Sorption and extraction studies using the same diluents were then carried out. The diffusion coefficients for sorption were found to be in the range (1.7-15.0) × 10-12 m2 s-1 and depended on both Mc and Md. The amount of diluent absorbed at equilibrium was between 10 and 70%, which is in good agreement with predictions from the Flory equation for dilation in networks, with account of constraints on crosslink fluctuations.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230914
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  • 4
    Electronic Resource
    Electronic Resource
    Analysis of stress-induced crystallization in high-cis-1,4-polybutadiene (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2109-2118 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Stress-induced crystallization of a crosslinked polybutadiene with a high 1,4-cis content is investigated, at room temperature. The change in the fraction of crystallinity with deformation is evaluated by two different methods. The first is based on simultaneous measurement of birefringence and stress. The second is based on calorimetric analysis. The data on crystallinity obtained by these two methods are in good agreement in the range of low deformations, while, in the range of higher deformation (λ 〉 5), the degree of crystallinity obtained by calorimetry is higher than that obtained by the optical method. Qualitative information on the crystallization was also obtained by optical analysis of the hysteresis behavior. The hysteresis data show the presence of ordering phenomena at deformations at which there seems to be no crystallinity according to both quantitative methods.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180231009
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  • 5
    Electronic Resource
    Electronic Resource
    Comparative study of dielectric, mechanical, and nuclear magnetic relaxations in linear polyethylene. II. Relaxation spectroscopy of the α, β, and γ loss bands with special emphasis on fine structure (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 809-824 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dielectric, mechanical, and NMR retardation (correlation) spectra for relaxations in linear polyethylene were calculated in normalized form and intercompared. For each of the two local-mode relaxations in the γ region, called γ1 and γ2, these spectra are found to be in excellent agreement. For the α region, the spectra for two mechanical processes, called α1 and α2, two NMR processes, called α′ and α, and one dielectric process α were calculated. Excellent agreement is found between the spectra for the dielectric α and NMR α′ processes and also spectra for the mechanical α2 and NMR α processes, due to molecular motion in the interior of crystals. However, the spectrum for the mechanical α1 process is different from that for the dielectric α and NMR α′ processes, though the activation energy for the first process is almost the same as for the other two. This behavior is interpreted on the assumption that the dielectric α and NMR α′ processes are caused by molecular motion in lamellar surface layers while the mechanical α1 process is due to grain-boundary slip with viscous resistance of the surface layers in the boundaries. The shapes of the spectra, including the spectrum for the β process, are not affected by diluent.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230414
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  • 6
    Electronic Resource
    Electronic Resource
    Coherent elastic scattering of a reptating chain in a melt during transient relaxation (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 833-844 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We calculate the elastic scattering of a long chain in a polymer melt during the process of relaxation after a sudden deformation, i.e., the return to equilibrium with time, while the deformed shape is maintained. The scattering thus depends on the duration t of the relaxation, as well as on the scattering vector, and is a physical quantity characteristic of the dynamics of long chains. The reptation model of de Gennes is used as developed for deformed melts by Doi and Edwards: the chain is confined by other chains in a tube, from which disengagement by the ends is the only way of renewing its configuration. The tube diameter is taken as a parameter. We give both an analytic form and numerical evaluations. On comparison with calculations based on the Rouse model, in which the chain is assumed to be free in a viscous medium, it is seen that the experimental data (given elsewhere) should enable one to distinguish between the two models.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230501
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  • 7
    Electronic Resource
    Electronic Resource
    Spectroscopic characterization of acetylene-terminated sulfone resin (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 845-859 
    Details
    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 was used to characterize the thermal polymerization of the acetylene-terminated (AT) resin, bis[4-(3-ethynylphenoxy)phenyl]sulfone. Spectral processing techniques (including the method of factor analysis) were utilized in the analysis of the infrared data. The degree of cure was quantitatively monitored as the resin was thermally polymerized. Factor analysis indicated that only one reaction product is spectroscopically distinguishable. Further band analysis indicated the formation of predominantly trans conjugated polyene structures. No evidence for cyclotrimerization was found.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230502
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  • 8
    Electronic Resource
    Electronic Resource
    Quantitative aspects of internal reflection spectroscopy: Polymer surface composition measurementThis paper was presented in part at the FACSS XI meeting, Philadelphia, Pennsylvania, 1984. (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 861-871 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The use of band-ratioing techniques in internal reflection spectroscopy (IRS) for a wide variety of polymer surface composition and orientation measurements is discussed. It is shown that quantitative data can be obtained under a wide range of experimental conditions. The effects of variations in sample contact, internal reflection element, and angle of incidence are considered in detail. The applicability and limitations of calibration procedures for the determination of surface composition under various experimental conditions are considered. The requirements for obtaining quantitative results by IRS are shown to be far more lenient than is typically assumed.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230503
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  • 9
    Electronic Resource
    Electronic Resource
    Fracto-emission from filled and unfilled polybutadiene (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 873-888 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We further examine the mechanisms involved in the emission of electrons and positive ions from polybutadiene accompanying fracture. Experimental evidence is given in support of a previously presented model involving a microdischarge accompanying fracture which excites the fracture surfaces by particle bombardment. Calculations of the time dependence for the emission from such excitations for both isothermal and thermal stimulation from a simple trap model are presented. We conclude that both filled and unfilled polybutadiene are experiencing the same excitations except at a considerably reduced intensity for the unfilled material.
    Additional Material: 13 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230504
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  • 10
    Electronic Resource
    Electronic Resource
    Effect of polydispersity on the cloud-point curves of polymer mixtures (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 917-924 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A method is presented for the calculation of cloud-point curves of polymer-polymer mixtures when the polymers involved are polydisperse. The method is based on the Flory-Huggins free energy of mixing with a concentration-independent χ parameter. Numerical results are given for cases in which the molecular weight distributions are represented by the Schulz-Flory type. When the two polymers have similar average molecular weights and polydispersities, the cloud-point curves become flatter as the polydispersity increases. When the two polymers have similar average molecular weights but differ in polydispersity, the cloud-point curves become more skewed as the difference in the polydispersity increases. The results point out that, if the polydispersity effect is not properly accounted for, the value of χ deduced from experimental cloud points is liable to be in error, especially with regard to its temperature coefficient and its concentration dependence.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230506
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  • 11
    Electronic Resource
    Electronic Resource
    Percolation and effective-medium theories for perfluorinated ionomers and polymer composites (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 933-953 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Percolation and effective-medium theories are applied to model the transport and elastic properties of perfluorinated ionomers. The composite nature of these polymers is emphasized. The effective-medium theory is generalized to track continuously the evolution from lamellar to fibrillar morphology. The predicted dramatic difference in ion selectivity between lamellar and spherical morphology is verified quantitatively in perfluorinated ionomer blends. The limitations and potential improvements of the effective-medium theory and its relationship to percolation theory are discussed. Applications of these theories to other multiphase polymer systems are also discussed.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230508
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  • 12
    Electronic Resource
    Electronic Resource
    Effect of molecular weight on the refractive index increments of polystyrene, poly(ethylene glycol), poly(propylene glycol), and poly(dichlorophenylene oxide) in solution (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 925-931 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The variation of refractive index increments with molecular weight has been studied using solutions of polystyrene (2.2 × 103 〈 Mw 〈 1.8 × 106), poly(ethylene glycol) (1.0 × 103 〈 Mw 〈 2.0 × 104), and poly(dichlorophenylene oxide) (3.3 × 103 〈 Mw 〈 4.8 × 105) in toluene and poly(propylene glycol) (1.2 × 103 〈 Mw 〈 4.0 × 103) in benzene. The refractive index increments of polyglycols containing aliphatic ether moieties are negative in these solvents. However, poly(dichlorophenylene oxide) polymers, which contain aromatic ether moieties, give positive values. Linear and branched halogenated poly(phenylene oxide)s show an asymptotic approach of the refractive index increment to the same limiting value, but the approach is more rapid for the branched polymer.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230507
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  • 13
    Electronic Resource
    Electronic Resource
    Sorption and diffusion of toluene in isotropic and oriented linear polyethylene (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 973-989 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Sorption and diffusion of toluene vapor in linear polyethylene with mass-fraction crystallinity between 0.48 and 0.82 and draw ratios λ up to 10 have been studied at 30°C. The sorbed concentration in the amorphous phase Ca is little affected by crystallinity, indicating that the free-volume fraction is roughly the same for all isotropic samples. However, the diffusion path becomes more tortuous with increasing crystalline content, thereby leading to a sixfold drop in the zero-concentration diffusion coefficient D0. Drawing has more drastic effects, reducing Ca and D0 by factors of 4 and 60, respectively, as λ increases to 10. These large changes result from the transformation of the initially spherulitic material into a fibrous structure, which is composed of aligned microfibrils with taut tie molecules lying on the outer boundaries. The effects of crystallinity and orientation on the concentration dependence of the diffusion coefficient are also discussed.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230510
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  • 14
    Electronic Resource
    Electronic Resource
    Morphological studies of liquid-crystalline cellulose derivatives. II. Hydroxypropyl cellulose films prepared from liquid-crystalline aqueous solutions (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1053-1064 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A morphological study of hydroxypropyl cellulose (HPC) was performed on solid films prepared by casting from a liquid-crystalline aqueous solution at rest or under shear. Electron microscopic observations reveal that many round particles composed of stacked disks are densely packed in the interior of a quiescently cast HPC film, while on the film surface formation of fibrous textures is also noted. Shear-deformed HPC films exhibit some interesting morphological features according to the shearing conditions. It is found by electron microscopy that the originally round particles become more and more elongated as shear stress increases. The resulting rodlike fibrillar entities are considerably aligned in the shear direction (SD), but form a banded structure with periodic discontinuities of molecular orientation distribution along the SD. A new mechanism of structural transformation is proposed in order to interpret these results.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230515
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  • 15
    Electronic Resource
    Electronic Resource
