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  • Articles  (977)
  • Physics  (977)
  • Inorganic Chemistry
  • LUNAR AND PLANETARY EXPLORATION
  • 1980-1984  (977)
  • Physics  (977)
  • Biology  (1)
  • 1
    Electronic Resource
    Electronic Resource
    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 
    Details
    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.
    Additional Material: 22 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.180220101
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  • 2
    Electronic Resource
    Electronic Resource
    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 
    Details
    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.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.180220105
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  • 3
    Electronic Resource
    Electronic Resource
    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 
    Details
    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.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.180220208
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  • 4
    Electronic Resource
    Electronic Resource
    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 
    Details
    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.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.180220209
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  • 5
    Electronic Resource
    Electronic Resource
    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 
    Details
    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
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.180220212
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  • 6
    Electronic Resource
    Electronic Resource
    Configurational studies on amylose. I. Scattering functions (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 1551-1559 
    Details
    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.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.180220901
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  • 7
    Electronic Resource
    Electronic Resource
    The heat of fusion of 66 nylon (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 1615-1621 
    Details
    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.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.180220905
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  • 8
    Electronic Resource
    Electronic Resource
    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 
    Details
    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.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.180220908
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  • 9
    Electronic Resource
    Electronic Resource
    Tearing of unvulcanized natural rubber (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 1623-1634 
    Details
    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.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.180220906
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  • 10
    Electronic Resource
    Electronic Resource
    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 
    Details
    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.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.180220907
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  • 11
    Electronic Resource
    Electronic Resource
    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
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.180220910
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  • 12
    Electronic Resource
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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 
    Details
    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.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.180221002
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  • 13
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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.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.180221004
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  • 14
    Electronic Resource
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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.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.180221102
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  • 15
    Electronic Resource
    Electronic Resource
    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.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.180221104
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  • 16
    Electronic Resource
    Electronic Resource
    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.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.180221103
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  • 17
    Electronic Resource
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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.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.180221106
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  • 18
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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.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1984.180221105
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  • 19
    Electronic Resource
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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.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.180221107
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  • 20
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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.
    Additional Material: 14 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1984.180221108
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  • 21
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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.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1984.180221110
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  • 22
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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.
    Additional Material: 9 Ill.
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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.
    Additional Material: 8 Ill.
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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.
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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 
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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: 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.
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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 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A series of poly(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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    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 
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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 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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    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 
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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 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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    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 
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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: 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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    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 
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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: 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.
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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 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Two 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.
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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.
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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 
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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: 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.
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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 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The thermally 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.
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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 
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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 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.
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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 
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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: 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).
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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 
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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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    Studies of TSD of polyethylene electrets by a differential technique (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 21-32 
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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 determination of charge storage and charge decay processes in polyethylene electrets by means of TSD techniques alone seems to be limited by deficiencies in resolving power and reproducibility. Therefore, in the present work, we describe a new differential technique which cancels the effects of parasitic currents and improves the reproducibility of the measurements. The dependence of the shape of thermograms on experimental poling conditions has been studied. The comparison of discharge currents from the differential technique and from the usual one has also been found to be an interesting means of investigating the charge decay processes.
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    Morphology of conducting organic polymers: Polythiophene and poly(3-methyl thiophene) (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 33-39 
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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: Polythiophene and substituted polythiophene can be electrochemically generated as very adhesive thin films or as thick powdery deposits. The homogeneity of the thin films is very high, but it decreases when the film thickness is increased. Scanning electron microscopy shows that the nature of the dopant strongly influences the film morphology. Transmission electron microscopy reveals mainly a fibrillar structure, with a fibril diameter of 200 Å in the undoped state, and 800 Å in the doped conducting state.
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    A far-infrared study of ionic interactions in poly(styrene sulfonic acid) ionomers (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 67-77 
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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 far-infrared spectra of poly(styrene sulfonic acid) (PSSA) ionomer films containing alkaline and alkaline earth ions have been studied, and strong, broad bands, whose frequencies are cation dependent, have been observed and assigned to cation motion. The force field elements for cations vibrating at sulfonate-containing sites have been obtained for different models of the cation-motion vibration. The effects of hydration, dehydration, and thermal annealing are discussed in light of ion clustering in these materials.
