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  • 1
    Electronic Resource
    Electronic Resource
    Microstructure and unit-cell orientation in α-polypropylene (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 97-110 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The microstructure of melt-grown dendritic aggregates of the monoclinic α phase of isotactic polypropylene has been examined by optical microscopy, electron microscopy, and electron diffraction. Whereas the tightly crosshatched structure of such dendrites grown in the usual manner from the melt had not heretofore permitted unequivocal determination of unit-cell orientation, crystallization on mica at high temperatures eliminates this problem by suppressing branching and allowing lamellae to grow uninterruptedly to many micrometers in length. In this manner, it is shown that the preferred growth direction in single crystals of α-polypropylene is a*. X-ray diffraction analysis of unidirectionally crystallized specimens shows that the a* axis becomes radial in spherulites of this polymorph. Implications of this growth axis in terms of the branching model and of the crystallographic identification of the amorphous surfaces are discussed. Addition of large amounts of melt diluents is found to impart a distinct curvature to the dendritic crystals, causing their concave sides to face preferentially toward the centers of the resulting spherulitic aggregates.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1983.180210107
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  • 2
    Electronic Resource
    Electronic Resource
    Dynamics of adsorbed polymer chains subjected to flow: The dumbbell model (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 151-157 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dumbbell model of an adsorbed polymer segment is analyzed in order to investigate the response of such segments to a velocity gradient imposed at the solid/liquid interface. It is demonstrated that exact expressions for the time-dependent moments of the distribution function describing the conformation can be obtained. Both a dangling end and an attached loop can be represented and several bulk properties of a polymer film subjected to flow are evaluated.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1983.180210111
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  • 3
    Electronic Resource
    Electronic Resource
    The numerical solution of fujita's integral equation to provide estimates of molecular weight distributions (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 123-139 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A standard model of the behavior of polymers under ultracentrifugation results in Fujita's equation for their molecular weight distribution. Fujita's and related equations are examples of Fredholm integral equations of the first kind and are thus ill posed. Two methods are described for solving the equations numerically and hence providing estimates of the molecular weight distribution. The first method involves expanding the distribution in terms of orthogonal polynomials whose coefficients are calculated from estimates of the moments of the distribution. In the second method the distribution is reconstructed by using matrix singular-value decomposition techniques combined with an approximant expressed as a sum of B-splines. The potential and practical limitations associated with the methods are illustrated by numerical results from a series of tests on four problems designed to represent distributions with different modal properties.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1983.180210109
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  • 4
    Electronic Resource
    Electronic Resource
    A structural model for high-modulus polyethylene derived from entanglement concepts (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 165-188 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Starting from the concept that the entanglement network is a controlling factor in polymer deformation, a molecularly based model has been constructed for polyethylene, drawn or extruded to high extension ratios λ. It predicts the experimentally observed form of the increase of Young's modulus E with λ: E-1 = B + Cλ-2. The model structure consists of imperfect crystalline microfibrils 10-30 nm in diameter and length αλ2, about 1 μm at λ = 30. The microfibrils terminate at clusters of entanglements, and are embedded in a matrix of low modulus. This structure is very similar to that derived from solution-grown shish-kebab material. Available melting-point data for highly extended material fit the structural model well.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1983.180210201
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  • 5
    Electronic Resource
    Electronic Resource
    Concentrated solutions of polydisperse rodlike polymers in the isotropic and lyotropic liquid-crystalline phases. II. Model simulation of the dielectric relaxation behavior of poly(n-alkylisocyanates) in toluene and comparison with experimental results (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 213-231 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A simulation has been made of the dielectric relaxation behavior of poly(n-hexylisocyanate) in solution covering the isotropic, biphasic, and anisotropic ranges. The simulation incorporates the Flory-Abe statistical mechanical theory for the phase behavior of rodlike macromolecules in solution and the Warchol, Vaughan, Wang, and Pecora theory for the dynamics of a rodlike molecule in a virtual cone prescribed by the neighboring molecules. It is shown that asymmetric Gaussian, Gaussian, or Poisson distributions of molecular weight do not lead to dielectric behavior of the type observed experimentally by Moscicki, Williams, and Aharoni but addition of a high-molecular-weight “tail” to such distributions and taking account of the dependence of relaxation time on molecular length gives a simulation of the dielectric increment Δε, the loss maximum ε″m, and frequency of maximum loss fm, which vary with polymer concentration in a manner entirely consistent with the experimental data.
    Additional Material: 16 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1983.180210204
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  • 6
    Electronic Resource
    Electronic Resource
    Photon correlation spectroscopy of polystyrene as a function of temperature and pressure (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 605-611 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Photon correlation spectroscopy is employed to study the slowly relaxing density and anisotropy fluctuations in bulk atactic polystyrene as a function of temperature from 100 to 160°C and pressure from 1 to 1330 bar. The light-scattering relaxation function is well described by the empirical function φ(t) = exp[-(t/τ)β], where for polystyrene β = 0.34. The average relaxation time is determined at each temperature and pressure according to 〈τ〉 = (τ/β)Γ(1/β) where Γ(x) is the gamma function. The data can be described by the empirical relation 〈τ〉 = 〈τ〉0 exp[(A + BP)/R(T - T0)] where R is the gas constant and T0 is the ideal glass transition temperature. The empirical constant A/R is in good agreement with that determined from the viscosity or the dielectric relaxation data (1934 K). The empirical constant B can be interpreted as the activation volume for the fundamental unit involved in the relaxation and is found to be comparable to one styrene subunit (100 mL/mol). The quantity B appears to be a weak function of temperature. The use of pressure as a tool in the study of light scattering near the glass transition now has been established.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1983.180210410
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  • 7
    Electronic Resource
    Electronic Resource
    Thermal annealing of doubly oriented nylon 11 in contact with formic acid (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 625-645 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The most striking feature of the mechanism of thermal annealing of doubly oriented samples of low-density polyethylene (LDPE) and probably of high-density polyethylene (HDPE) is a progressive tilt of lamellar crystals around their crystallographic b axis. Such a rotation does not occur on thermal annealing in doubly oriented nylons. However, this rotation mechanism occurs during the thermal annealing of doubly oriented samples of nylon 11 in contact with a solvent below its dissolution temperature. As for oriented samples of polyethylene (PE), a correlation between the changes of macroscopic dimensions and long spacing obtained from the small-angle x-ray pattern is difficult to establish. In doubly oriented samples of nylon 11, the basal faces of the lamellar crystals are parallel to the a axis of the unit cell. Nevertheless, simple Miller indices cannot be assigned to the basal planes of the lamellae. On thermal annealing in formic acid, the basal planes of the lamellar crystals are, in some cases, parallel to (00l) planes. Annealing in formic acid at room temperature induces a phase transition: the chain c axis remains oriented along the rolling direction and the (00l) planes become parallel to the limiting planes of the lamellar crystals. Bulk doubly oriented samples of nylon 11 annealed in formic acid just below the “dissolution temperature” have the same texture of orientation as filter mats of single crystals grown from dilute solution; moreover, as these bulk specimens remain doubly oriented, they can be used for further physicochemical investigations. The usual interpretation of the small-angle x-ray pattern is also discussed on the basis of the results reported in this paper.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1983.180210412
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  • 8
    Electronic Resource
    Electronic Resource
    Optical absorption spectrum of PMMA via laser calorimetry (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 647-655 
    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 absorption spectrum of poly(methyl methacrylate) (PMMA) has been obtained in the wavelength range 570-780 nm via laser calorimetry (employing a dye laser source). Because of the low thermal conductivity of PMMA, the complete solution to the heat conduction equation (carried out numerically) was required in the analysis of the data. At the wavelength of minimum absorption (near 647 nm), the absorption coefficient had the value 153 dB/km.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1983.180210413
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  • 9
    Electronic Resource
    Electronic Resource
    Thermal expansion of oriented poly(methyl methacrylate) (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 657-665 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The thermal expansivities along (α∥) and perpendicular (α⊥) to the draw direction of poly(methyl methacrylate) (PMMA) with extrusion draw ratios 1 ≤ λ ≤ 4 have been measured between 150 and 298 K. As λ was increased from 1 to 4, α∥ decreased 2-3 times, whereas α⊥ increased only 20-35%. The orientation function f calculated from thermal expansivity using the aggregate model is found to change linearly with birefringence, indicating that each property provides a sensitive measure of molecular orientation. For PMMA, however, only thermal expansivity can give an absolute f, with results at 150 K in reasonable agreement with previous studies using other techniques. At higher temperature, i.e., above ambient, PMMA side-group motions are excited, expanding volume, and calculations based on the aggregate model may not be valid.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1983.180210414
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  • 10
    Electronic Resource
    Electronic Resource
    Preoriented poly(ethylene terephthalate) yarns: Influence of the gauche-trans transformation on crystallization (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 717-723 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Effects of macromolecular orientation on the crystallization of preoriented poly(ethylene terephthalate) filaments were studied. Infrared spectrophotometry and differential scanning calorimetry analyses showed that macromolecular segments in the trans conformation begin to crystallize below the glass transition temperature. Since filaments prepared by stretching at room temperature have different degrees of orientation, it is possible to evidence correlations between crystallization from an anisotropic matrix and the resulting morphology.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1983.180210504
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  • 11
    Electronic Resource
    Electronic Resource
    Localized volume deficiencies as an effect of spherulite growth. I. The two-dimensional case (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1299-1312 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Two-dimensional spherulite growth leads to the encirclement of regions of molten polymer in a polymer film. On further crystallization localized volume defects arise, resulting in thin spots in the film. Since this effect lowers the mechanical strength of films, we call these volume defects “weak spots.” A computer program is developed to evaluate the number, size, and shape of such volume defects for athermal, thermal, and mixed modes of primary nucleation of spherulites. It is shown that the total area of weak spots exceeds 10% of the sample area for all types of nucleation studied. The largest weak spots arise in samples crystallized via athermal and mixed nucleation; their size is of the same order as that of an average spherulite. Formation of weak spots is observed in thin films of poly(ethylene oxide) and poly(methylene oxide). The disadvantageous role of weak spots is confirmed by observation of electric breakdown occurring preferentially in weak spots in polypropylene films.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1983.180210803