    Time dependence of mechanical and transport properties of drawn and annealed linear polyethylene (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1217-1234 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Linear polyethylene both as drawn, or drawn and subsequently annealed with free ends, changes its length, density, crystallinity, elastic modulus, sorption, and diffusivity as the sample stands completely unrestrained at room temperature. Most of these changes occur during the first few hours. But they are important on a molecular scale since they suggest strongly that drawn, and drawn and annealed samples are far from equilibrium. As a consequence of the tendency of each mobile tie molecule in the amorphous conformation to retract and to crystallize, the specimen approaches but does not reach complete equilibrium. The transient seems to be caused by slow crystallization of tie molecules which creates crystalline bridges across the amorphous layers.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230613
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  • 16
    Electronic Resource
    Electronic Resource
    Random-coil configurations of aromatic polyesters: Birefringence of poly(triethylene glycol terephthalate) networks in elongation (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1235-1245 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Hydroxyl-terminatd poly(triethylene glycol terephthalate) was crosslinked with an aromatic triisocyanate. Birefringence-stress-strain experiments, performed on the networks at 70°C, showed an anomalous increase in the modulus and a downturn in the birefringence-strain isotherms at high elongations. These results suggest that crystallinity is not responsible for the non-Gaussian behavior of the chains at high extension. The same kind of experiments were performed over the range 20-70°C. Values of the optical configuration parameter Δa of the order of 13.3 × 10-24 cm3 with negligible temperature coefficient were found for these networks. The quantities Δa and d In Δa/dT were calculated by means of the rotational isomeric state model. Better agreement between the theoretical and experimental values of these parameters was found for poly(triethylene glycol terephthalate) than for poly(diethylene glycol terephthalate). Since the polarities of the two chains are similar, intermolecular interactions involving terephthaloyl residues may be responsible for the discrepancies observed between theory and experiment for Δa in aromatic polyesters.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230614
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  • 17
    Electronic Resource
    Electronic Resource
    Dilute-solution properties of trans-1,4-polyisoprene (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1255-1262 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Trans-1,4-polyisoprene was fractionated by both fractional precipitation and preparative gel permeation chromatography to obtain possibly sharp fractions of narrow molecular weight distribution. Selected fractions were characterized by light scattering, viscosity, and gel permeation chromatography. Necessary corrections for molecular heterogeneity were applied. Some of the characteristic relations between [η] and Mw are [η] = 1.81 × 10-4 Mw0.722 in benzene at 30°C, [η] = 1.38 × 10-4 Mw0.711 in n-hexane at 30°C, which are found to be in good agreement with literature data when corrected for molecular heterogeneity.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230616
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  • 18
    Electronic Resource
    Electronic Resource
    Concentration distribution of elements in heterogeneous polymer systems determined by electron microprobe analysis (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1485-1494 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A technique for analysis of composition variations in heterogeneous polymer systems permits investigation of materials with both uniform and nonuniform distribution of heterostructural components. To illustrate the method, determinations have been made of concentration profiles of dibromo-diallyl-phthalate formed in porous PVC in two different ways.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230802
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  • 19
    Electronic Resource
    Electronic Resource
    Dilute solutions of poly(vinyl alcohol) derived from vinyl trifluoroacetate (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1703-1712 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dilute-solution behavior of poly(vinyl alcohol) (PVAVTFA), derived from vinyl trifluoroacetate, in water-dimethylsulfoxide (DMSO) mixtures was investigated. With solvent mixtures ranging from 10 to 20 vol % DMSO, the relation between the reduced viscosity ηsp/C and the polymer concentration C was linear for polymer concentrations above 0.2 g/dL, whereas in solutions in mixed solvents of other compositions the dependence was linear for polymer concentrations above 0.1 g/dL. The relation between the intrinsic viscosity [η] obtained for aqueous solutions of PVAVTFA and the molecular weight M estimated from viscosity measurements in solutions of poly(vinyl acetate) (PVAVTFA), obtained by acetylation of PVAVTFA, was given by [η]30°Cwater = 7.34 × 10-4 M0.63. The value of [η] was greatest for the solvent mixture with 10 vol % DMSO and smallest for about 50 vol % DMSO, and Huggins constants k were smallest and greatest for these two cases, respectively. The turbidity of the solutions of low-molecular-weight PVAVTFA, was higher than that of high-molecular-weight PVAVTFA up to 30 vol % DMSO, and the reverse relation held for 40-70 vol % DMSO.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180230821
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  • 20
    Electronic Resource
    Electronic Resource
    Application of a new structural theory to polymers. I. Uniaxial stress in crosslinked rubbers (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2243-2271 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A continuum rheological theory, endowed with generalized structural significance, has recently been developed. Based on nonequilibrium thermodynamics, it relates stress σ, strain rate \documentclass{article}\pagestyle{empty}\begin{document}$\dot \varepsilon$\end{document} and temperature in terms of material evolution through a series of structural states. The theory has previously had success in dealing with crystalline metals and surface physics, and here it is applied to crosslinked rubbery polymers in the nominally amorphous condition. Structure is believed to be related to interchain associations, chain entanglements, chain ends, and other defects in the hypothetical ideal network which by itself would lead to neo-Hookean predictions in uniaxial deformation, σnH ∝ λ2  -  λ-1, where λ is the stretch ratio. Predictions are made for σ(λ) in both tension and compression and shown to be more compatible with data than either σnH(λ) or the Mooney - Rivlin expression σMR(λ). Only two parameters are required, moduli Go (reflecting initial structure) and Gs (the steady-state condition), and rate effects are incorporated through Go(\documentclass{article}\pagestyle{empty}\begin{document}$\dot \varepsilon$\end{document}) and Gs(\documentclass{article}\pagestyle{empty}\begin{document}$\dot \varepsilon$\end{document}). The phenomena of yielding and stress softening in cyclic tensile loading are also predicted, suggesting advantages to this approach relative to conventional viscoelastic continuum models.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.180231102
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  • 21
    Electronic Resource
    Electronic Resource
    Linear polymers in nonhomogeneous flow fields. I. Translational diffusion coefficient (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 73-87 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The translational diffusion coefficient D, needed in treatments of flow-induced polymer migration phenomena, is studied. Explicit results are reported for bead-spring model macromolecules with two, three, and four beads, respectively. If the number of beads is large, an integral formulation is used. The results obtained show that D depends upon the hydrodynamic interaction parameters h* and h*N1/2. Nondraining behavior of D is predicted irrespective of h if h* is close to 0.2357. Approximations for D are obtained and the error involved is estimated.
    Additional Material: 7 Ill.
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    Thermoplastic elastomers: Structural and morphological aspects of ether-esteramide copolymers (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 49-57 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polyesteramide 6NT6-polytetramethylene ether glycol (PTMEG) copolymers, precipitated from dilute solution, have been studied by small-angle x-ray scattering (SAXS) and wide-angle x-ray scattering (WAXS) with variation of the PTMEG content. A comparison of the structural characteristics of these materials has been made with those of the 6NT6 homopolymer. Chain folding is assumed as the crystallization mechanism for the low-PTMEG-content copolymers, with possible inclusion of polyether segments within the 6NT6 crystal lattice. WAXS data support the view of a weakening of the 6NT6 crystalline packing in the equatorial planes as the reason for broadening of the diffraction peaks, for changes in their relative intensities, and for the increase in the equatorial interplanar distances in the high-PTMEG-content samples. The annealing behavior has also been investigated.
    Additional Material: 5 Ill.
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    Diffusion study of a polymer-diluent system using the optical mass transport method (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 253-261 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Thermotropic polymers and low-molecular-weight mesogens share many common textural features. This circumstance is exploited to determine diffusion coefficents in a system consisting of a cholesteric polymer and a low-molecular-weight nematogen using the recently developed optical mass transport method. The self-diffusion coefficient and its concentration dependence were determined by using a distance-time approach, whereas the time dependence of the mutual diffusion coefficient was evaluated by a conventional concentration-distance analysis of the diffusion profile. Comparison with literature data indicates satisfactory agreement. The coefficient of the scaling law relating the self-diffusion coefficient and concentration is in accord with the value predicted by de Gennes for semidilute polymer solutions.
    Additional Material: 6 Ill.
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    Carbon-13 NMR relaxation and transitions in polymers (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 367-385 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: High-resolution proton-decoupled carbon-13 nuclear magnetic resonance relaxation parameters have been obtained as a function of temperature for a set of completely amorphous polymers, semicrystalline polymers, and a series of ethylene-vinyl acetate copolymers. With these samples the nature of the glass temperature, other postulated amorphous transitions, and the β transition were investigated. For the completely amorphous polymers, the average correlation times depend on temperature according to the Williams-Landel-Ferry relation. Spectral collapse occurs at temperatures whose ratio to Tg is in the range 1.2-1.4 and corresponds to a correlation time of about 10-7s. The loss of resolvable spectra is demonstrated to be a consequence of experimental methods and is not due to the occurrence of another amorphous transition. Both the methylene and methine carbons can be resolved for the ethylenevinyl acetate copolymers. Although the correlation time for the methylene carbon is continuous and resolvable through the β transition region, the methine branch-point resonance is lost. The implication of these results to the molecular nature of the β transition is discussed.
    Additional Material: 14 Ill.
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    NMR self-diffusion study of polyethylene and paraffin melts (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 387-404 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The self-diffusion coefficient D of paraffin and polyethylene melts - covering the range between N = 19 and 103 where N is the number of monomeric units - was measured by the pulsed-magnetic-field-gradient NMR method for diffusion times between 3 ms and 1 s. For the paraffins, D is proportional to N-2 though the molecular weights are smaller than the critical molecular weight for entanglement. In polyethylene, melts a strong dependence of the diffusion coefficient on the diffusion time is observed, whereas no such dependence is found in paraffin melts. A mathematical formalism for describing spin-echo attenuation in terms of a velocity autocorrelation function is shown to yield qualitative agreement with the experimental results.
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    Rheo-optical Fourier-transform infrared spectroscopy of polymers. VII. Uniaxial deformation of heat-set poly-(ethylene terephthalate) film (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 405-411 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(ethylene terephthalate) (PET) film was uniaxially stretched to a draw ratio of 2.5. Two samples were prepared from this oriented film by heat-setting it at 493 K while free to relax and when held at constant length. The structural changes occurring during uniaxial elongation up to fracture of these two oriented crystalline samples and their stress-strain characteristics were simultaneously monitored by rapid-scanning Fourier-transform infrared (FTIR) spectroscopy. In the free-annealed sample, the orientation of the molecules in the amorphous phase shows a gradual improvement throughout the test, while chain unfolding occurs above 20% strain. This indicates that the predominant mechanism of deformation in this sample could be chain uncoiling in the amorphous phase followed by longitudinal slip processes within the sample. In the taut-annealed sample, chain unfolding occurs at low strains accompanied by slight improvements in amorphous and crystalline orientation. Thus, in this sample longitudinal slip would appear to be the main deformation mechanism. The results of the FTIR measurements are discussed with reference to the dependence of the deformation mechanisms on the initial structure of the samples.
    Additional Material: 5 Ill.
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    Estimation of crystalline tie molecules in ultradrawn polyethylene extrudates (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 429-435 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1985.180230215
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    The effect of pressure on the mechanical properties of polymers. IV. Measurements in torsion (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 623-651 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Stress relaxation was studied in torsion under superposed hydrostatic pressure using a newly constructed device. Two materials, a styrene-butadiene rubber and a butadiene rubber, were studied in the range from -60 to 30°C at pressures up to 500 MPa. The time-temperature-pressure superposition of the data can be described by the FMT form of the free-volume theory which uses input from relaxation experiments at high pressure. The applicability of the Havlíček-Ilavský-Hrouz form of the Adam-Gibbs theory was also examined. This theory, which does not require information from high-pressure relaxation experiments, offers less flexibility than the FMT theory and is less successful in predicting superposition. The data are also examined in light of an adaptation of the Simha-Somcynsky equation of state to the free-volume theory. Prediction of the effect of pressure by the theory requires a single adjustable parameter. It was possible to calculate the free-volume parameters of several polymers without use of information from high-pressure experiments.
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    Crystallization in oriented poly(ethylene terephthalate) fibers. I. Fundamental aspects (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 653-674 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The nature of crystallization- and mobility-induced changes during annealing of melt-spun poly(ethylene terephthalate) precursor fibers of a range of orientations has been examined. The kinetics of crystallization and the accompanying orientational changes have been studied under conditions of constant, low tensile stress, with the accompanying dimensional changes and under a constraint against shrinkage in length, with the stress developed being monitored. The effects of precursor orientation and externally imposed constraints on the course of the fundamental crystallization and orientational relaxation processes are revealed. Oriented crystallization has been shown to have a significant effect on the stress developed and on the dimensions of oriented precursor fibers, with a strong tendency to spontaneously extend as a consequence of the reorientation of crystallizing segments predominantly along the preferred fiber direction. The sequence in which crystallization and major orientational relaxation, if any, occur is found to have a profound effect on the structure and thus the deformability of oriented fibers after annealing above the glass transition temperature.
    Additional Material: 20 Ill.
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    Relaxation of chemical potential and a generalized diffusion equation (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 675-682 
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    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 slow structural relaxation in a solvent of high viscosity on the chemical potential driving the diffusion of penetrant molecules is described by a generalized diffusion equation with a memory term. The linearized version of this equation is solved for some special cases, and the correlation function of concentration fluctuations in thermodynamic equilibrium is calculated. As a result of the memory term, for very slow relaxation two different stages of the diffusion process can be distinguished.
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    Energy absorption in polymer crazing (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 683-693 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The total energy absorbed by a craze during its development in creep is analyzed and calculated on the basis of a time-dependent theory of crazing. Experimental measurements of the craze length have been utilized in the energy calculations. For polystyrene the initial energy absorption in the craze region is found to be several hundred times that in the uncrazed medium. This ratio decreases sharply in a short period of time to about 50 to 1 and less and remains low afterward. For polycarbonate, somewhat similar behavior has been found. The initial strain energy absorption by crazing is about 200 times that in the uncrazed region. The energy ratio reduces rapidly to about 55 to 1 and tends to level off thereafter. However, in general, the amount of strain energy absorbed does increase as a function of time, as it should.
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    Bead-spring model for adsorbed polymer chains in shear flow: Hydrodynamic interaction (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 695-707 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We consider the hydrodynamic interaction between two absorbed polymer chains in a simple shear flow, each modeled by a bead connected to the wall by a linear spring. It is concluded that hydrodynamic interaction between the beads or between the beads and the wall cannot be responsible for the experimentally observed increase in hydrodynamic thickness.
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    Crystallization of poly(m-xylylene adipamide) induced by sorption of water (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 743-750 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Sorption of water in quenched amorphous poly(m-xylylene adipamide) has been studied at 50°C. The sorption process is nearly Fickian at low humidity. At relative humidities higher than about 58%, however, extremely abnormal behavior, such as a decrease in moisture uptake and a change in appearance from transparent to opaque, is found. From x-ray diffraction analysis, these changes can be attributed to crystallization. Thermal analysis of moistened samples confirmed that the crystallization is due to a drop in crystallization temperature caused by sorption of water. From the relation between the reduction in moisture uptake and the increase in volumetric crystallinity, it is proposed that the change in moisture uptake is caused by the exclusion of water from the crystalline phase.
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    A study of the gas barrier properties of highly oriented polyethylene (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 709-731 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Measurements of permeability and diffusivity have been undertaken for the gases helium and oxygen in a range of highly oriented polyethylene films. The solubilities deduced for both gases are proportional to the amorphous volume fraction, showing that the noncrystalline regions are the transport medium in all instances. The changes in diffusion coefficient are more complex. A large reduction in diffusion coefficient is observed with increasing draw ratio, and this is particularly marked in the case of the larger oxygen molecule, where significant differences are also observed for different grades of polymer and different drawing conditions. These changes in diffusion coefficient are discussed in the light of previous studies of diffusion in polymers and present knowledge of the changes in structure produced by drawing.
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    Structural studies on the polymorphism of nylon 3 (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 733-742 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The structure and morphology of crystalline nylon 3 [poly(β-alanine)] have been studied by electron microscopy and x-ray diffraction. Two clearly defined forms are detected. Form I appears as spherulites made up of ribbonlike lamellae upon crystallization at high temperature from a solution in phenol-butanediol-1,4. They have monoclinic unit cell with a = 9.60 Å, c = 8.96 Å, and β = 122.5°. The hydrogen-bonded planes run parallel to the long dimension of the crystals. Form II is observed when the samples are prepared from formic acid solution at room temperature. A second type of spherulite with a microfibrillar structure is formed in this case. The isolated crystalline structures obtained from Form II appear to grow along the intersheet direction rather than along the hydrogen bond direction, which constitutes anomalous behaviour. Our results for this second form are consistent with an orthorhombic lattice with a = 9.56 Å and c = 7.56 Å. No clear information is obtained on the b dimension of the unit cell (chain axis) in either case. We assume a value of 4.78 Å, which corresponds to fully extended chains. The two forms coexist in films prepared from a formic acid-water solution as well as in samples recovered immediately after polymerization.
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    Elastic moduli of ultradrawn polyethylene (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1759-1780 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The five independent elastic moduli C11, C12, C13, C33, and C44 of oriented high-density polyethylene with draw ratio λ from 1 to 27 have been determined from -60 to 100°C by an ultrasonic method at 10 MHz. At low temperature the sharp rise in the axial extensional modulus C33 with increasing λ and the slight changes in the other moduli result from chain alignment and the increase in the number of intercrystalline bridges connecting the crystalline blocks. At high temperature (say, 100°C) the transverse extensional modulus C11, as well as the axial (C44) and transverse (C66) shear moduli, also show substantial increases, reflecting the prominent reinforcing effect of stiff crystalline bridges in this temperature region where the amorphous matrix is rubbery. If the crystalline bridges are regarded as the fiber phase, the mechanical behavior can be understood in terms of the Halpin-Tsai equation for aligned short-fiber composites.
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    Statistical description of spherulite patterns (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1723-1748 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A statistical description of spherulitic morphology and its formation resulting from primary nucleation and radial propagation is presented. Two- and three-dimensional cases are considered. The general formulas are valid for any time-dependent mode of primary nucleation and can be modified for a time-dependent propagation rate. Various distance distributions of boundaries and inner points of the final pattern and at intermediate stages of its formation as well as the degree of conversion and the distance correlation of primary nuclei are derived. Detailed derivations are carried out for three model modes of primary nucleation, athermal, thermal, and mixed. It is also shown that the degree of conversion from mixed-mode nucleation does not follow the Avrami plot. The total surface of boundaries in bulk, total length of boundaries on a plane, and numbers of multiple boundary points are also calculated for all modes of primary nucleation. The relations are confirmed by computer simulation of primary nucleation and radial propagation of spherulites on a plane and in bulk.
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    Depolarization field effect on the ferroelectric behavior of polymers (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1781-1791 
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    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 depolarization field in crystallites on the ferroelectric behavior of polymers is discussed on the assumption that the crystallite is a prolate ellipsoid with its major axis directed along the electric field. The theory relates the polarization P and the electric field E in the crystallite to the overall values P and E for the polymer. The determination of the P-E hysteresis of a crystallite from the P-E hysteresis is given with examples for poly(vinylidene fluoride) (PVDF) and vinylidene fluoride (VDF)-trifluoroethylene (TrFE) copolymer. The ratio R = J/(Ps - P), with J the switching current density and Ps the saturation polarization of polymer, is proved to be free from the depolarization field effect and the plot of logR against logarithmic time is shown to have merit for characterization of switching behavior. Examples of the curves are given for PVDF and VDF-TrFE copolymers. The temporal change of local electric field in the unreversed domains in the crystallite in the course of polarization reversal is predicted by the theory and this change is proved to be a significant mechanism of switching acceleration.
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    Sorption and diffusion of a tribasic acid dye in nylon 6 membrane in the presence of NaCl (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1813-1822 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Measurements of sorption and diffusion of a tribasic acid dye in nylon 6 membranes in the presence of NaCl are reported and critically analyzed by the dual-mode sorption and diffusion models consisting of either simple partition plus ion exchange, or simple partition plus “Langmuir” modes. It is shown that the former treatment, which is the physically more realistic one, also provides a generally better fit to the data.
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    Rheological and DSC changes in poly(vinyl alcohol) gels induced by immersion in water (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1803-1811 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(vinyl alcohol) (PVA) gels were prepared by freezing and thawing aqueous solutions at temperatures from -20 to 15°C. The temperature was varied periodically by use of a computer. The endothermic DSC peak was observed for the PVA gels at about 60°C for five specimens of different degrees of saponification (DS). Another endothermic peak was also observed in the range 67-80°C, and this peak shifted to higher temperature with increasing DS. These endothermic peaks shifted to lower temperature on immersion of the PVA gels in water. The dynamic Young's modulus E′ at room temperature was also decreased by immersion of PVA gels in water; E′ decreased monotonically with increasing temperature for PVA gels without immersion in water, while it increased up to a certain temperature and then decreased with increasing temperature for PVA gels in water. The X-ray diffraction showed a characteristic crystalline pattern for PVA gels of higher DS, and this peak was intensified by stretching the gel.