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  • 12
    Electronic Resource
    Electronic Resource
    Thermoluminescence from extended-chain crystals of polyethylene (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1347-1356 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Thermoluminescence (TL) has been observed in γ-irradiated extended-chain crystals of polyethylene above room temperature. The TL curve, which exhibits four peaks at 50, 90, 120, and 140°C, is different from that given by folded-chain crystals, in both shape and intensity. In particular, a shape, strong glow peak is observed at 140°C, corresponding to the melting temperature of the extended chain crystals. These results are discussed in relation to independent measurements by differential scanning calorimetry and electron spin resonance.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1983.180210807
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  • 13
    Electronic Resource
    Electronic Resource
    Localized volume deficiencies as an effect of spherulite growth. II. The three-dimensional case (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1313-1322 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: As in the two-dimensional case, the density change due to crystallization leads to a buildup of internal strain in some regions of a polymer melt occluded by growing spherulites. The occluded parts of the sample are called “weak spots.” Computer simulation of spherulite growth in bulk samples shows that the largest weak spots have the size of an average spherulite. The total volumes of weak spots are 0.47, 0.094, and 0.119% of the sample for athermal, thermal, and mixed primary nucleation, respectively. The weak spots in the bulk material exhibit distance correlation. Within weak spots, internal strain is released (Raman spectroscopy), and holes develop. Polypropylene bulk spherulite samples contain holes distinctly visible under a microscope with infrared optics and illumination. The number of visible holes is in agreement with the computer prediction. The increase of impact strength with decreasing spherulite size is explained in terms of changes in the number and size of weak spots.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1983.180210804
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  • 14
    Electronic Resource
    Electronic Resource
    Ab initio calculation of polyethylene deformation including electron correlation effects (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1341-1346 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The longitudinal acoustic elastic modulus of polyethylene has been calculated with the aid of the ab initio crystal orbital method applying corrections also for electronic correlation effects. The basis set and correlation dependence of the elastic modulus have been investigated. The best theoretical value of 305 GPa of this modulus is in reasonable agreement with the published experimental values. At an elongation of ca. 0.1 the deviation from Hooke's law is found to be substantial.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1983.180210806
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  • 15
    Electronic Resource
    Electronic Resource
    Effect of amorphous sequences on the longitudinal acoustic modes in partially crystalline polymers. I. Transfer matrix method (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1357-1380 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A novel theoretical scheme is developed which enables the determination of the LAM-like vibrations of polymer chains made up of crystalline and amorphous parts as they occur in partially crystalline structures. The boundary conditions effective at the junction points are formulated in terms of the compliances of the associated amorphous sequences. These compliances can be derived from their eigenfrequencies and eigenvectors in a disconnected state. The treatment uses a matrix formalism which can be extended to include bending and torsional motions in a general state of vibration of the crystalline stem. A first numerical example demonstrates that the LA mode of a crystalline stem can be strongly perturbed by the coupling to the adjacent amorphous sequences. Interpretation of frequencies and line shapes of observed LA modes should always include these coupling effects; their neglect can lead to considerable errors.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1983.180210808
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  • 16
    Electronic Resource
    Electronic Resource
    EXAFS studies of nickel nafion ionomers (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1389-1401 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Nafion membranes neutralized with Ni2+ have been examined by extended x-ray absorption fine-structure (EXAFS) and x-ray absorption near-edge-structure (XANES) spectroscopy. The results indicate that in both the dry and water-soaked membranes, the nickel is in an octahedral site with six oxygen atoms as nearest neighbors. The degree of disorder in the Ni—O distance is comparable to that in ionic crystals in both the dry and hydrated materials. A contribution from a second shell of neighbors is very weak in the dry samples but, surprisingly, this contribution is strongly accentuated in the hydrated membranes. The data indicate that this contribution is due to neighboring Ni2+ cations. Thus the water absorption seems to enhance the local ordering of the cation environment. The local structure does not depend strongly on the concentration of ionic groups in the materials.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1983.180210810
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  • 17
    Electronic Resource
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    Relationship between the cohesive strength and the tack of elastomers (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1415-1425 
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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 autohesion (tack) and cohesion of a random styrene-butadiene elastomer have been examined as a function of test temperature and speed using a T-peel geometry. Both properties have been reduced to a single master curve by horizontally shifting the data with the same set of shift factors. The cohesive strength increases with increasing reduced test rate RaT and appears to approach a plateau at the highest rates. Tack also increases with RaT but decreases abruptly at a critical rate and peeling the occurs in a stick-slip fashion. Tack again increases at sufficiently high test rates. In the range of rates where tack is maximized, its value is essentially the same as its cohesive strength. Above or below this range, tack is substantially less than the elastomer's cohesive strength. Mechanisms are proposed to explain why relative tack (i.e., tack divided by cohesive strength) is not a simple measure of the extent of completion of a tack bond and may indeed be equal to one in spite of incomplete tack bond formation.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1983.180210812
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  • 18
    Electronic Resource
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    Retardation of spherulitic growth rate in the crystallization of isotactic polystyrene due to the presence of nucleant (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1403-1413 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Although the rate of heterogeneous nucleation of crystallization in isotactic polystyrene, as studied by photomicroscopy, is markedly increased by addition of fine-particle silica, the rate of subsequent radial growth of spherulites formed is diminished. The latter observation is rationalized on the basis of a modified Hoffman-Lauritzen treatment wherein the nucleant is depicted as a quasicrosslink which impedes the transport of polymer segments.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1983.180210811
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  • 19
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    Properties of semidilute polymer solutions: Investigation of an optically labeled three-component system (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1381-1388 
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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 three-component system containing a polymer (2), a good solvent (1) for that polymer, and a second polymer (3) that is compatible with component (2) and isorefractive with the solvent (1) has been studied by static and dynamic light-scattering methods. In concentrated toluene (1) solutions of poly(vinyl methyl ether) (3), where appreciable chain overlap occurs and excluded-volume effects are reduced, polystyrene (2) may be studied in the dilute-solution limit. Consequently, these light-scattering measurements provide an explicit measure of both thermodynamic and hydrodynamic changes that occur as the total polymer concentration is increased from dilute to concentrated solution. Precise numerical coefficients, correct scaling exponents, the radius of gyration, and the effective hydrodynamic radius can be measured directly along with the observation of long-wave single-chain reptation motions and short-range cooperative motions in semidilute and concentrated solutions.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1983.180210809
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  • 20
    Electronic Resource
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    Thermal expansivity of oriented poly(ethylene terephthalate) (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1427-1438 
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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 linear thermal expansivity of poly(ethylene terephthalate) extruded at 50 and 90°C to extrusion ratios λ of 1-4.8 has been measured between 120 and 300 K. With increasing λ, the expansivity along the extrusion direction (α∥) decreases sharply, while that in the transverse direction (α⊥) shows a slight increase. For λ 〈 3, the large drop in α∥ and the accompanying increase in the axial Young's modulus E∥ can be ascribed to chain alignment in the crystalline regions and to an increase in number and tautness of intercrystalline tie chains. At higher λ, however, the crystalline orientation apparently becomes saturated, so that taut tie molecules are solely responsible for further changes in both α∥ and E∥. On the other hand, α⊥ is mainly determined by crystalline orientation for all λ, thus showing very little increase at large λ. For the highly oriented samples (λ ≥ 3), the Takayanagi model provides a reasonable description of the behavior of α∥ and α⊥.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1983.180210813
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  • 21
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    An analysis of local flow effects in flow-induced orientation and crystallization (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1473-1492 
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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: An analysis is presented of the effects of external flow kinematics on the so-called local flow in seeded, flow-induced crystallization and orientation. The flow field around a growing crystal or nucleation seed is modelled by the Stokes flow equations past a prolate ellipsoid of high aspect ratio. Exact solutions for various flow kinematics, worked out elsewhere by the singularity method, are applied here to the analysis of local gradients. The results show that along the symmetry axis of the spheroid, the extensional gradients which result for various free-stream velocity fields are primarily the result of the constant-velocity free-stream component. However, free-stream, extensional flow can significantly enhance the region of such high gradients. Along the symmetry plane of the spheroid, primarily shearing gradients result, with small extensional gradients occurring when the free-stream flow has extensional components. Results of chain extension and birefringence calculations are also presented and discussed.
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    Inclusion of mobile crosslinks and lateral crystallite growth in the theory of stress-induced crystallizationCorrected proofs received October 18, 1982 (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 45-53 
    Details
    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 stress-induced crystallization is broadened to include a reshuffling of crosslink positions as a result of changing sizes of crystalline domains and multiple crystallites of varying lateral dimensions (i.e., lateral growth). A continuous state of equilibrium throughout the amorphous component of the stretched network is postulated and, consequently, effected by requiring crosslinks to anchor about their most probable locations, which vary continuously as crystallization changes. Such features incorporated into Flory's model of stress-induced crystallization broaden its theoretical base, placing it on a stronger, more realistic foundation.
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    Crystallization under stress: A theory of fibrillar crystallizationCorrected proofs received October 18, 1982 (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 55-63 
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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 theory of crystallization in stretched polymer networks is developed. In it, four principal features are incorporated: (i) crosslinks are displaced by growing crystallites, (ii) network chains are constrained to positions compatible with fixed sample shape and volume, (iii) some network chains remain amorphous, and (iv) the relative direction of a chain through a crystallite may not be the same for all chains. The derived network force exhibits a V or U shape with changing temperature in the crystallization zone that is a close replica of the behavior of gutta percha networks. Postulates of fibrillar-lamellar transitions are not introduced into the calculations.