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    Study of spin-lattice relaxation and local motion in dissolved poly[2,2-propanediylbis(3,5-dimethyl-4, hydroxyphenyl)carbonate] (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1793-1802 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Proton and carbon-13 spin-lattice relaxation times are reported for 10-wt % solutions of tetramethyl bisphenol-A polycarbonate. The relaxation times for both nuclei were measured at two Larmor frequencies and as a function of temperature. These relaxation times are interpreted in terms of three motions: segmental motion, restricted rotational diffusion, and backbone methyl-group rotation. The Hall-Helfand correlation function is used to describe the segmental motion. Internal rotation is described by the usual Woessner approach and restricted anisotropic rotational diffusion by the Gronski approach. As demonstrated by its higher activation energy, correlated segmental motion appears to be slower than the unsubstituted polycarbonate of BPA. In addition, the single-transition processes seem to be still less important than correlated backbone transitions. Phenylene-group rotation is described in terms of restricted rotational diffusion instead of complete anisotropic rotation. The time scale for backbone methyl-group rotation is comparable to that in BPA, a fact indicative of weaker cooperativity between this motion and the other motions. Rotation of the methyl group attached to the phenylene ring is too fast to significantly contribute to relaxation except by partially averaging the dipole-dipole interactions. The higher activation energies for segmental motion observed in solution for this methyl-substituted polycarbonate relative to the unsubstituted polycarbonate parallel a significant increase in the glass transition temperature observed for the substituted material. The restricted pheylene-group rotation in solution is also parallelled by a large upward shift of the low-temperature loss peak in the glassy polymer.
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    The role of molecular diffusion in the adhesion of EPDM and EPR elastomers (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1823-1830 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Adhesion of lightly crosslinked sheets of EPDM (ethylene-propylene-diene terpolymer) to themselves and to a Mylar substrate has been investigated over wide ranges of peel rate and test temperature. The effect of incorporating ethylene-propylene copolymer (EPR) before crosslinking, to yield a loose macromolecular network containing dissolved linear EPR macromolecules, was also studied. The self-adhesion of these materials was found to be much greater than their adhesion to Mylar, over a wide range of effective peel rates. This is attributed to interdiffusion of EPR and EPDM molecular strands. At extremely low peel rates the enhancement of adhesion was smaller, probably because of back-diffusion, and at high rates, the strength of adhesion became high in all cases. These results are compared to those obtained previously for polyisobutylene-co- isoprene networks containing linear polyisobutylene molecules. The enhancement of self-adhesion at intermediate rates of peel was considerably greater for the EPDM-based materials, probably because of a lower degree of crosslinking and a greater tendency to form molecular entanglements.
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    Differential sorption in viscoelastic fluids (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1831-1855 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The diffusion of organic solvents in concentrated polymer solutions often deviates from the predictions of Fick's second law, especially when the solution is in the glassy state; such behavior is called anomalous or non-Fickian. This paper analyzes the one-dimensional sorption of a solvent into a concentrated polymer solution under a small driving force. The treatment includes the effect of an entanglement network on the process as postulated by Thomas and Windle. The deformation of the entanglement network during sorption creates a normal stress on the solvent equivalent to an osmotic pressure. Including the osmotic pressure gradient in the driving force for solvent diffusion leads to a linear, third-order partial differential equation for solvent concentration distributions. By evaluating the physical constants in the theory for the system methyl acetate/poly(methyl methacrylate) at 30°C the treatment is shown to predict the anomalous characteristics found experimentally.
    Additional Material: 10 Ill.
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    A SAXS study of a single crack and craze in plasticized polystyrene (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1857-1867 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Small-angle x-ray scattering (SAXS) was used to study the structure along a single craze that had broken down to form a crack along part of its length. This study was made possible by use of radiation from the synchrotron source CHESS which is sufficiently intense to permit examination of just a single craze. The total scattering from the craze was in excellent agreement with that expected from a knowledge of its dimensions and fibril volume fraction and width. This fact adds confidence to the interpretation of the scattering pattern of the craze as part diffraction, part reflection, and demonstrates that SAXS is a technique that may be used to measure craze volume within a sample. The craze was shown to grow in width by surface drawing with a constant structure, and then the fibrils broke to form a crack. The broken fibrils contracted and their diameters increased but they appeared to stay parallel with a constant fibril-axis radial distribution function.
    Additional Material: 9 Ill.
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    Far-infrared studies of microphase separation in sulfonated ionomers (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1869-1881 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Far-infrared spectra of a series of un-neutralized and neutralized lightly sulfonated polystyrenes with varying sulfonation levels have been investigated to seek spectroscopic evidence for microphase separation known to control the physical properties of these polymers. Broad, strong absorbance bands, not found in the spectrum of unmodified polystyrene, are observed in the spectra of the sulfonated analogs. The effects on the far-infrared spectra both of sulfonation level and of the mass and charge of the neutralizing cation are discussed in terms of cation motion and the formation of ion-rich domains.
    Additional Material: 7 Ill.
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    Small-angle scattering analysis of hard-microdomain structure and microphase mixing in polyurethane elastomers (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1883-1913 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The microdomain structure of a series of segmented polyurethane block copolymers is characterized by small-angle x-ray and neutron scattering analyses. The materials contain hard segments formed from 4,4′- diphenylmethane diisocyanate (MDI) and butanediol (BD), and range in hard-segment content from 20 to 80% by weight. The results provide evidence for a transition from discrete to continuous hard-microdomain morphology as the hard-segment content is increased above ca. 50%. The measured concentration dependences of the interdomain spacing, specific interfacial area, diffuse microphase boundary thickness, and scattering invariants are used to examine the validity of present models for hard-microdomain structure. The observed behavior corresponds well with the general predictions of a lamellar model wherein partially coiled hard-segment sequence configurations are allowed. The thickness of the hard microdomains extracted from the model corresponds to approximately four hard-segment repeat units. Scattering invariant calculations are used together with determinations of the soft-microphase glass transition temperatures to examine possible models for microdomain mixing. These calculations suggest that both the hard and soft microphases are phase mixed.
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    Dynamic behavior of flexible polymers at a solid/liquid interface (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1997-2008 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The mean time spent by a macromolecule at a solid/liquid interface is analyzed in the region of adsorption saturation. The method consists of carrying out preliminary adsorption with radioactively labeled high-molecular-weight polyacrylamide and subsequently exposing the surface to a solution of unlabeled polyacrylamide. It was found that, apart from a small fraction of polymers “loosely” attached, the exchange between labeled and unlabeled polymers takes place at the interface at a very slow rate. Furthermore, desorption of surface molecules occurs only in the presence of a solution, and then the rate of desorption increases proportionally to the number of molecules in the solution. A mechanism based on a bimolecular chemical exchange process is proposed.
    Additional Material: 8 Ill.
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    Miscibility and deformation behavior in some thermoplastic polymer blends containing poly(styrene-co-acrylonitrile) (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1975-1995 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Miscibility in blends of poly(styrene-co-acrylonitrile) (PSAN) with several other polymeric components has been investigated over a range of compositions by means of thermal analysis and transmission electron microscopy. Systems in vestigated were (i) PSAN/polycarbonate (PC), (ii) PSAN/styrene-maleic anhydride-methyl methacrylate terpolymer (S/MA/MM), (iii) PSAN/polynorbornene nitrile (PNN), and (iv) PSAN//S/MA/MM//PC. PSAN/PC was demonstrated to be partially miscible in all proportions over the PSAN copolymer composition range 23-70 wt % AN, while the miscibility or lack thereof of PSAN//S/MA/MM depended on the relative AN and MA contents of the PSAN and S/MA/MM, respectively. In contrast, PSAN/PNN was found to be immiscible in all proporations, while the system PSAN//S/MA/MM//PC was shown to be partially miscible. Deformation studies performed on rubber-modified versions of these blends defined deformation mode and microstructural deformation behavior. Dual extensometer tensile testing yielded relative contributions of crazing and of plastic flow, which correlated both with blend composition and with toughness. TEM observations of deformed specimens indicated a deformation process in the multiphase matrix blends consisting of craze initiation and propagation in the rubber-containing phase, craze arresting in the ductile second matrix phase, and coordinated extensive deformation of the matrix phases and of the rubber particles, where the ability to support the latter coordinated forms of deformation were observed to increase with increasing proportion of plastically deforming phase.
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    Evidence for sorption-desorption phenomena during thermal cycling in highly hydrated perfluorinated membranes (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2009-2020 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Perfluorinated ionomer membranes can absorb large amounts of water. DSC experiments show the existence of exothermic or endothermic peaks for water contents larger than 8 wt % at room temperature in Nafion 1200 EW in the acid form. Changes in the number of mobile protons versus temperature have been measured by NMR spectroscopy. A desorption process with an activation energy of 6 kcal/mol is proposed during the sample cooling. Such an explanation quantitatively explains both the DSC and NMR results and is also consistent with the other results obtained from mechanical experiments, low-temperature sorption isotherms, and ESR spectroscopy.
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    Determination of the geometric structure of three substituted polyacetylenes: Polymethylacetylene, polypentylacetylene, and poly(tbutylacetylene) (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2031-2041 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The geometric structure of polymethylacetylene (PMA), polypentylacetylene (PPA), and poly(t-butylacetylene) (PTA) was investigated by 1H NMR, 13C NMR, and IR spectroscopies. It was shown that both NMR techniques can be used to determine the trans isomer content of PPA and PTA, whereas the 1H NMR and IR methods can be used for PMA. A calibration curve was constructed by using the 965- and 720-cm-1 bands of the IR spectrum of PPA, and could be used in future work for the same purpose if the samples had molecular weights similar to that of the one used in this study. The isomerization kinetics of PTA was investigated and cis→ trans activation energies of 88 and 121 kJ/mol were calculated in solution and in the solid state, respectively. Heat treatment of the PMA and PPA samples always leads to a cis→ trans isomerization with a 100% trans content under extreme conditions. Moreover, a cis→ trans isomerization of PTA was induced in CCl4, CDCl3, toluene, and benzene, but a trans→ cis isomerization was induced in decalin. The reversible isomerization of PTA covered a trans isomer concentration ranging form 25 to 60%.
    Additional Material: 8 Ill.
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    Spectroscopic study of α- and β-phase isotactic polypropylene and of atactic polypropylene in solution (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2043-2057 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Raman spectroscopy is used to investigate the conformation and packing of isotactic crystalline α-phase polypropylene compared with lower-order β-phase isotactic polypropylene and to study the solution behavior of atactic polypropylene. The high-frequency region of the spectrum is analyzed in light of a normal-mode calculation that takes into account the methyl-group vibrations. This region is sensitive to both chain conformation and packing, and because of the high intensity of the methyl and methylene high-frequency stretching modes, it can be used to probe small changes in intermolecular or intramolecular order. Differences in the thermal behavior between the two solid isotactic polypropylene samples are explained interms of packing defects which exist in the β-phase form. In the solution study, we demonstrate that, for molecules in which bands sensitive to intermolecular interactions exist, as is the case of the methyl and methylene vibrations of polypropylene, spectroscopic techniques can be used to estimate the minimum overlap concentration.
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    The effect of spherulitic truncation on small-angle light scattering (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2059-2084 
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    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 spherulitic truncation on the Hv small-angle light-scattering (SALS) patterns are determined by computer simulation of spherulite nucleation and growth. The simulation is carried out for simultaneous and sporadic nucleation of two-dimensional spherulites and simultaneous nucleation of three-dimensional spherulites. The scattered intensity differences between truncated spherulites and round spherulites are determined as functions of the type of growth and the volume (or area) fraction of spherulites. Methods for the determination of certain geometrical characteristics of spherulites systems by SALS are developed. These characteristics include the volume (or area). fraction of spherulites, the average spherulite radius, and the average spherulite volume (or area). The results of this study are essential in the quantitative analysis of Hv SALS from spherulitic systems. The simulation process is readily extendable to the examination of other morphological phenomena by SALS.
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    Quantitative small-angle light scattering studies of the melting of poly(ethylene terephthalate) (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2085-2107 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Quantitative Hv small-angle light-scattering (SALS) studies of the melting of poly(ethylene terephthalate) (PET) have been performed. The results are compared with those from differential scanning calorimetry (DSC). It is found that fully grown spherulites melt over a temperature range of about 20°C without change in spherulite size, number, or internal disorder. The decrease in Hv SALS intensity is due to a decrease in spherulitic crystallinity over the melting range. The corrected experimental intensities are lower than, but in reasonable agreement with, the theoretically predicted intensities based on the DSC results. Procedures are presented for the quantitative analysis of Hv SALS intensities from spherulitic systems, including the corrections for the experimental, external disorder, and internal disorder effects.
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    Thermal and mechanical properties of short-segment block copolyesters and copolyether-esters (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2119-2147 
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    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 chain structure and processing variables on the microstructure and linear viscoelastic behavior of a series of copolyether-ester block polymers are described. In addition, the random copolyester analogs of the hard block are examined. The ester segments are composed of two isomers, poly(tetramethylene terephthalate) (PTMT) and poly(tetramethylene isophthalate) (PTMI), which possess significantly different crystallization kinetics. The ratio of PTMT to PTMI in the series has been systematically varied to alter the crystallizability without changing the chemical composition. The results of differential scanning calorimetry, wide-angle x-ray diffraction, and dynamic mechanical characterization are presented. Copolymerization of a second ester shortens the average sequence length of the first ester, resulting in melting-point depression for crystals of the first polyester and substantial lowering of the dynamic mechanical storage modulus above the glass transition of the intercrystalline phase. The melting-point depression may be predicted by using Flory's model for random copolymers, but the calculated heats of fusion are significantly lower than those obtained from diluent melting-point depression.
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    Melting of water/poly(ethylene oxide) systems (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2149-2158 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The transition temperatures of poly(ethylene oxide) (PEO)/water systems were studied over the temperature range from -90 to 110°C by differential scanning calorimetry. The composition of the systems and the average molecular weight of the PEO were varied over a wide range. The systems under study tend to supercool and become partially or completely glassy depending on the cooling rate, composition, and PEO molecular weight. The glassy phases crystallize on being heated above their glass transition temperature. Systems containing about 60 wt % of PEO are most readily super cooled without crystallization. The dependence of melting temperatures and enthalpies on composition was studied and their isobar phase diagrams were drawn. They show that at a definite polymer content (about 50 wt %), which is molecular weight dependent, the systems behave as binary eutectic mixtures. The results confirm the idea that PEO forms quite stable molecular complexes with water.
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    Relation of internal rotational isomerism barriers to the flow activation energy of entangled polymer melts in the high-temperature Arrhenius region (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2159-2180 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A strong correlation between internal rotational isomerism barriers and the flow activation energy of entangled polymer melts in the high-temperature Arrhenius region is observed. This correlation is predicted by a coupling model but is not expected by any other model that we are aware of.
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    Glass and subglass transitions in a series of poly(itaconate ester)s with methyl-terminated poly(ethylene oxide) side chains (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2181-2191 
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    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 poly(itaconate ester)s containing methyl-terminated poly(ethylene oxide) side chains with lengths ranging from 1 to 5 ethylene oxide units has been synthesized. Both heat capacity Cp and dynamic mechanical measurements have been carried out on these polymers using differential scanning calorimetry (DSC) and torsional braid analysis (TBA), respectively. The resulting data for this polymer series are discussed, and comparisons are made with work previously published for the corresponding di-n-alkyl itaconate ester polymers where appropriate.
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    Polymerization of furil in the solid state by reaction with AsF5 at the solid-gas interface (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2193-2201 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Solid-state polymerization of furil, induced by reaction with AsF5 at the solid-gas interface, has been investigated by means of vibrational analysis of the reactant and the product. Infrared spectra are consistent with the mode of Polymerization which involves an α,α′ linkage and subsequent loss of hydrogen atoms. The C/H elemental analysis suggests that the polymer consists of around six or seven monomeric units. The reaction product is found to be unstable at high temperatures; a prolonged annealing at this temperature leads to a different structure, possibly, by the opening of the furan rings. The x-ray powder diffraction study shows that the polymeric furil is crystalline, with a lattice similar to that of the monomer, but contains a considerable amount of disorder.
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    Spectroscopic studies of polymerized surfactants: 1,2-bis(10,12-tricosadiynoyl)-sn-glycero-3-phosphocholine (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2203-2216 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Spectroscopic studies have been performed on aqueous dispersions of the surfactant 1,2-bis(10,12-tricosadiynoyl)-sn-glycero-3-phosphocholine before and after polymerization with ul-traviolet light. Monomers of this lipid can, under certain conditions, convert from the expected spherical liposomal form to a unique phase consisting of hollow tubules. To determine the molecular conformation of these structures we have used Raman and infrared spectroscopies to probe the structure of the hydrocarbon chains and head groups of the lipids, and used absorption spectroscopy and resonance enhanced Raman scattering of the colored polymer to monitor the length and structure of the diacetylenic polymer backbone. Unusual C—H stretch-ing Raman bands imply that the hydrocarbon chain packing in the monomeric bilayers is different from that observed in other phosphatidylcholines, and that a distrubance in alkyl chain packing occurs on polymerization. Depending on irradiation conditions and the dispersal state of the lipid the polymer chains may be of at least three different colors, from which distinct resonance Raman spectra are obtained. The effective bond conjugation lengths range from quite short in the yellow polymer produced in sonicated vesicles to extremely long in a blue component seen in polymerized tubules.
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    Dependence of chain conformation and solution thermodynamics on composition for poly(ortho ester)s prepared from ketene acetals and mixtures of diols (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2217-2226 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The solution properties of a series of random copolymers prepared from ketene acetals with mixtures of diols have been characterized by dilute solution light scattering, chromatographic, and viscometric techniques. Five solvents with refractive indices ranging from 1.4 to 1.5 were used to obtain the correct weight average molecular weight. Changes in the unperturbed radius of gyration, obtained by combined size exclusion chromatography and low-angle light scattering techniques, parallelled that predicted by simple considerations of changes in repeat unit size. Thus the relative contributions of differing copolymer-solvent interactions and changing unperturbed radii of gyration to the hydrodynamic volume of random copolymers of different compositions were evaluated.
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    Cyclization of methacrylate-functional silane on particulate clay (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2227-2242 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Physically absorbed γ-methacryloxypropyltrimethoxysilane (γ-MPS) deposited from aqueous alcohol on particulate clay exists as low-molecular-weight cyclic, caged polysilsesquioxanes. These structures are incapable of forming high-molecular-weight chains or networks because of this internal cyclization tendency. The behavior is extremely different from that found in bulk solutions or when organofunctional silanes are adsorbed on low-surface-area glass or metal substrates. Fourier-transform infrared spectroscopy and gel permeation chromatography were used to characterize the silane species deposited in bulk and on the surface of particulate clay. The cyclization tendency is postulated from analysis of the behavior of hydrolyzed γ-methacryloxypropyltrimethoxysilane upon cocondensation with other organofunctional silanes and under variable cure conditions.
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    Comparative study of dielectric, mechanical, and nuclear magnetic relaxations of linear polyethylene. I. Broad-line NMR investigation of the fine structure of the α and γ loss bands observed by dielectric and mechanical measurements (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 787-808 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Detailed investigation of the linewidth, second moment, and mobile fraction by straightline decomposition of NMR spectra of linear polyethylene from ca. -160 to ca. 100°C reveals five molecular processes denoted γ1, γ2, β, α′, and α. Relaxation maps show that the γ1, γ2, and β processes correspond to the dielectric and mechanical relaxations given the same names, while the α and α′ processes correspond respectively to the mechanical α2 process due to molecular motion in the interior of crystals and to the dielectric α process. Close relations are found between the mass fractions of protons for the γ1 and β processes and also between those for the γ2 and α′ processes. From the effects of diluent on these processes and the annealing-time dependence of mass fractions of protons, the γ1, and β processes are attributed to two modes of molecular motion in an interlamellar amorphous region, while the γ2 and α′ processes are attributed to motions in the lamellar surface layers. The surface-layer thickness obtained by applying the two-phase model for the data on mobile fraction agrees quite well with that reported in the literature. The Bergmann-Nawotki three-component analysis of NMR spectra and symmetric-line decomposition for determining mobile fraction are shown to be unsuitable for studying the fine structure of the α and γ loss bands.