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    Structure-property relationships in polycaprolactone-polyurethanes (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 65-95 
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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-property relationships of polycaprolactone-based segmented polyurethanes were studied using differential scanning calorimetry (DSC), small-angle x-ray scattering (SAXS), wide-angle x-ray diffraction (WAXD), dynamic mechanical, and stress-strain testing. The materials studied varied in hard-segment type [4,4′-diphenylmethane diisocyanate/butanediol (MDI/BD) or 4,4′-dicyclohexyl methane diisocyanate/butanediol (H12MDI/BD)], soft-segment molecular weight (830 or 2000 MW polycaprolactone), hard-segment content (23-77% by weight), and thermal history. The materials with aromatic (MDI/BD) hard segments had semicrystalline hard-segment domains, while the materials with aliphatic (H12MDI/BD) hard segment had mostly amorphous domains. Materials with the shorter polycaprolactone soft segment (830 MW) exhibited thermal and mechanical behavior which indicated a considerable degree of hard- and soft-segment compatibility. The materials which contained a 2000-MW polycaprolactone soft segment exhibited better-defined microphase separation. SAXS was used to characterize the microphase structure of each system. The effects of hard-segment content and soft-segment molecular weight were similar for the aromatic (MDI) and aliphatic (H12MDI) hard-segment-based block copolymers. Changing the hard segment from aromatic to aliphatic gave materials with larger interfacial area and slightly higher tensile strength. A range of morphologies between isolated hard domains in a rubbery matrix and isolated rubbery domains in a hard matrix was observed.
    Additional Material: 19 Ill.
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    Radiation chemistry of polybutadiene and butadiene-styrene block copolymers. II. Kinetics and mechanisms of free-radical decay reactions (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 111-121 
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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 decay of free radicals produced in polybutadiene, polystyrene, and block copolymers of butadiene and styrene by γ irradiation at 77 K has been studied at -110°C in the case of polybutadiene and at -95°C for the other samples. The free-radical decay rate is best interpreted in terms of an equation based on a second-order decay mechanism of a fraction of the free radicals decaying in the presence of other nondecaying free radicals. Hydrogen gas accelerates the free-radical decay. Increase of radiation dose increases the fraction of the radicals that decay, while increase of the fraction of styrene segments decreases the decaying fraction. In pure polybutadiene the higher the cis content, the greater fraction of decaying free radicals, but the second-order decay constant is less in the high-cis-content polybutadiene and is also less at the higher dose, probably owing to the hindrance of the radiation-produced crosslinks on the free-radical decay. The decrease of the second-order constant with increase of dose is also true for all the block copolymers studied.
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    Interdependence of motional processes in polymers: correlation functions for nmr relaxationCorrected proofs received November 22, 1982 (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 263-274 
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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 roles of both anisotropic motion and the interdependence of multiple motions in leading to nonexponential correlation functions for NMR relaxation data are explored. A motional model is developed in which rotational motions of segments of various lengths are controlled by the formation and disappearance of a suitable conformation. Such a model gives correlation functions which can be made, through adjustment of parameters, to be almost identical to correlation functions from other, quite different, models. The ability of NMR relaxation data to identify unique motional models is thus questioned.
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    Particle morphology in the radiation-induced heterophase polymerization of vinyl chloride with solvent added in small amounts (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 251-262 
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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: Investigations were carried out on the polymer particle morphology obtained in the early stages of radiation-induced bulk polymerization of vinyl chloride with solvent added in small amounts over the temperature range of -10 to 70°C under quiescent conditions. At low temperatures, when the polymerization is carried out in the absence of solvent, there is flocculation of irregular aggregates of two types depending on polymerization conditions: (i) small primary particles that remain finely dispersed and (ii) large flocs that undergo rapid sedimentation. By addition of increasing amounts of solvent a gradual change towards single small spherical particles that remain finely dispersed is obtained. With more than 3% w/w THF, spherical particles in latexlike dispersions are obtained in polymerizations at -10 and 22.8°C, and show a small change in size with increasing amounts of THF. In the high-temperature range, 50-70°C, where spherical particles can be obtained in the absence of solvent, no significant changes are produced by addition of THF. The results are discussed in the terms of a marked increase in particle plasticization by the solvent, enabling the coalescence of flocculated particles of small size to occur also in polymerization at low temperature.
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    Polymorphic structure and physical properties of the polyester/ether poly(ethylene-1,2-diphenoxyethane-p,p′ -dicarboxylate) (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 275-284 
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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: X-ray diffraction studies of fibers of the polyester/ether poly(ethylene-1,2-diphenoxyethane-p,p′ -dicarboxylate) (PEET) produced by high-speed melt spinning show the existence of two polymorphic forms, designated α and β, in the solid state. The α form is obtained by annealing filaments melt spun at takeup speeds below 3000 m/min and is also found in samples crystallized from the melt and from dilute solutions. The α form has a monoclinic unit cell with dimensions a = 7.83, b = 10.33, c = 18.68 Å, and β = 83.1°. The equilibrium melting temperature and heat of fusion of the α form are 288.3°C and 19.1 cal/g, respectively. The β form predominates in highly oriented filaments obtained at takeup velocities above 6000 m/min. The unit cell is orthorhombic with dimensions a = 7.28, b = 5.65, and c = 18.64 Å. The β form does not transform to the α form on annealing.
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    A Raman-spectroscopic study of solution-crystallized polyethylenes (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 285-294 
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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: An analysis of the Raman internal modes of dilute-solution-crystallized homopolymers and co-polymers of ethylene has been made, similar to the work previously reported for the bulk-crystallized polymers. The crystallite structure can be described in terms of the relative amounts of the crystalline orthorhombic phase, the liquidlike amorphous phase, and the interfacial region. These quantities change with the molecular constitution of the chains and the crystallization conditions. The level of crystallinity decreases significantly with increasing counit content as would be expected. In addition, an appreciable interfacial structure develops in copolymers as compared with the homopolymers. A possible relationship between the interfacial content and the relaxation transitions in polyethylene is discussed.
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    The heat of fusion of poly(ethylene terephthalate) (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 295-299 
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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: By use of the Clapeyron equation for the dependence of the melting point on pressure, the heat of fusion was found to be 32.5 cal/g, in good agreement with values determined by other methods. An equation for the dependence of the melting point on the degree of polymerization gave a heat of fusion of 27.6 cal/g when applied to hydroxyl-terminated oligomers. This simple relation applied all the way down to the smallest member of the series, di(hydroxy ethyl) terephthalate.
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    Photon correlation spectroscopy of polymer solutions (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 807-820 
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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 polynomial subdistribution method for analyzing the correlation profile in photon correlation spectroscopy of polymer solutions is described. This method generates a continuous distribution function from the measured photoelectron time-correlation function, which can be related to particle size or molecular weight distribution of solute. The method is tested using simulated data for unimodal and bimodal distributions and compared with cumulant and histogram methods, respectively. The polynomial subdistribution method has an advantage in that it not only generates a continuous distribution curve but also works well for bimodal distributions whose peaks are close together.
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    One-dimensional models of polymer dynamics. II. A dashpot-spring model (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 787-806 
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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 assumption of Clark and Zimm that coupled dashpots and springs can be used to model the dynamics of polymer molecules is here applied to a model different from that of Clark and Zimm. The precise differences are given in the preceding paper. The dielectric relaxation spectrum of the model is computed in time and frequency domains. The relaxation spectrum can be fitted reasonably well by the empirical Williams-Watts and Havriliak-Negami functions. The best-fit Williams-Watts and Havriliak-Negami parameters are given as functions of the parameters of the model. The model is compared with several related models found in the literature and possible interpretations are given.
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    The melt anisotropy of ultrahigh-molecular-weight polyethylene (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 821-830 
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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: In the course of melt-flow crystallization studies with ultrahigh-molecular-weight polyethylene (UHMWPE), we observed that the melt of UHMWPE is highly anisotropic above its equilibrium melting point and has a tendency to fibrillate. An examination of the melt anisotropy of UHMWPE by optical, Thermal, and x-ray analysis indicates that the melt anisotropy persists at 345°C, i.e., the temperature at which the polymer degrades under nitrogen, and appears similar to a smectic liquid-crystalline phase.
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    Ionic conductivity of hybrid films composed of polyacrylonitrile, ethylene carbonate, and LiClO4 (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 939-948 
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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 electrical conductivity of hybrid films consisting of polyacrylonitrile (PAN), ethylene carbonate (EC), and LiClO4 was investigated. In these films, EC and LiClO4 are found to be molecularly dispersed in PAN, forming solid solutions over a wide composition range. The ionic character of the electrical conductivity is demonstrated. The conductivity is not correlated with the content of LiClO4 or of PAN, but primarily with the mole ratio [EC]/[LiClO4] in the films. An increase in the [EC]/[LiClO4] ratio enhances the conductivity. When the ratio is about 2, the conductivity attains 10-4-10-5 S cm-1 at 25°C. This change in conductivity results from a change in carrier mobility. PAN makes the films solid without decreasing the carrier mobility. In the hybrid films, the carrier mobility and the macroscopic viscosity are not related by Walden's rule. The high conductivity is due to regions in the film characterized by a low microscopic viscosity. This is determined by the mole ratio [EC]/[LiClO4] and largely controls the carrier mobility.
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    Radiation chemistry of linear low-density polyethylene. I. Gel formation and unsaturation effects (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 949-956 
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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: Quenched and annealed samples of linear low-density polyethylene (LLDPE) were irradiated with 60Co γ rays in vacuo at room temperature. The data follow rather accurately Charlesby's equation s = k/r, where s is the soluble fraction, r the dose, and k a constant from which G(X), the G-value for crosslinks, was calculated. Crosslinking in the LLDPE is about twice as extensive at equal doses as in LHDPE. Production of vinylene unsaturation was approximately the same in the two types of polyethylene.