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    Influence of tacticity on Tβ, Tg, and TLL in poly(methyl methacrylate)s by the method of thermally stimulated current (TSC) (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 889-916 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The thermally stimulated-current method (TSC) has been employed to determine the temperatures and intensities of Tβ, Tg, and T 〉 Tg for pure isotactic, pure syndiotactic, and five atactic specimens with syndiotactic triad content from 49.5 to 75%; Tg was found to increase linearly with syndiotactic triad content as Tg (°C) = 48.0 + 0.856 (% syn), with R2 = 0.970 standard error 5.6°C; Tg for the syndiotactic specimen is 136.6°C measured, 133.6°C calculated. Several atactic specimens exhibit a second glass temperature 15 to 35 K above the regression line ascribed to some pure syndio content, and/or some isotactic-syndiotactic stereocomplexes. All specimens exhibited the liquid-liquid or TLL transition (relaxation) which increases linearly with 100-% isotactic triad content. Isotactic PMMA shows a T′LL relaxation 50 K above TLL. The Tg and TLL values obtained correlate extremely well with values from differential scanning calorimetry (DSC) determined in a separate study, as well as with most literature data. Intensities of Tg and TLL by TSC are greatest for isotactic, next for syndiotactic, with a broad, low minimum for atactic materials. The intensity of a β relaxation increases slowly from isotactic to syndiotactic. The TLL found by TSC compares well with literature values for isotactic PMMA obtained by several methods, and TLL in the atactic region compares well with literature values for atactic material. The ratio TLL/Tg ranges from 1.09 to 1.20 with no dependence on tacticity. Tg follows simple Arrhenius behavior with enthalpies of activation about one-half of the values normally calculated from dielectric and mechanical loss. The frequency dependences of TLL and T′LL follow a Vogel-WLF relationship with temperature. The origin of TLL is discussed in terms of the Frenkel hypothesis of segment-segment interaction. Evidence for TLL and TLL from a variety of methods indicates that these two temperatures are not artifacts of the TSC method.
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    Polymer migration in newtonian fluids (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 955-971 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The theory of Freed and Edwards is used to investigate polymer migration in nonhomogeneous flow fields with confined geometry. Polymer migration from the main flow originates in three effects: (i) nonhomogeneous flow-field effect, (ii) the confined-geometry effect, and (iii) the concentration effect. General correlation function formulas for these three effects are explicitly derived. Some specific examples are illustrated and solved by using the harmonic dumbbell and Rouse-Zimm models.
    Additional Material: 2 Ill.
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    Conformational behavior of styrene-dymethylsiloxane block copolymers in dilute solution (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 991-1000 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: To determine the behavior of a copolymer is dilute solution, a viscosity study has been performed on a polystyrene-polydimethylsiloxane block copolymer in three solvents presenting different thermodynamic conditions. The results are discussed in relation to a mixture of homopolymers and a segregated model. The unperturbed dimensions, obtained by the Stock-mayer-Fixman method, are intermediate between those of the parent homopolymers. The intrinsic viscosity measured in a good solvent, toluene, was close to the weighted averages of those of the corresponding homopolymers of equal molecular weight, but higher in decalin and in butanone, θ solvents for PS and PDMS, respectively. According to the low value obtained for the interaction parameter, the chain is slightly expanded as a result of the interactions between the unlike monomer units. Both segregation and random conformation would probably occur, depending on the quality of the solvent.
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    Influence of the interphase on block copolymer thermodynamics: Extension of the leary model (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1001-1029 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The Leary-Williams model for the microphase thermodynamics of triblock ABA copolymers has been modified to accommodate deviations from homogeneous random-coil configurations in the B-chain dimensions as well as in those of the A chains, and has also been extended to cover the case of diblock AB copolymers. Only planar morphology is considered, but qualitative conclusions reported herein are expected to hold for other morphologies as well. The focus is on interphase thickness ΔT, with predictions made also for separation temperature Ts and planar repeat distance D. Results are presented as systematic functions of copolymer composition (0 ≤ φA ≤ 1), total molar volume (25,000 ≤ Ṽ ≤ 4 × 106 cm3/g mol), block architecture (AB vs. ABA), temperature (298, 373 K), and for five different interphase composition profiles. In most cases, A represents a polystyrene block and B a butadiene block in these calculations. Predictions for ΔT increase with temperature and depend on architecture, profile, and Ṽ; comparisons with data are close, in the range 15-30Å. It is shown that Ts depends strongly on profile choice and φA, reaching a maximum in the φA midrange but always with φA 〉 0.5. The major parameter influencing D (at constant Ṽ) is architecture, with D(SB) ≈ 2D(SBS), and D(Ṽ) varies from D ∝ Ṽ0.75 at low Ṽ to D ∝ Ṽ0.5 at high Ṽ.
    Additional Material: 15 Ill.
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    Morphological studies of liquid-crystalline cellulose derivatives. I. Liquid-crystalline characteristics of hydroxypropyl cellulose in 2-hydroxyethyl methacrylate solutions and in polymer composites prepared by bulk polymerization (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1043-1052 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The formation of liquid-crystalline structure in hydroxypropyl cellulose (HPC) in the solvent 2-hydroxyethyl methacrylate (HEMA) is described. In addition, an attempt is made to preserve the ordered structure of HPC in a composite by polymerizing the solvent. Optical evidence, including refractive index, absorption spectra, polarized-light microscopy, and x-ray diffraction, indicates that HPC-HEMA solutions exhibit the cholesteric nature of the mesophase over limited concentration and temperature ranges. The polymer composite (HPC-PHEMA) prepared from the liquid-crystalline solution by polymerization of HEMA is endowed with anisotropic organization reflecting liquid-crystalline character. Detailed morphological observations of the composite by electron microscopy show many round particles composed of parallel-stacked, disklike lamellae, and aggregate bodies developed by coalescence of neighboring particles.
    Additional Material: 7 Ill.
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    Stress-optical behavior of poly(cis/trans-1, 4-cyclohexane dimethanol-alt-formaldehyde) (PCDO) networks (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1031-1041 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Two samples of poly(cis/trans-1,4-cyclohexane dimethanol-alt-formaldehyde), having fractions of trans configuration of cyclohexylene rings Ft = 0.1 and 0.7, were synthesized by polycondensation of the appropriate mixtures of glycols with paraformaldehyde. These two samples were crosslinked by a chemical reaction using 2,4-bis(p-isocyanatebenzyl) phenylisocyanate as the crosslinking agent. The stress-optical behavior of the resulting networks was studied at several temperatures in the range 10-80°C. The values of the optical configuration parameter Δα were 9.9 and 7.2 in units of 10-24 cm3 for Ft = 0.7 and 0.1, respectively. The temperature coefficient of this quantity was roughly zero. Theoretical analysis, performed using the rotational isomeric state model, proved that the only parameters that have an appreciable effect on the calculated values of Δα are those concerning the cyclohexane ring (i.e., Ft and the optical parameter ΓCC = ΔαCC - 2ΔαCH). Conformational energies, geometrical parameters, and contributions to the optical anisotropies from the oxymethylene oxide have no noticeable effect on the value of Δα calculated for the polymer. In fact, values of Δα calculated for the polymer at Ft = 0 and 1 are very close to those obtained, respectively, for cis and trans cyclohexane dimethylene. The theoretical values of Δα are roughly one order of magnitude lower than the experimental results; however, the theory reproduces satisfactorily both the variation of Δα with Ft and its temperature coefficient.
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    An investigation of the effect of sample preparation on the thermal behavior and the small-angle x-ray scattering of a polyurethane block copolymer (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1065-1077 
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    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 varying sample preparation parameters on the thermal behavior and on the small-angle x-ray scattering (SAXS) properties of a polyether polyurethane were investigated. The polyurethane studied was a methylene bis(p-phenyl isocyanate) (MDI)/butanediol/poly(tetramethylene oxide) (PTMO) system synthesized in a 6/5/1 mole ratio by a two-step solution polymerization. The PTMO had a nominal molecular weight of 2000. The samples were compression molded under different conditions for the SAXS experiments. The preparation parameters studied included molding time and temperature, sample thickness, and quenching rate from the molding temperature. The molding temperature has the greatest effect on the SAXS data. In this case the domain size was observed to increase as the molding temperature increased from 130 to 200°C. The thermal properties were also found to be strongly dependent on the molding temperature, as measured by differential scanning calorimetry (DSC). An endotherm related to the annealing that occurs during the molding process appears in each sample near the molding temperature. The other preparation parameters have little or no effect on the SAXS and thermal properties of this sample.
    Additional Material: 2 Ill.
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    Dynamic structure factor of a dilute solution of dumbbells in simple shear flow (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1079-1083 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1985.180230517
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    Mechanochemical reactions in an epoxy resin system (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1087-1097 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Mechanical degradation of the MY720/Eporal (CIBA GEIGY) epoxy resin system was investigated by stress mass spectrometry. Resin coupons were strained to fracture in a unique mass spectrometer system in which the clamping jaws of an Instron tensile tester are located inside the ion-source housing of a time-of-flight mass spectrometer. Several compounds are released at the instant of fracture. However, only one compound, SO2, is not an impurity in either the starting material or the cured resin. A sensitive gas-chromatographic technique was used to search for SO2 indigenous to the starting material and the unstressed cured resin. The data indicate that SO2 is a mechanochemical reaction product generated during main-chain bond cleavage of the glassy epoxy resin network.
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    The effect of heating rate on the melting of polytetrafluoroethylene (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1177-1185 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: When virgin polytetrafluoroethylene is heated at intermediate rates, two melting peaks are observed. As the heating rate is increased, the higher-temperature peak grows at the expense of the lower-temperature one without any significant change in the total heat of fusion. It is suggested that the higher-temperature peak represents a transition to a strained melt which subsequently changes to the more stable equilibrium melt. After recrystallization from the melt, there is only a single melting peak which occurs at a lower temperature than peaks for the virgin polymer. All of these transitions are subject to superheating.
    Additional Material: 9 Ill.
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    The determination of longitudinal crystal moduli in polymers by spectroscopic methods (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1201-1215 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Experimental methods for determining longitudinal crystal moduli of polymers were evaluated in light of recent proceesing methods that produced macroscopic Young's moduli which exceeded ultimate values as found by the x-ray diffraction method. The spectroscopic techniques of Raman and coherent inelastic neutron scattering yielded higher longitudinal crystal moduli than x-ray diffraction, and from calculations described herein it is concluded that these spectroscopic values are better estimates of the maximum Young's moduli in fully aligned and crystalline polymeric materials.
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    Molecular interactions in the poly(vinyl chloride)-di-n-butylphthalate system determined by infrared spectroscopy (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1187-1192 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Infrared studies of the poly(vinyl chloride) (PVC)/di-n-butylphthalate (DBP) system are reported. Spectra of DBP in different solvents seem to be indicative of the ability of DBP to interact with PVC chains in the same way as with polyesters and of competitive interactions between DBP molecules and DBP with PVC. Plots of the width at half-height of the carbonyl stretching vibration, measured at 25 and at -180°C, as a function of composition, show a sudden change of slope at about 60% PVC concentration by weight, indicating that above this polymer composition interaction between DBP and PVC dominates that between DBP molecules. This change corresponds to a “singularity” observed in the dependence of the glass transition temperature on composition.