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    Radiation chemistry of linear low-density polyethylene. II. Kinetics of alkyl and allyl free-radical decay reactions (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 957-967 
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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: Quenched and annealed samples of linear low-density polyethylene (LLDPE) were γ irradiated in vacuo at 77 K; the kinetics of the alkyl free-radical decay reactions were studied at room temperature, and of the allyl free-radical reactions at 60, 70, and 80°C. The ESR signals saturate at a slightly higher microwave power in the LLDPE than in high-density polyethylene (HDPE), and the alkyl radicals start decaying at a lower temperature in the LLDPE than in the HDPE. As in the HDPE the decay of the alkyl free radicals at room temperature in the LLDPE follows the kinetic equation for two simultaneous first-order reactions with the fraction of the faster-decaying component being slightly greater in the quenched than in the annealed samples. In the case of the allyl free radicals the decay at 60°C follows the equation based on one fraction of the radicals decaying according to second-order kinetics in the presence of other nondecaying radicals. At higher temperatures the data are best understood in terms of a second-order rate equation with a continuously variable time-dependent rate constant as suggested by Hamill and Funabashi.
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    Small-angle x-ray scattering studies of crazed glassy polymers (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 969-982 
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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 small-angle x-ray scattering (SAXS) study of the relaxed craze structure in polystyrene was performed using the Oak Ridge National Laboratory 10-m SAXS facility. Coupled with known results from transmission electron microscopy studies, the SAXS patterns can be interpreted as scattering from an open-cell foam with void spaces interspersed among the fibrils. Results have shown the scattering centers in crazed polystyrene can be modeled as cylinders the axes of symmetry of which are parallel to the tensile axes. Scattering centers are bimodal in their size distribution, with aspect ratios of 1.0 and 2.6. Crazes in lower-molecular-weight polystyrene have more and larger scattering centers than crazes in higher-molecular-weight polystyrene, while variations in strain rate and test temperature during craze formation have no effect on the relaxed craze morphology. A comparison of SAXS patterns from polystyrene and polycarbonate indicates that the morphologies of their respective crazes are significantly different.
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    An investigation of the compatibility and morphology of semicrystalline poly(ε-caprolactone)-poly(vinyl chloride) blends (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 999-1010 
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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: Blends of poly(ε-caprolactone) (PCL) and poly(vinyl chloride) (PVC) were investigated at concentrations of PCL greater than 50 wt % using purified materials. For these concentrations, PCL partially crystallizes with degrees of crystallinity ranging from 50% for pure PCL to 〈 10% for the 50% mixture. Small-angle x-ray scattering was used to characterize the resultant morphologies. Model calculations for the interference functions and for the integrated scattering indicate that PVC is incorporated between the PCL lamellae and that the two polymers form a homogeneous mixture in the amorphous phase. These results were compared to previous results on the same system using the identical technique. Purification of the two homopolymers proved to play a critical role in the overall mixing characteristics of PVC and PCL
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    The swelling interface number as a criterion for prediction of diffusional solute release mechanisms in swellable polymers (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 983-997 
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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 glassy polymer containing a uniformly dispersed solute is brought in contact with a penetrant, solute diffusion will be associated with the transport mechanism and penetration velocity of the penetrant in the polymer. Analysis and prediction of mechanisms of diffusional solute release may be obtained through a new dimensionless number, the swelling interface number, Sw, which compares the relative mobilities of the penetrant and the solute in the presence of macromolecular relaxations in the polymer. It is shown that a sufficient and necessary criterion for time-independent diffusional solute release rates from these swellable systems is that the Sw be smaller than 10-2. The swelling interface number Sw may be related to easily determined structural and thermodynamic parameters of the solute/polymer/penetrant system. Preliminary experimental results of dynamic water swelling of poly(2-hydroxyethyl methacrylate-co-methyl methacrylate) and diffusional release of theophylline from initially glassy copolymers show that decreasing values of Sw are related to increased pseudo-case-II transport kinetics of the solute.
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    Friction coefficients in self-diffusion, velocity sedimentation, and mutual diffusion for poly(ethylene oxide) in aqueous solution (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1029-1039 
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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 concentration dependences of the friction coefficient(s) for poly(ethylene oxide) have been determined on well-defined fractions in dilute aqueous solution. Three independent techniques have been used: FT-pulsed field gradient NMR (self-diffusion), photon correlation spectrosccpy (mutual diffusion), and velocity sedimentation, in the concentration range 1-25 kg m-3. The results establish that, at a given concentration, the friction coefficient in self-diffusion is appreciably smaller than that operating in mutual diffusion and sedimentation; the friction coefficient in the latter processes are identical within experimental error.
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    Electrostatic contribution to heat capacity of polyelectrolyte solutions (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1563-1566 
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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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    A simple, cost-effective automatic capillary viscometer system (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1559-1562 
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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
    Additional Material: 2 Ill.
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    Flow-induced crystallization by surface growth of polyethylene fibers (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1513-1526 
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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 experiments has been carried out investigating several features of the surface growth method for observing longitudinal growth of polyethylene fibers in Couette geometry. Attempts to obtain limiting steady-state takeup rates using a Teflon rotor were hampered by fiber breakage; however, maximum growth rates before breakage were found to be considerably higher than those observed in previous studies. Growth rates were also obtained using a static method, and for the Teflon rotor indicated above a critical concentration a linear growth rate equal to the stirrer velocity with rates essentially independent of temperature. With a silanized glass rotor, the same method gave much lower growth rates at comparable stirrer speeds and temperatures and showed a temperature dependence suggestive of a nucleation-controlled mechanism. The implications of these results for other studies of the mechanisms of growth by the surface method are also discussed.
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    Carbon-13 NMR spectra of solid chlorinated polymers (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1569-1572 
    Details
    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.1983.180210824
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    Elastic modulus of syntactic foams (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1567-1568 
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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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    Polymer single crystals of poly(4-hydroxybenzoate). I. Morphology (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1599-1609 
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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(4-hydroxybenzoate) was prepared from 4-acetoxybenzoic acid, 4-pivaloyloxybenzoic acid, and 4-trimethylsiloxy benzoyl chloride by condensation without the addition of a catalyst. Although various reaction conditions were used the products were always crystalline. The morphology of the as-polymerized crystals has been studied by transmission electron microscopy as a function of molecular weight and end-group type. It was possible to detect morphological features during the course of reaction from oligomers to polymer which enabled us to determine the mechanisms that are likely to control chain growth for different regimes of polymerization kinetics.
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    Studies on dilute solutions of rodlike macroions. I. Light scattering, densitometry, and cryoscopy (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1573-1597 
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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: Total integrated and photon correlation light scattering have been used to study two samples of poly(1,4-phenylene-2,6-benzobisthiazole) (PBT) representing two methods of precipitation to recover the polymer from the polymerization solvent. Some details of the light-scattering instrument are given. It is found that the PBT sample is rodlike, with persistence length of at least 50 nm, but that the postpolymerization processing method influences the state of interchain aggregation. The data are augmented by measurements of freezing-point depression to estimate the degree of protonation of PBT in sulfuric acid, and by measurements of partial specific volume to provide an estimate for the geometric diameter of the chain in solution. The results show a degree of protonation of 2-4 protons per repeating unit, and partial specific volumes that are appreciably smaller than the specific volume determined for the polymers. Similar data and results are reported for poly(1,4-phenyl-ene-2,6-benzobisoxazole) and poly(1,4-phenylene terephthalamide).
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    Diffusion of iodine into PE and PET (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1635-1646 
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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 show that the Rutherford backscattering technique is very useful for studying the kinetics of diffusion processes in polymers. We have measured the diffusion of iodine into low-density polyethylene (LDPE) by optical absorbance and by Rutherford backscattering. The optical results appear to be normal, and show no electric field dependence, but the backscattering results reveal that this is misleading, because there is fast diffusion in the bulk accompanied by large surface concentrations of iodine. We have studied PET by the backscattering technique, and in this case the behavior corresponds to a weakly concentration-dependent diffusion coefficient with no observable surface effects. Neither set of results gives support to the domain theories of low-frequency electrical oscillation in these materials.
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    Polymer single crystals of poly(4-hydroxybenzoate). II. A contribution to crystal structure and polymorphismDedicated to Professor H.-J. Cantow on the occasion of his 60th birthday. (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1611-1633 
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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: Electron diffraction has been used to investigate the structure of a wide range of as-polymerized crystals of poly(4-hydroxybenzoate) [systematic name: poly(1,4-oxybenzoyl)]. The chemical composition and the degree of polymerization (DP) have been varied and some samples have been thermally treated. At room temperature two crystalline modifications with orthorhombic unit cells coexist. The chains adopt a 21 helical conformation in both forms, but there are differences for oligomer and polymer crystals. Oligomers of low DP have an extended chain-conformation, whereas in polymers a shortening of the repeat distance along the chain is observed as a function of both the DP and the crystallization conditions. From the most extensive data sets we have derived the lattice parameters a = 7.52, b = 5.70, and c = 12.49 Å for polymer crystals of phase I, and the subcell parameters for oligomer crystals of phase II a = 3.77, b = 11.06, and c = 12.89 Å. Both phases contain two chains per unit cell. In addition to modifications I and II several defect structures exist the unit cells of which contain more than two chains. At temperatures which depend on the degree of polymerization, a phase transition to a third modification takes place. The large difference between the densities of phase III as compared to both phase I and II suggests that torsional degrees of freedom exist in phase III which allow a certain mobility of the phenyl and ester groups. This mobility enables the end groups of adjacent layers in interlamellar regions of oligomer crystals to undergo transesterification reactions and therefore to increase the molecular weight of the samples.
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    C-13 NMR analysis of polystyrene from low-molecular-weight model compounds (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1667-1674 
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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: Methylene and phenyl C1 carbon signals of polystyrene are assigned on the basis of the signal assignments of styrene oligomers. Polystyrenes prepared with benzoyl peroxide, n-butyllithium, and trifluoroboron etherate catalysts have random distributions with probabilities of racemic dyads of 0.54, 0.56, and 0.45, respectively.
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    The effect of dye sorption on electromechanical properties in sodium poly(L-glutamate) (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1661-1665 
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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: Piezoelectric constant, Young's elastic modulus, and dielectric constant of undyed and dyed films of poly(L-glutamate) were measured at 10 Hz over the temperature range -120 to 120°C. The temperature of the maximum in -d″14 shifts toward higher temperature up to 0.6 mg/g polymer of dye uptake and then shifts toward lower temperature by further dye sorption. The variation of the piezoelectric modulus was interpreted by the change of mobility of impurity ions in the sample.
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    Existence of a distribution of hole-trap activation energies in FEP-Teflon (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1691-1701 
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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 FEP-Teflon samples are electron irradiated at room temperature in open circuit and stored in that state for varying times following the end of irradiation, the temperature of the first current peak of the short-circuit TSC plot increases with increasing storage time. A new model is presented to explain this phenomenon, its main features being (i) a quasicontinuous distribution of hole-trap activation energies, the “center of mass” of the trapped hole population moving toward the deeper end of the distribution during the storage time, and (ii) an electron/hole recombination coefficient much smaller than that implied in an earlier model. It is shown that the assumption of a single dominant type of hole trap implies an unrealistically large frequency factor.
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    Thermotropic homopolyesters. III. Preparation and properties of polymers based on 4′-hydroxyphenyl-4-hydroxycinnamate (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1851-1872 
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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: Low-molecular-weight 4′-acetoxyphenyl-4-acetoxyoinnamate, as well as several polyesters synthesized from this monomer and aliphatic dibasic acids, exhibit thermotropic nematic phases. DSC heating curves for all of the polymers exhibit multiple transitions. The amount of crystallinity of these polymers at room temperature is small and the degree of order along the chain axis in the crystalline phase is poor. For the lower homologues the nematic phase exists over a broad temperature range of approximately 100°C. The polyester from chiral (+)-3-methyl adipate forms a thermotropic cholesteric phase. Both the diacetoxy monomer and azelate polymers of low molecular weight adopt the homeotropic texture on glass slides, but with increasing molecular weight the planar texture becomes preferred. Investigation of the effects of electric fields in the conduction regime upon the nematic phase of the diacetoxy monomer revealed that Williams domains are formed only with difficulty. In most cases, a stationary pattern appeared instead. At higher voltage the dynamic scattering mode (DSM) was obtained, and above this a field-induced transition to the isotropic phase. The azelate polyesters exhibited Williams domains and the DSM in the conduction regime. The formation time for Williams domains was fairly short for polymers having ηinh 〈 0.44 dL/g, but increased to 80 min when ηinh = 0.68 dL/g. The DSM was only observed for polymers having ηinh 〈 0.61 dL/g. For these polymers the critical frequency separating the conduction and dielectric regimes exhibits a stronger temperature dependence than that of low-molecular-weight nematogens. A new instability pattern is reported for the azelate polyesters in the dielectric regime.
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    Photon correlation spectroscopy of polymers in the glassy state (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1897-1902 
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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: Photon correlation spectroscopy has proven to be a very useful technique for studying slowly relaxing density and optical anisotropy fluctuations in bulk polymers near the glass transition. When some of the fluctuations achieve relaxation times much longer than the typical averaging time for the intensity autocorrelation function (104 s), the result must be treated in the partially heterodyned limit. Also, when the sample is near the glass transition but not at equilibrium the correlation function is not stationary in time because the system is relaxing as a whole toward the equilibrium state. The above effects are discussed theoretically and demonstrated experimentally in polystyrene as a function of temperature and pressure. Light scattering with coherent excitation also fluctuates in space as well as in time (as shown in the accompanying paper). The consequences of this effect are discussed. When most of the intensity is associated with fluctuations whose relaxation times are very long in polystyrene, there is still a broad relaxation function evident. This is characteristic of a secondary relaxation process.
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    An analysis of the reflective component of small-angle X-ray scattering patterns from crazed polystyrene (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1913-1926 
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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: An investigation of the reflective component of small-angle x-ray scattering patterns of polystyrene crazes is performed. It is shown that the strong streak parallel to the tensile axis consists predominantly of reflected radiation, while the remaining pattern is composed entirely of diffracted radiation. X-ray reflection off unparallel regions of crazes is discussed and the nature of the reflection is also considered in terms of collimation quality. An analysis methodology based on craze tip angular distribution is proposed.
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    Microstructure rearrangement during the heat-treatment of melt-drawn poly(ethylene terephthalate) fibers (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1927-1953 
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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: Melt-spun poly(ethylene terephthalate) fibers were isothermally heat-treated at constant length. Microstructural changes occurring during the heat-treatment were monitored using specific gravity, wide-angle x-ray scattering (WAXS), small-angle x-ray scattering (SAXS), optical birefringence, and static mechanical testing. Major changes in the density of the most highly oriented fiber examined occurred in times below 100 ms. For less oriented fibers, the time scale for significant density change increases to the 1-10 s range. The course of birefringence increase approximates that of the density. WAXS measurements show that crystallinity develops at essentially constant crystal perfection, but that the orientation of the crystallites first decreases and then increases with time. SAXS results show development of a four-point pattern, the azimuthal angle of the lobes decreasing with initial orientation, with temperature, and with time. A streak transverse to the fiber axis develops more rapidly than do the lobes. A two-stage transformation process is envisaged, the first stage being the formation of defective crystal fibrils and the second being internal rearrangement of the fibrils to form more perfect crystallites, separated by more amorphous zones. Changes in the crystallite orientation are related to constraints of the noncrystalline material on the crystallites.
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    The effect of temperature on the infrared spectra of poly(ethylene terephthalate) (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2067-2083 
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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: Reversible and irreversible spectral changes are observed on heating of solvent-cast films of poly(ethylene terephthalate) (PET) between 30 and 230°C. The irreversible changes are due to the gauche-trans isomerization of the ethylene glycol segments and the corresponding changes in the symmetry and resonance characteristics of the aromatic rings. On the other hand, there are thermally reversible spectral changes. These reversible effects are primarily observed for the modes of the aromatic ring and the trans ethylene glycol segment. These reversible spectral changes include intensity variations and frequency shifts and are found to be linearly dependent on the measurement temperature. These reversible changes arise from changes in intermolecular and intramolecular forces as the temperature changes.
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    Modeling the structure of chain-molecule liquids: A computer simulation of the n-alkanes C8-C30 (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2379-2387 
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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: Computer models of a series of liquid n-alkanes were generated, allowing for continuous variation of torsion angles and of atomic positions. Torsional and intramolecular and intermolecular non-bonded potentials were introduced. Calculated fractions of gauche bonds are slightly higher than those calculated from a rotational isomeric state model. Calculated radial distribution functions exhibit peaks in good agreement with experimental data. No directional correlation between chains is found, except at very short distances. Calculated end-to-end distances and radii of gyration indicate random coil conformations. These results are unaffected by extension of the range of interaction to the attractive region and by variations of temperature and density.
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    Study of light-scattering changes induced in tRNA solutions by a strong optical field of picosecond pulses (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2465-2471 
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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 in the light-scattering components (λ = 0.53 μm) induced by a strong picosecond optical field (λ = 1.06 μm) applied to macromolecular transfer ribonucleic acid (tRNA) solutions were studied. Two beams were polarized vertically, and the intensity of the vertical and horizontal components of the light (λ = 0.53 μm) scattered at an angle of 90° were measured. The electric field of the strong 30-ps laser pulse was 5.0 × 103 esu cgs. The experimentally determined changes allowed for calculation of the mean third-order optical polarizability c, and its anisotropy δc. The measurements were performed in three different solutions: salt free, with magnesium ions, and without magnesium ions. Changes in tRNA structure reflected in changes of nonlinear light scattering, third-order optical polarizability, and its anisotropy were observed.
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    Birefringence and glass transition temperatures of poly(diethylene glycol terephthalate) networks (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2473-2482 
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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: A series of polymer networks were prepared by trifunctionally endlinking poly(diethylene glycol terephthalate). The elastomeric properties of these materials were studied at constant temperature using experiments that involve both the elastic force and birefringence. Whereas the stress-strain isotherms show an anomalous increase in the modulus at very high elongation ratios, a downturn appears in the birefringence-strain isotherms at the same extensibilities. These results suggest that the upturn that appears in the force should be attributed to maximum chain extensibility rather than to strain-induced crystallization. A variety of additional thermoelastic experiments were carried out on these networks, to elucidate the dependence of the glass transition temperature on strain. It was found that for the elongation ratios at which the networks exhibit Gaussian behavior, the free-volume effects on the glass transition temperature Tg (decreasing Tg with increasing free volume) offset the conformational effects (increasing Tg with decreasing entropy). However, the contrary occurs in the region where the stress increases anomalously with increasing strain.
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    Line broadening in the 13C NMR spectra of bulk polymers above Tg (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2551-2559 
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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 magic-angle sample spinning (MAS), high-power decoupling, and resonance frequency on the 13C NMR linewidths of bulk polyisobutylene and bulk trans-polybutadiene are examined. The 13C linewidths increase with resonance frequency, are unaffected by high-power decoupling, and are reduced to different extents by MAS. The dominant contribution of the natural linewidth of the polyisobutylene lines is confirmed. The two carbons of trans-polybutadiene have approximately equal linewidths under all conditions, a result that eliminates residual chemical shift anisotropy as a major contributor to the linewidths. The large reduction of the trans-polybutadiene linewidths with MAS, coupled with the above result, suggests that microscopic variation of magnetic susceptibility is the major factor for this semicrystalline polymer. Cross-polarized 13C spectra of trans-polybutadiene were obtained with and without MAS. With MAS, resonances due to the crystalline and amorphous components were resolved. The principal components of the chemical shift tensor of the vinylene carbons were obtained from the spectrum without MAS.