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    Orientation behavior of high-modulus polyoxymethylene produced by microwave heating drawing (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1193-1200 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The orientation behavior of high-modulus polyoxymethylene tapes produced by tensile drawing with microwave heating has been investigated over the draw ratio range 10-29. Young's modulus E increases monotonically with draw ratio λ and reaches 55 GPa. The volume fraction of taut tie molecules (TTMs) in the amorphous phase has been estimated by using a Takayanagi model for oriented tapes. The increase in E at draw ratios of less than 10 is mainly due to the increase in crystalline orientation (crystalline orientation function, 0.00 → 0.99). The increase in E at draw ratios of more than 10 is due to the increase both in crystallinity (volume-fraction crystallinity, 0.84 → 0.95) and in TTM (TTM fraction, 0.14 → 0.40). The maximum Young's modulus obtainable by this method of drawing is estimated to be ca. 72 GPa from the relation between 1/E and 1/λ2.
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    Interpretation of photon correlation spectroscopy data: A comparison of analysis methods (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1393-1447 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Properties of solutions and colloidal suspensions such as molecular and particle dynamics, diffusivities, and size distributions may be determined through dynamic light-scattering experiments. Here a number of methods for predicting the details of the linewidth distribution from photon correlation spectroscopy data are reviewed. Their performance on simulated data (with and without noise added) and experimental data from polystyrene latex standards (including a mixture of two standards) is compared. Methods which do not assume a specific form for the distribution are considered. These include cumulants, histograms, exponential sampling, subdistributions, a non-negatively constrained histogram, and Provencher's constrained regularization. Constrained regularization was found to be most robust to noise present in the autocorrelation function and therefore most reliable for analyzing experimental data; however, the method sometimes oversmoothed the distribution. For bimodal distributions the histogram method performed well in our testing, especially when the approximate peak locations were known a priori. Two linear least-squares fitting methods, exponential sampling and the non-negatively constrained histogram, yield accurate values for the overall mean and standard deviation and can be implemented easily on a microcomputer. The linear subdistribution method, although computationally fast, sometimes was not as accurate as other methods.
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    Small-angle polarized light scattering by spherulites (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1467-1476 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The light-scattering matrix for a three-dimensional spherulite is derived within the Ray-leigh-Gans-Debye light-scattering approximation. New expressions for the polarized, small-angle light-scattering intensities IVV and IVH are derived from the scattering matrix. These expressions are compared with the IVV and IVH expressions derived for a spherulite by Stein and Rhodes. For the case of a weakly anisotropic spherulite having an average refractive index mismatch with its surroundings, the two sets of expressions predict different IVV and IVH intensities. In particular, our expressions show that the IVVand IVH patterns usually attributed to the spherulitic anisotropy and crystallinity are also predicted for an isotropic sphere. This is in accord with recent experiments.
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    Crystallographic changes in cryogenically pulverized polymers (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1449-1466 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Cryogenic pulverization of polymers in liquid nitrogen results in a variety of physical and chemical changes, of which crystallographic transformations are among the earliest. These have been investigated in detail for isotactic polystyrene using x-ray and calorimetric techniques. Amorphization was found to occur rapidly, but with concomitant decreases in crystallite sizes of only a limited extent. These changes can to a large degree be reversed upon annealing at high temperature. Similar behavior is seen also in other polymers possessing stronger intermolecular cohesion, such as polyesters and polyamides. In polymers susceptible to mechanically induced phase transformations, cryogenic pulverization causes polymorphic changes en route to amorphization: these include formation of the monoclinic phase in polyethylene and of the β phase in poly(vinylidene fluoride). Based on these results, a model is proposed for the mechanism of pulverization that incorporates both thermal and mechanical effects; this model suggests a two-phase structure of the pulverized, particles, consisting of an amorphous skin that surrounds a damaged crystalline core.
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    Application of the method of brather for the determination of complex dielectric permittivity from measurements of isothermal polarization current (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1505-1511 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Some years ago, Brather proposed a method for calculation of the real and imaginary parts of the complex dielectric permittivity starting from measurements of isothermal polarization current. This method shows some advantages over the Hamon method, which is normally used. Both methods are applied in this work to the β relaxation of poly(butyl methacrylate). It is concluded that, with the usual accuracy of measurement, a combination of the two methods is advisable; Hamon's method is taken to be a first approximation to that of Brather. Results following the two procedures are compared, and their respective advantages and disadvantages are discussed.
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    Model calculation of the thermal conductivity of polymer crystals (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1495-1504 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A linear lattice model without adjustable parameters provides an accurate description of the magnitude and temperature dependence of the thermal conductivity of Kc of polyethylene crystals parallel (∥) and perpendicular (⊥) to the chain direction. The model shows that heat is transported principally by phonons polarized transverse (T) to the chain direction. Phonons polarized longitudinal (L) to the chain direction contribute about 20% to the heat transport along the chain direction, and negligibly to heat transport perpendicular to the chain direction. Thermal resistance is caused by LTT three-phonon umklapp scattering in the parallel direction, and by TTT scattering in the perpendicular direction. The calculated values for large crystals are Kc∥ = 465 W m-1 K-1, Kc∥ = 0.16 W m-1 K-1 at 300 K, in agreement with experimental estimates and implying an anisotropy ratio of Kc∥/Kc⊥ ≈ 3000. The axial thermal conductivity of polyethylene crystals is extremely high and comparable to that of copper. Comparison with experimental data on semicrystalline samples at lower temperature yields a crude value of mean free path for boundary scattering of about 50 nm, agreeing in order of magnitude with the size of crystalline blocks.
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    Analysis of the effect of electrical conductance of ferroelectric polymers on D-E hysteresis curves measured by the sawyer-tower method (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1513-1521 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The D-E (electric displacement vs. field) hysteresis curve of a ferroelectric polymer is conventionally measured by the Sawyer-Tower method. The effect of the electrical conductance of the polymer on the measured hysteresis curve is theoretically analyzed and a new method is proposed for elimination of the error arising from the conductance. Examples of original and corrected hysteresis curves of vinylidene fluoride-trifluoroethylene copolymer are presented.
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    Study of poly[bis(p-toluene sulfonate) diacetylene] films prepared by a modification of the Langmuir-Blodgett technique (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1523-1532 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Coherent this films of poly[bis(p-toluene sulfonate) diacetylene] were successfully formed by modified Langmuir-Blodgett techniques using two methods: (i) Photopolymerization of the monomer film at the gas/liquid interface and then transfer to a solid substrate, and (ii) transfer of the monomer film to the solid substrate and subsequent photopolymerization on the substrate itself. The films thus obtained were characterized by traditional force-area isotherms while on pure water subphases. Segments were transferred at either 1 or 10 dyn/cm surface pressure, in different stages of photopolymerization, to glass or germanium substrates. The films on the substrate were characterized by the methods of multiple attenuated-internal-reflection infrared spectroscopy, ellipsometry, contact-potential measurement, and laser Raman spectroscopy. Our results show that the films are multimolecular and about 100 Å thick. Of special interest were the observation of significant anisotropy of oriented dipoles and the ability to obtain excellent spectral data for these very thin oriented films. Raman spectroscopic features are similar to those observed for the bulk polymer, even in the low-frequency region. Polarized Raman spectroscopy confirmed the presence of local anisotropy in these films.
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    Wetting properties of polyacetylene films (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1555-1562 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The wetting characteristics of free-standing polyacetylene films were determined by using a standard series of wetting liquids. As-prepared films of cis-polyacetylene were found to contain a significant polar contribution to the surface free energy, which became nearly entirely dispersive upon thermal isomerization to the trans form. Both isomeric forms are characterized by a critical surface tension of wetting γc ≈ 51 mN/m, which is considerably higher than that normally obtained from organic polymers. These results have been interpreted with respect to surface oxidation and tested by examining an oxidized film.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1985.180230808
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    Rough-surface crystallization: Some applications to poly(ethylene oxide) (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1533-1554 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A model incorporating a rough (disordered) crystal growth surface is capable of treating many of the observations and measurements on the crystal growth of short chains of poly(ethylene oxide) from the melt. A simple preliminary treatment if presented which aims primarily to analyze the growth rate data within one growth “branch,” i.e., for a regime in which crystal thickness is approximately constant. Under these conditions the growth rate is approximately linear with crystallization temperature, as expected for rough growth surfaces, but not for smooth (faceted) ones. Simulation results are included which are in agreement with a simple equation and with experiment. The analysis enables the growth rates for different branches to be compared in a systematic way. A very steep decrease in growth rate with increasing crystal thickness is clearly illustrated, together with some influence of molecular weight. The general trend for chain folding can be seen as a consequence of this steep decrease. Parallel work on systems in which crystal thicknesses vary continuously with crystallization temperature led to the realization that “rounding off” will occur at the crystal perimeter and that this will give rise to an entropic barrier for the crystal advance. This argument is presented in the context of extended-chain and once-folded crystallization, from which it is clear that growth rates should be much lower as crystal thicknesses increase, and for folded-chain as compared with extended-chain crystals. Different morphologies are interpreted in terms of changes in surface structure which are probably due to kinetic as well as equilibrium effects.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1985.180230807
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    Unit-cell dilation in model ethylene copolymers (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1563-1572 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Single crystals of model ethylene copolymers have been grown in dilute solution. The effects of narrow molecular weith distribution (MWD) and a perfectly random distribution of ethyl branches (ca. 17 per 1000 main-chain carbon atoms) on the unit cell of this ethylene copolymer analog were examined. X-ray diffraction on dried powder samples revealed expansions of up to 1.5% in a and 0.5% in b. a increased as a mild function of molecular weight; the dependence of b on MW was not as clearly defined. Electron diffraction studies on isolated suspensiongrown single crystals yielded lattice parameters much more strongly expanded. The large expansion in the basal plane of the unit cell is hypothesized to be accompanied by a fore-shortening of the projected c-axis distance. This is accomplished by and orthorhombic-to-hexagonal polymorphic transformation in which the chains are hypothesized to adopt a disordered helical conformation. The driving force for this transformation is electron irradiation damage of the single-crystal specimens. The rapidity of the transformation is believed to be due to the model polyethylene crystals being in a higher-energy, defect-containing condition prior to irradiation.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1985.180230809
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    Relationship between the functional group concentrations and the infrared reflection-absorbance of polyacrylonitrile films (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1573-1584 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The optical constants n and k of polyacrylonitrile (PAN) were determined in the infrared region 3100-700 cm-1 by using theoretical calculations and experimental reflectance spectra. Tests of the validity of the results obtained showed excellent agreement between the measured and the predicted k values. One k value was determined experimentally (k = 0.6155 at V = 2285 cm-1) and showed excellent agreement with that calculated theoretically (k = 0.6153). The p-polarized light was found to be more sensitive than the s-polarized light to the absorbance of PAN films at 77° incidence angle. This sensitivity increased rapidly with p-polarized light for film less than 0.5 μm thick. From the optical constants obtained for p-polarized light at 77° angle of incidence, the sensitivity of the infrared reflection-absorbance (IR-RA) measurements to changes in the functional group concentrations in PAN films was determined for film thicknesses in the region 0.01-10.0 μm. The IR-RA measurements of the —C≡N group and the skeletal mode were for a PAN film thickness of about 0.1 μm.