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    A theoretical investigation of chain packing and electronic band structure of the rigid-rod polymer trans-poly(p-phenylene benzobisthiazole) in the crystalline state (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2543-2549 
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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 extended Hückel method was employed to calculate electronic band structures in trans-poly(p-phenylene benzobisthiazole) (trans-PBT) in an attempt to elucidate the packing and electronic properties of these chains in the crystalline state. The unit-cell energies thus calculated indicate that the most stable arrangement for trans-PBT corresponds to the chains in planar configurations, at an interplanar spacing of 3.5 Å, and shifted axially by 3.0 Å relative to one another. These calculated results are in good agreement with experimental results obtained on the polymer and on relevant model compounds. No discernible dispersion of the energy bands perpendicular to the planes is observed, indicating that the neighboring chains are electronically noninteractive, as was found earlier for trans-polyacetylene and polyethylene. Similarly, the band gap of 1.69 eV in the axial direction for one of a pair of chains was nearly the same as that, 1.73 eV, calculated previously for an isolated trans-PBT chain. These values are in the range 1.4-1.9 eV reported for trans-polyacetylene, which has been extensively studied because of its promise as a semiconductor.
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    Flow characteristics of poly(ethylene terephthalate) deduced from pressure drop measurements (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 1-19 
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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 unique capillary die was designed which made possible the measurement of extrusion pressure at various locations along the capillary length. Entrance pressure drops, exit pressures, and other rheological characteristics were determined for the flow of poly(ethylene terephthalate) through this extrusion apparatus. The effect of die entrance angle, extrusion temperature, throughput rate and polymer molecular weight were considered. Two samples differing in molecular weight exhibited power-law behavior at shear rates below 1000s-1. The entrance pressure drops and exit pressures were observed to increase with increasing molecular weight; furthermore, at a specific temperature, both-increased with increasing shear rate. The values for entrance pressure drop obtained using Bagley analysis were consistently higher than those obtained from direct measurements.
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    Silicone networks with junctions of high functionality and the theory of rubber elasticity (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 49-55 
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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: Results of Krik, Bidstrup, Merrill, and Meyers on polydimethylsiloxane networks of high functionality φ yield values of the reduced force [f*] in the high-extension limit that are directly proportional to (vs/V) (1 - 2/φ) where vs/V is the number of effective chains in volume V. The contention that trapped entanglements contribute significantly to the modulus is refuted by adherence of the results to this proportionality down to the lowest degrees of interlinking. Features of the relationship of stress to strain that appear to be in conflict with current theory are attributable to crowding of chains about the junctions of high functionality and of large linear dimension in the networks investigated by these authors.
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    Transport of hydrogen and carbon monoxide in highly crosslinked poly(propylene glycol) networks (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 237-243 
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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: Previous interpretations of gas transport data in crosslinked networks have been hindered by an inability to accurately control and evaluate the network parameters. We have recently prepared a series of model networks by reacting poly(propylene glycol) with a triisocyanate crosslinking agent. The poly(propylene glycol)s had narrow molecular weight distributions and average molecular weights between 425 and 3000, so the resulting networks had uniform average molecular weights between crosslinks. Hydrogen and carbon monoxide permeabilities in membranes formed from these networks increase with decreasing crosslink density. These results indicate increased cooperative molecular motions in the networks with longer average chain lengths between crosslinks. Increasing the average molecular weight between crosslinks also reduces the discrimination between these two gases so that the separation factors decrease. For networks prepared from mixtures of poly(propylene glycol)s with different molecular weights the gas permeabilities (but not the separation factors) depend on the molecular weight distribution.
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    Piezoelectricity and viscoelastic crystalline dispersion in highly oriented poly(vinylidene fluoride) (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 245-254 
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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 poling temperature on piezoelectricity and its thermal stability were investigated on the basis of the thermal molecular motion associated with the crystalline region. This was done by using a film of highly oriented poly(vinylidene fluoride) containing form-I crystals. The film was prepared by a zone-drawing apparatus of the forced-quenching type. The piezoelectric stress constant e31 is a monotonically increasing function of the poling temperature which becomes steeper above ca. 320 K and again at ca. 400 K. The degree of orientation of the crystal b axis generated by poling also increases more steeply with poling temperature above ca. 320 K and again at 400 K. These temperatures correspond, respectively, to the crystalline dispersion temperature at 11 Hz, designated as αc, and the initiation temperature Tpm of large-scale molecular motion corresponding to premelting of form-I crystals. Thus the effect of poling temperature on piezoelectricity closely reflects the moleculer motion in form-I crystals. The annealing temperature T'a at which e31 decreases to 70% of that of unannealed sample by annealing a poled sample increases with the poling temperature and again this increase is steeper above poling temperatures of ca. 320 K and ca. 400 K. Thus the decay of piezoelectricity depends on both the αc temperature and Tpm.
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    Distribution of polymer chain lengths inside a spherical volume: Solution in terms of a diffusion problem (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 279-284 
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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 probability W(t) that a given number t of segments of an infinite chain lie within a given sphere can be expressed in terms of the single-pass length probability and the probability of reentrance into the sphere. The problem of calculating these two probabilities is equivalent to that of a diffusing particle exiting or entering the sphere after a given time, when the surface of the sphere is an absorbing wall. It is shown that the boundary condition, c = 0, usually applied to an absorbing surface cannot be used for the present purpose. The boundary condition used instead is the so-called radiation condition ∂c/∂z = kc; it is shown that when k approaches infinity the final answer for W(t), which is given in the form of an infinite series, approaches the correct limit. In this same limit the ratio 〈t〉2/〈t〉2 has the value 2.4
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    Configurational studies on amylose. I. Scattering functions (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 1551-1559 
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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: Scattering functions for amylose chains have been calculated as a statistical mechanical average over eligible configurations based on the rotational isomeric state approximation. Main emphasis has been placed on an intermediate-angle range (0.1 〈 h = (4π/γ)sinθ 〈 1.0 Å-1) where the scattering function is sensitive to local chain configurations. In order to avoid overestimation of the regularity of chain configurations, the rotational isomeric states for each glycosidic bond have been defined by a set of discrete torsion angles at intervals of 5°. Pair correlation functions for atoms separated by sequences shorter than 31 glucose units are evaluated by the Monte Carlo method, while the interference for longer sequences is calculated by a series expansion in the even moments of the chain. All carbons and all skeletal oxygens are treated as point scatterers in order to incorporate all the interferences between atoms in unit pairs in the calculations. The calculated scattering function shows appreciable oscillation at intermediate angles, reflecting the characteristic helical tendency of the configurations. The Debye function is found to be inadequate in the intermediate-angle region owing to the non-Gaussian character of the distribution function and to breakdown of the assumption that the mean-square distance between a pair of atoms is proportional to the number of bonds between them, because of the bulkiness of the glucose unit.
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    The heat of fusion of 66 nylon (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 1615-1621 
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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 heat of fusion ΔHf of 66 nylon has been determined by use of the Clapeyron equation. Measurements of ΔHf and the unit-cell parameters on molding pellets show that this material contains the α2 crystal phase, which is less dense than the α1 phase obtained by crystallization from solution. The value of ΔHf-45-46 cal/g, is in good agreement with earlier reports.
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    On the CO2 permeation of uniaxially drawn polymers (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 1645-1653 
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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 CO2 permeation coefficient and the difficient were measured using the permeation time-lag method for films of atactic polystyrene and high-density polyethylene, each as a function of uniaxial draw ratio. The reduction of permeability with draw ratio is observed for polystyrene and for polyethylene. In the latter it is associated with an increase in crystallinity. In both cases the premeability decreases and the solubility constant remains unchanged. The reduction of permeability is thus caused only by the reduction in diffusion of CO2 in the drawn polymers. The mechainism is different for the two polymers, as is confirmed by measurements of birefringence, glass transition temperature, and crystallinity.
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    Tearing of unvulcanized natural rubber (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 1623-1634 
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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 tear behavior of unvulcanized natural rubber has been studied by using established techniques normally adopted for the study of vulcanized rubbers. Unvulcanized rubber has been found to tear in a relatively steady manner, in contrast to the stick-slip tear behavior of the vulcanized rubber, the tearing energy being dependent on the rate of tearing. Crystallization seems to be an important factor in determining the tear behavior since it has not been found possible to tear unvulcanized SBR under the same conditions. The effect of the pronounced imperfect elastic nature of the material was studied under conditions where the driving force for tearing was solely governed by the rate of release of elastic energy. Under such conditions, it has been found that the tearing energy is determined not by the strain energy required to stretch the material but by the energy which can be recovered on retraction. The set developed in the test piece, due to imperfect elasticity, has also to be taken into account.
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    Continuous measurement of dynamic tensile mechanical properties in polymer solids over a wide range of frequencies. III. Effect of absorbed water on nylon 6 at 23°c (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 1635-1643 
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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 dynamic tensile mechanical properties (E′, E″, and tanδ) of nylon 6 have been studied over the frequency range 10-25-102 Hz and water content up to 12.6 wt % at a constant temperature of 23°C. From the dispersion maps in the coordinates of frequency and water content, the relaxation behavior can be classified into three regions of water content: (A) dry to 2 wt %, (B) 2-5 wt % and (C) 5 wt % to wet. For region B, it is found that the logarithmic frequency shift Δ logfα/Δx of the α dispersion per 1 wt % change of water content is 1.7. Taking into consideration that the change of glass transition temperature per 1 wt % change of water content Δ Tg/Δx is 3.7°C (according to Kettle), we find Δ logfα/ΔTg = 0.5. For regions A and C, such an evaluation cannot be made. The effect of absorbed water on the dynamic mechanical properties at 23°C is discussed in terms of two kinds of processes: (a) formation of water-amide hydrogen bonds with free amide groups and (b) scission of amide-amide hydrogen bonds.
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    Compatibility of poly(butylene terephthalate) with a liquid-crystalline copolyester (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 1697-1699 
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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
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    The influence of strain deformation on the solubility of ethyl acetate vapor in poly(vinylidene fluoride) (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 1719-1725 
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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 degree to which a polymer film develops plastic flow depends largely on the total strain ∊ and the elongation time th. The magnitude and the time dependence of the elastic component ∊e of the total deformation are controlling factors, respectively, in the solubility and diffusion processes. The plastic deformation ∊pl seems not to contribute to the transport properties. The nonlinearity in solubility due to ∊ may be conveniently handled. In this study, the solubility of ethyl acetate vapor in poly(vinylidene fluoride) was determined as a function of pressure and total elongation at 30°C. These results suggest that the strain magnitude and time de pendence of the component deformations play important roles in transport behavior.
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    Properties and chain flexibility of poly(dl-isobornyl methacrylate) (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 1745-1751 
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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 glass transition temperature and characteristic ratio of poly(dl-isobornyl methacrylate) have been determined. The results indicate that in the case of certain polymethacrylates the chain flexibility depends mostly on the bulkiness of the side group, while the glass transition temperatures depend mostly on side-group rigidity.
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    Miscible blends of amorphous polymers (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 1857-1870 
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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: Thirty-five polymethacrylate/chlorinated polymer blends were investigated by differential scanning calorimetry. Poly(ethyl), poly(n-propyl), poly(n-butyl), and poly(n-amyl methacrylate)s were found to be miscible with poly(vinyl chloride) (PVC), chlorinated PVC, and Saran, but immiscible with a chlorinated polyethylene containing 48% chlorine. Poly(methyl) (PMMA), poly(n-hexyl) (PHMA), and poly(n-lauryl methacrylate)s were found to be immiscible with the same chlorinated polymers, except the PMMA/PVC, PMMA/Saran, and PHMA/Saran blends, which were miscible. A high chlorine content of the chlorinated polymer and an optimum CH2/COO ratio of the polymethacrylate are required to obtain miscibility. However, poly(methyl), poly(ethyl), poly(n-butyl), and poly(n-octadecyl acrylate)s were found to be immiscible with the same chlorinated polymers, except with Saran, indicating a much greater miscibility of the polymethacrylates with the chlorinated polymers as compared with the polyacrylates.
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    Interpretation of anomalous sorption kinetics in polymer-penetrant systems in terms of a time-dependent solubility coefficient (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 1885-1900 
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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 formulation of the molecular relaxation model of anomalous diffusion in polymers, in terms of a time-dependent solubility coefficient, which was previously introduced and studied by us, is discussed here in greater detail. A full account of the methods of application of the treatment is given and the prediction of typical absorption and desorption kinetic features characteristic of glassy polymer-good swelling agent systems, including Case II absorption, is demonstrated.
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    Longitudinal acoustic mode in polymers. VII. Surface structure from swelling studies of freeze-dried polyethylene single crystals (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 1871-1884 
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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 longitudinal acoustic mode (LAM) spectra have been obtained from freeze-dried polyethylene single-crystal samples swollen in decalin. The changes in ν(LAM) have been studied as a function of molecular weight, temperature of crystallization, and temperature of measurement. These data, together with knowledge of how terminal “defects” influence ν(LAM) of the trans stems, lead to the conclusion that surface folds and cilia are the components responding to the swelling agent. The analysis also shows what the relative effects of these structures are as a function of molecular weight and crystallization temperature. This study indicates that cilia are primarily responsible for the large increases in x-ray long period observed for swollen single-crystal mats.
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    Electron crystallography of epitaxially grown paraffin (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 1919-1929 
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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: Three-dimensional electron diffraction data from the epitaxially crystallized paraffin n-C36H74 are investigated in a structure analysis and are found to give a reasonable image of the structure, in agreement with the earlier x-ray determination. An inconsistency in the refined isotropic temperature factors from different zonal projections, however, indicates the necessity for a more accurate physical model for epitaxially grown crystals which will account for a large spread of diffraction peaks along reciprocal lattice lines parallel to the projection axis.
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    A quantitative electron microscopic study of the crystallite structure of molecular weight fractions of linear polyethylene (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 1901-1917 
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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: Utilizing thin-section techniques, transmission electron microscope studies were performed on a series of bulk-crystalized fractions of linear polyethylene covering the range M = 5 × 103-6 × 106. The crystallization conditions were varied from long-time isothermal to rapid quenching. Quantitative analysis could be carried out on such samples crystallized under controlled conditions. The crystallite thickness distributions and long periods are presented in terms of histograms. From these data the degree of crystallinity can be calculated and was found to compare favorably with that from other methods. The amorphous thickness increases significantly with molecular weight for all modes of crystallization. On the other hand, the crystallite thickness is essentially independent of molecular weight for very rapid crystallization, and shows a complex dependence on chain length for isothermal crystallization. The tilt angle, the angle of inclination of the chain axis with the lamellar basal plane, has also been determined. There is a tendency for this angle to increase with decreasing crystallization temperature. This observation can be related to the crystallization mechanisms.
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    High-resolution electron microscopy of polyethylene and paraffin crystals: Stability in the electron beam (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 1931-1951 
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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: Uncollapsed polyethylene pyramids (200-1500 Å) in length are irradiated with the electron beam of a 100-kV transmission electron microscope. Their high stability is remarkable compared to the stability of 1-10 μm crystals collapsed on the substrate, usually taken as a reference. Therefore, the maximum magnifications (300,000-750,000 X) of the microscope can be used and high-resolution images can be obtained. No lattice defects can be detected in the images of PE pyramids. Irradiation with Dc 〉 800 C/m2 induces the orthorhombic → hexagonal transition, and slight lattice distortions appear in the high-resolution image of the hexagonal phase. For an irradiation dose Dc ≈ 2400 C/M2, the diffraction pattern disappears. Normal C36 orthorhombic and monoclinic paraffins have the same stability as orthorhombic PE and high-resolution patterns are obtained. These exceptional stabilities are discussed in detail. From the diffraction pattern of these uncollapsed pyramids, the fold surfaces of PE pyramids have been indexed as the {111} and paracrystalline distortions in the orthorhombic PE have been measured at low irradiation dose. Along the a and b axes g is ca. 5% and along the chain axis c it is ca. 17%; these values agree with the previous x-ray determinations of PE crystallized from the melt. The large difference between these two distortion factors may be interpreted in terms of packing.
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    The role of molecular diffusion in the adhesion of elastomers (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 1953-1968 
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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: Butyl rubber (polyisobutylene-co-isoprene) mixed with polyisobutylene was crosslinked to yield elastomeric macromolecular networks containing dissolved linear macromolecules. Adhesion of these materials to themselves (self-adhesion) and to an inert substrate was investigated over a wide range of peel rates and test temperatures. Greatly enhanced self-adhesion was found when linear polyisobutylene molecules of high molecular weight were present, but the strength of adhesion to a rigid inert substrate was hardly affected. The enhancement of self-adhesion is attributed to interdiffusion of polyisobutylene molecules. It was greatest at intermediate peel rates and temperatures, becoming insignificant at extremely low rates, probably because the diffusing species can then migrate readily, and at high effective rates of peel when the polymer approaches the glassy state and the strength of adhesion is high in all cases. A transition to somewhat lower levels of adhesion at relatively high rates of peel is tentatively ascribed to the onset of molecular fracture in place of pullout. The presence of large amounts of low-molecular-weight polyisobutylene (M̄v = 50,000 g/mol) increased the level of self-adhesion and of adhesion to an inert substrate to a similar degree, over a broad range of peel rates. This effect is attributed primarily to enhanced viscous losses in the elastomeric layer during separation. Application of these results to crack and weld-line healing in glassy plastics is discussed.
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    Molecular aggregation and mechanical properties of Kapton H (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 1979-1985 
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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: Molecular aggregation of Kapton H (KH) was investigated by small-angle x-ray scattering (SAXS). Superstructure parameters were estimated using a one-dimensional model, taking into account that the SAXS from KH is anisotropic out of the film plane. The results show that KH has a two-phase structure with a volume ratio of the ordered to the less-ordered phase of about 1:1. The β dispersion in dynamic mechanical properties is reasonably ascribed to oscillations of p-phenylene groups in the main chain.
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    Crystallinity and thermal properties of polyamides containing cis- and trans-1,3-cyclohexane rings (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 1969-1977 
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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 cyclohexane ring-containing polyamide 1,3-CBMA-6 was synthesized from 1,3-cyclohexane-bismethylamine (1,3-CBMA) and adipic acid (6), and effects of cis/trans isomers of the ring on crystallinity and thermal properties were studied. Polymers with high cis and high trans contents, respectively, were made by polymerizing the 1,3-CBMA-6 salts of 98% cis and 93% trans derived from the salt of 75/25 (cis/trans) by fractional crystallization. A polymer with 97% cis content was highly crystalline, with a melting temperature of 253°C, while one with 93% trans contents was amorphous. In contrast to this, little difference was found in the glass transition temperature of 97 and 84°C. These results indicate that the isomers affect the conformation of the molecular chains, which determines the crystallinity and melting temperature, but they do not much affect the mobility of the chains as manifested by the glass transition.
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    The influence of carbonyl and ether linkages on the conductivity of polymers (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 1987-1989 
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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
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    The dynamics of mechanical relaxation in polyisobutylene (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 1991-2008 
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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 published data on the mechanical response of a set of samples prepared from a single batch of polyisobutylene have been examined and three relaxation/retardation processes have been characterized in the temperature region above the glass transition temperature. It is shown that the time/frequency dependences can be explained in terms of the cooperative theory of relaxation/retardation. It is also shown that the values of the fractional power-law indices of relaxation/retardation, which are a characteristic feature of the cooperative approach, are independent of the technique used in their observation.