    Additional Material: 10 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1985.180230810
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    Electron-beam-induced fracture of polymers (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2273-2293 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: When a notched polymeric material is stressed, the notch opens into a wide crack tip, exposing a region of high stress concentration. The consequences of electron bombardment of the tip of such a stressed material under vacuum are explored here for the first time. Evidence is presented for electron-induced crack growth at stress far below that needed for crack growth due to stress alone. The electron current densities used in these experiments are sufficiently small that thermal heating of the zone near the crack tip is minimal. To provide information on the phenomena involved, we present simultaneous measurements of electron current, gas pressure, and sample load in response to periodic bombardment of the sample. Experiments involving the bombardment of un-notched polymers under stress are also described. Fractography of the unique structures obtained by fracture due to the combination of electron bombardment and stress are presented and interpreted in terms of a crosslinking mechanism.
    Additional Material: 14 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1985.180231103
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    The application of gas barrier and thermal expansion techniques to study structural changes on annealing (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2295-2306 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Changes occur in the structure of drawn polyethylene when it is annealed at temperatures close to that of the drawing process. Measurements have been made of the oxygen barrier properties and of the thermal expansion coefficient in the draw direction on samples over a wide draw ratio range both before and after annealing at various temperatures. The results are augmented by density, creep modulus, and shrinkage observations. All samples show a drop in the barrier properties and an increase in the thermal expansion after annealing. However, whereas high-draw-ratio samples show relatively small effects, the changes observed at low draw ratios are very large, with some barrier properties even lower than those of the isotropic feedstock. The effects are larger at the higher annealing temperatures. The diffusion and expansion measurements are greatly influenced by the amorphous regions in the polymer; these results are interpreted as a relaxation of internal stresses giving rise to greater accessibility of the intercrystalline regions. Further experimental work is required to exploit these techniques.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1985.180231104
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    Polydimethylsiloxane-polyurethane elastomers: Synthesis and properties of segmented copolymers and related zwitterionomers (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2319-2338 
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    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 polyurethane block polymers based on hydroxybutyl-terminated polydimethyl-siloxane soft segments of molecular weight 2000 were synthesized. The hard segments consisted of 4,4′-methylenediphenylene diisocyanate (MDI) which was chain extended with either 1,4-butanediol (BD) or N-methyldiethanolamine (MDEA). The MDEA-extended materials were ionized by using 1,3-propane sultone. The weight fraction of hard segments was in the range 0.13-0.39. The morphology and properties of these polyurethane elastomers were studied by a variety of techniques. All of these short-segment block copolymers showed nearly complete phase separation. The zwitterionomer materials exhibited ionic aggregation within the hard domains. Hard-segment crystallinity or ionic aggregation did not affect the morphology. Hard-domain cohesion was found to be a more important factor than hard-domain volume fraction in determining the tensile and viscoelastic properties of these elastomers.
    Additional Material: 13 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1985.180231106
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    Polyethylene fiber formation in tubular flow. II. Discussion of precursor formation and nucleation time analysis (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2359-2368 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: This is a continuation of the preceeding paper, Part I, and presents a discussion of the nature of the precursor structure formation process observed in the flow-induced crystallization experiments described in I. A discussion of stress-induced crystallization theory as applied to these experiments is also given and a first-order analysis of crystal nucleation rates is presented. Conclusions regarding the nature of flow-induced crystallization and our current ability to quantitatively model the overall process are also presented.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1985.180231108
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    Polyethylene fiber formation in tubular flow. I. Observations of growth pattern and fiber properties (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2339-2358 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The process of seeded growth of fibrillar polyethylene crystals has been studied in a tubular flow geometry for 0.01-wt % solutions of a high-molecular-weight polyethylene in xylene. The transformation sequence has been followed visually by using polarized-light illumination in conjunction with a video camera. Data are presented to show that transformation is initiated by the formation of a concentrated, unoriented, amorphous precursor fiber within which oriented birefringent crystals subsequently grow in consequence of the stresses transmitted by the flowing solution. Time constants for the precursor formation, birefringence initiation, and completion of birefringence were measured as functions of temperature and flow rate over a range of growth conditions. Wide-angle x-ray diffraction, overall birefringence, and optical hot-stage melting data were also obtained on the grown fibers. The net result of these observations is to conclude that fibrillar crystal growth during flow is always preceded by the formation of a liquidlike phase transformation which produces the concentrated, unoriented precursor. Subsequent orientation is in consequence of stress-induced crystallization with overall fiber orientation showing an increase with solution flow rate at a fixed temperature and a decrease with temperature at a fixed flow rate. At higher temperatures and lower flow rates, birefringence develops in an oscillatory fashion, indicating a remelting process possibly due to slippage of trapped chain entanglements formed by flow. A discussion is given of the implications of these observations for the understanding of flow-induced structure development, phase transformation, and oriented crystallization; this is expanded upon in a companion paper, Part II.
    Additional Material: 10 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1985.180231107
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    Estimation of the equilibrium modulus of rubber networks by nonlinear regression analysis (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2377-2385 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A nonlinear regression analysis is presented to estimate the equilibrium modulus of relaxing rubber networks from G'(ω) or G(t) data. Various semiempirical curve-fitting equations are tested with two-function minimization algorithms.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1985.180231110
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    Studies on the morphology and structure of aromatic polyester films (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2387-2393 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Oriented films of an aromatic polyester containing a triad ester mesogenic group and a decamethylene flexible spacer were studied by polarized light microscopy, small-angle light scattering, and polarized infrared spectroscopy to determine the nature of the alignment of the polymer chains, induced by shearing, which is responsible for the banded or striped morphology observed. The stripes are apparently composed of fibrils arranged in a zigzag manner containing polymer chains packed in a highly ordered, parallel alignment at an angle of ±26° to the shearing direction.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1985.180231111
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    A model for radiation-induced changes in ultrahigh-molecular-weight polyethylene (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2407-2409 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1985.180231113
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    Translational diffusion of polystyrene in cyclohexane at infinite dilution from 283 to 348 K (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2457-2468 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The translational diffusion coefficients are reported for polystyrenes with molecular weights 2000, 4000, and 9000 in cyclohexane at infinite dilution from 283.2 to 348.2 K. The results suggest that the hydrodynamic radii stay constant to within ±3% and that the real chain for molecular weight 9000 at 308.2 K is well represented by a Gaussian or Monte Carlo model involving the idea of statistical steps. Furthermore, the success of Hildebrand's free-volume empiricism has led to a correlation between Dμ0/T and M which represents the observed diffusivities to within ±2%.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1985.180231204
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    Tube relaxation: A quantitative molecular model for the viscoelastic plateau of entangled polymeric mediaThis paper is dedicated to Dr. Pierre Thirion on the occasion of his retirement. (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2423-2442 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The relaxation of an entangled polymeric medium in the viscoelastic plateau is investigated theoretically by using the slip-link representation of topological constraints. In addition to the chain retraction process introduced by Daoudi and investigated theoretically by Doi, we show that two processes contribute significantly to the relaxation: The first, “equilibration across slip-links,” is a longitudinal reequilibration between parts of the chain which have been differently extended or compressed, depending on their initial orientation relatively to the strain tensor. The second, “tube relaxation,” is a mean-field representation of the loss of topological constraints on one chain due to the retraction of the others. Closed analytical expressions for the stress accounting for these three processes are derived and compared with previous theories: the relaxation should be much more progressive than previously predicted, and the terminal time for retraction is reduced significantly by tube relaxation.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1985.180231202
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    Evaluation of theories for diffusion in polymer-solvent systems (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2469-2475 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A method is proposed for examining differences in the predictive capabilities of three versions of the free-volume theory of polymer - solvent diffusion using only a small amount of diffusivity data. The utility of the method is illustrated using a limited diffusivity data set for the methanol-poly(vinyl acetate) system.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1985.180231205
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    Temperature dependence of the crystal structures of nylon 11 (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2477-2482 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Careful examination of x-ray diffraction patterns from melt-crystallized nylon 11 films show significant discrepancies with the proposed α-form structure. These discrepancies do not disappear after the samples have been annealed. The temperature dependence of the d spacings of the two strongest peaks show further evidence that the melt-crystallized and solution-cast films (α form) possess different crystal structures. These results suggest a different crystal structure for the melt-crystallized films; this would help explain the rather low piezoelectric response of these films and also the failure to observe a rapid decrease in polarization at the transition temperature.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1985.180231206
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    Kinetics of wetting of a glass surface by molten polyethylene: An empirical approach (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2499-2504 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The spreading kinetics of molten polyethylene was studied on a flat type A glass surface. Empirical equations are known in the literature which fit the experimental data only at short times. We present a relationship between the surface free energy and the shape of the melt drop interpreted by the θ contact angle. Relating the experimental θ values obtained at different times with the surface free energy (F), we obtain curves F,t. Using isothermal data at 150°C, we could fit them with a linear relationship between In (F-F∞)/(F0-F∞) and In t/t0, where o and ∞ are related to initial and equilibrium conditions.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1985.180231208
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  • 100
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    Crazing as quasifracture in an oriented viscoelastic medium (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 2579-2597 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Crazes of different types occur in polymeric systems. Long, sparse crazes develop in less oriented molecular systems, while fine, short, dense crazes occur in highly oriented molecular systems. Different crazing mechanisms and different models may have to be studied for a better understanding of these differences. However, in this report, using one model and one theory, an analysis has been made of the differences in the geometry of craze development. By emphasizing the mechanism of molecular orientation, it is found that the basic differences are essentially attributable to the variation of the anisotropy of the material system as a result of large deformation rather than to any fundamental differences in the crazing mechanism.
    Additional Material: 10 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1985.180231214
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