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    Magic-angle 13C-NMR of cured and degraded acrylic copolymer/melamine formaldehyde coatings (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), 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: Magic-angle carbon-13 NMR has been used to probe the structure and dynamics of acrylic copolymer melamine formaldehyde crosslinked coatings. Changes in chemical composition that occur in conventional accelerated weathering tests were found to be dominated by hydrolysis of acrylic-melamine crosslinks and subsequent formation of melamine-melamine crosslinks. Evidence for photo-oxidation was also observed. These results are in substantial agreement with infrared measurements also made on these coatings. Gated high-power decoupling experiments were used to determine relative mobilities of the different carbon resonances as a function of acrylic copolymer composition and as a function of degradation. It was found that motion of the side-chain carbons on the acrylic copolymer was not sensitive either to the chemical composition of the coating or to the extent of degradation. Mobilities of the main-chain carbons of the acrylic copolymer decrease with increasing glass transition temperature of the acrylic copolymer. For acrylic copolymers containing styrene, it is found that the main-chain carbon mobilities decrease with weathering. The melamine triazine ring becomes very rigid after degradation consistent with the formation of short melamine-melamine crosslinks.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.180221202
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    Regularities in x-ray scattering patterns from amorphous polymersMMI contribution No. 217. (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 2043-2050 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It is known that the x-ray scattering pattern of an amorphous polymer may contain one or more halos corresponding to van der Waals spacings or larger. In this work we found that (i) the halo positions (and equivalent Bragg spacings) vary systematically with the cross-sectional area of the polymer chain in the crystal and (ii) there are at least two families of such halos with spacings larger than that of van der Waals contacts of atoms. From the wide variety and nature of the polymers considered, this behavior is believed to be representative of the amorphous state existing in polymeric samples. This work indicates that there is a degree of packing regularity in amorphous polymers that should be considered in models and theories of polymer chain conformation.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1984.180221204
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    Anomalous viscosity behavior of some poly(methyl methacrylate)s prepared by anionic polymerization (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 2105-2118 
    Details
    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(methyl methacrylate)s with molecular weights in the range 3.0 × 104-1.03 × 106 have been prepared by anionic polymerization and their limiting viscosity numbers determined in a variety of solvents. It was found that whereas the higher-molecular-weight polymers behaved normally, the lower-molecular-weight polymers showed anomalous behavior. First, the limiting viscosity numbers of the lower-molecular-weight polymers were much higher than expected, and, second, their number-average molecular weights as measured by gel permeation chromatography were considerably smaller than those determined by membrane osmometry.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1984.180221209
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    Preparation, fractionation, and dilute-solution behavior of ABA poly(methyl methacrylate-b-α-methylstyrene) block copolymers (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 2119-2138 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The preparation by anionic polymerization of six ABA poly(methyl methacrylate-b-α-methylstyrene) block copolymers and of sixteen poly(α-methylstyrene)s is described. The block copolymers, of similar molecular weight but with different chemical compositions, were fractionated by preparative gel permeation chromatography and their behavior in dilute solution was investigated using viscometry. The results obtained indicate that the intramolecular phase separation does not occur under the conditions utilized, the block copolymers assuming randomcoil configurations in all of the copolymer/solvent systems studied. Consequently the block copolymer molecules are more expanded than homopolymers of the same molecular weight. The series of poly(α-methylstyrene)s covered the molecular weight range 2.7 × 103-1.3 × 106 and enabled the determination of Mark-Houwink-Sakurada constants for poly(α-methylstyrene) in the solvents chosen for the block copolymer studies.
    Additional Material: 8 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1984.180221210
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  • 91
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    Analysis of the hysteresis curve of ferroelectric polymers by a phenomenological relaxation theory (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 2139-2144 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A simple relaxation theory for the displacement versus electric field hysteresis of ferroelectric polymers is developed in which the relaxation time is assumed to be a function of electric field, as has been experimentally evidenced by polarization-reversal switching. The theory gives an analytical expression for the hysteresis curve. The coercive field Ec predicted by the theory agrees well with data on Ec as a function of temperature for poly(vinylidene fluoride) from -60 to 20°C and with data on Ec as a function of frequency for vinylidene fluoride/trifluoroethylene copolymer (73/27 molar ratio) at 20°C over the range 0.01-0.7 Hz.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1984.180221211
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  • 92
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    Small-angle polarized light scattering from amorphous spheres (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 2159-2163 
    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 light-scattering measurements have been made using micron-diameter isotropic and spherical polymer latex particles placed between crossed polarizers. Four-leaf clover patterns are obtained, reminiscent of those commonly found for spherical birefringent scatterers. The experimental results compare closely with predictions of Mie scattering theory for isotropic spheres.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1984.180221213
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    Phase separation phenomena in solutions of poly(2,6-dimethyl-1,4-phenylene oxide). IV. Thermodynamic parameters for solutions in a series of homologous solvents: Toluene to hexylbenzene (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 2145-2157 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Melting-point curves for solutions of poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) in a series of homologous solvents (toluene to n-hexylbenzene) have been obtained from visual and differential scanning calorimetry measurements. The measured melting points were used to calculate thermodynamic interaction parameters. It was found that consistent values were obtained with the Flory-Hoffman melting-point depression equation, if the assumption was made that solvent molecules are incorporated in the crystal lattice. To this end, an adapted dependence of the enthalpy of melting per polymer unit on the cocrystallizing solvent was used. The values of the thermodynamic interaction parameters in the series of solvents and their dependence on polymer weight fraction are explained qualitatively with simplified versions of equation-of-state theory and solubility parameter theory.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1984.180221212
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    Analysis of the longitudinal acoustic mode in linear aliphatic polyesters (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 2185-2194 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Two intense modes are observed in the low-frequency Raman spectra of as-grown and annealed linear aliphatic polyester single crystals. Our experimental data in conjunction with theoretical normal mode calculations of several model oligomers reveal the two bands observed to be vibrations of the longitudinal acoustic mode type. The unbalanced mass units associated with the ester groups couple the transverse and longitudinal motions, giving rise to the multiple modes.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1984.180221216
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    Birefringence of amorphous polyoxides: Stress-optical behavior of poly(3-methyltetrahydrofuran) (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 2165-2174 
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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 stress-optical behavior of an unswollen elastomeric network of poly(3-methyltetrahydrofuran) was measured for elongation ratios a in the range 1.182-1.549, at several temperatures between 20 and 60°C. No evidence of strain-induced crystallization was found; moreover, the dependence of birefringence Δn on true stress f/A was linear in the interval of α investigated. Values of Δa ranged from 2.4 to 2.8 in units of 10-24 cm3, in the temperature range studied, with a temperature coefficient 3.1 × 10-3 K-1. Theoretical calculations carried out with the rotational-isomeric-state model gave values of Δa noticeably smaller than the experimental results; however, a small increase in the backbone valence angles θ improved the theoretical result of Δa without worsening that of the dipole ratio. Analysis of the Δa results seems to corroborate the conclusion obtained through the study of dipole moments concerning the preference for nucleophilic attack on the less hindered α carbon in the monomer. Theoretical and experimental values of the temperature coefficient of Δa were in clear disagreement; a qualitative explanation for this discrepancy is discussed.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1984.180221214
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    High-temperature aging of Halar film. II. Analysis of melting behavior (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 2175-2184 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Melting behavior of an experimental Halar film, a predominantly alternating 1:1 copolymer of ethylene (E) and chlorotrifluoroethylene (CTFE), has been studied. Differential scanning calorimetry (DSC) reveals single or double melting peaks, depending upon the thermal history. The lower-temperature melting peak Tm1 is produced only by the thermal treatment and shows a strong dependence on annealing time and temperature. On the basis of the DSC and x-ray data it can be suggested that Tm1 represents the melting of relatively small crystallites formed upon annealing. The higher-temperature melting peak Tm2 is always shown at 238°C. (Note: the specification for commercial Halar product is 240°C. The slightly lower melting temperature reported in this study is probably due to the fact that we are dealing with an experimental melt-processed material.) On the basis of the heating rate study we propose that Halar crystallizes with stable crystals (Tm2 = 238°C) regardless of the crystallization conditions, i.e., quenching, slow cooling, or even annealing. Crystals of Halar have a heat of fusion of approximately 35 cal/g or 146 kJ/kg. Detailed analysis of the melting behavior of Halar is presented.
    Additional Material: 8 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1984.180221215
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  • 97
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    Thermally induced cholesteric-isotropic transition in lyotropic polypeptide liquid crystals (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 2207-2213 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The thermally induced cholesteric to isotropic transition of lyotropic polybenzylglutamate liquid crystals in six solvent combinations was examined optically. The solvents chosen for study support both low and high pitch values, positive and negative pitch temperature coefficients, and polypeptide denaturation. The biphasic zone below the clearing temperature is broad and solvent dependent. Unusual large-scale phase separations and solution morphologies occur in some solvents. No evidence was found for pretransitional chiral orientational ordering near the clearing point in the high-temperature isotropic phase.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1984.180221218
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    New treatment of the theory for small-angle x-ray scattering with applications to polystyrene crazes (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 2215-2241 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The phenomenon of surface scattering of electromagnetic waves by single or multiple layers of films is reviewed and a special treatment for the total reflection of x rays is developed. This theory is applied to the analysis of the surface scattering observed in small-angle x-ray scattering (SAXS) studies of two-phase matter in polymers having lamella stacks or a flat interfacial boundary structure. Important features of this vector theory are the ability to calculate the surface scattering invariant, the absolute scattering intensity, and the surface roughness, which gives rise to dispersion of specular reflection from perfectly smooth surfaces. By considering the interfacial surface roughness of polystyrene crazes, the surface scattering spectrum is calculated theoretically and compared with some experimental results. Also the theory is presented in such a way as to compare surface scattering with volume scattering; i.e., both two- and three-dimensional scattering events can be simultaneously treated. This provides a new basis for quantitative analysis of crazes in polystyrene.
    Additional Material: 20 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.180221219
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    Synthesis and conductivity of poly acene quinone radical polymers (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 2243-2260 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polymers with conductivities from 8.6 × 100 to 7.3 × 10-6 (ω cm)-1 at 2-12 kbar were prepared by zinc-chloride-catalyzed condensation of polycyclic aromatic hydrocarbons, heterocycles, and quinones with pyromellitic dianhydride, tetrabromophthalic anhydride, and tetrachlorophthalic anhydride at 450°C. These materials are stable in air and exhibit strong electroactive character without addition of oxidizing or reducing agents (dopants).
    Additional Material: 8 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1984.180221220
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    Influence of polystyrene excimers on the excitation energy transfer in solid scintillating solutions (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 2275-2278 
    Details
    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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.180221222
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