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    Morphological and structural changes in a copolymer of glycolide and lactide occurring as a result of hydrolysis (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 57-66 
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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 changes in the structure and morphology of a random copolymer containing 92 mol % glycolide units and 8 mol % lactide units as a function of in vitro hydrolysis have been studied. A number of techniques, such as wide-angle x-ray diffraction, small-angle x-ray scattering, density measurements, infrared spectroscopy, and viscometry were employed in this study. The results showed that the hydrolytic attack was initiated in the amorphous areas of the polymer. After 28 days in the in vitro medium most of the amorphous areas had been chemically converted to lower-molecular-weight species such as oligomers of poly(glycolide-co-lactide). These low-molecular-weight species become water solble and are removed rapidly after day 28. Thus the fiber takes on a Swiss cheese character as the amorphous matter is hydrolyzed and eventually dissolved. As hydrolysis proceeds further, the crystalline areas of the polymer are attacked and eventually removed from the fiber by solubilization. The resulting voids in the fiber are eventually filled by a “collapse” of the structure. The role of the amorphous areas of the polymer in controlling the tensile strength of the suture is discussed.
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    The hexagonal phase and melt of low-molecular-weight polyethylene (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 175-182 
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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: Phase diagrams of low-molecular-weight polyethylene (M = 1000, 2000, 6500, 16,000) and polyethylene (M ≈ 1,000) after fuming nitric acid treatment have been determined from 20 to 300°C up to pressures of about 10 kbar. The fractions with molecular weights 1000 and 2000 do not exhibit the hexagonal phase, but the others do. Effects of molecular weight and fuming nitric acid treatment on the phase diagrams are discussed in terms of the entropy of the melt.
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    On the structure of polyurethane hard segments based on MDI and butanediol-1,4: X-ray diffraction analysis of oriented elastomers and of single crystals of a model compoundDedicated to Professor Herbert Grunewald on the occasion of his 60th birthday. (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 163-173 
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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: Single-crystal x-ray diffraction analysis is performed on a model compound (bisurethane of diphenylmethane-4-monoisocyanate and butanediol-1,4) for the thermoplastic polyurethane (TPU) hard segment formed from diphenylmethane-4,4′-diisocyanate and butanediol-1,4. The resulting structure is compared to structure models of corresponding TPU hard segments, especially to the structure proposed by Blackwell and Ross. Our results confirm this structure model showing a planar zigzag of the (CH2)4 group and planar hydrogen bonding between the urethane groups of adjacent molecules. X-ray diffraction analyses of polymeric TPU hard segments and of TPU elastomers with noncrystallizing soft segments lead to a revision of the dimensions of the proposed lattice cell, resulting in a more plausible value of 1.3226g/cm3 for the crystal density.
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    Application of the transverse differential swelling stress model to the interpretation of case II diffusion kinetics (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 183-189 
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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: Attention is called to an early observation of Case II diffusion kinetics during penetration of a liquid into a uniaxially prestretched polymer film along the axis of stretching. Application of a previously developed transverse differential swelling stress model to these experimental conditions is described. It is shown that the model can predict Case II diffusion kinetics in a physically meaningful manner and will also explain the transition of the kinetics of the above system into normal or hindered diffusion regimes as either the degree of stretching or its direction relative to that of penetration is changed.
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    The dependence of yield behavior on temperature, pressure, and strain rate for linear polyethylenes of different molecular weight and morphology (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 191-209 
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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 temperature, strain-rate, and pressure dependences of the yield stress have been determined for two polyethylene homopolymers of differing molecular weights and for a polyethylene copolymer. Samples were prepared by slowly cooling from the melt, and also by quenching in order to assess the effects of morphology on the yield behavior. The data have been analyzed on the basis of two Eyring processes acting in parallel. Comparison of all data sets reveals the existence in general of three distinct activated processes each with its own temperature, strain-rate, and pressure dependences. The relative contribution of each process is dependent on the molecular weight, morphology, etc. Also discussed is the relation of these three yield processes to the well-known loss processes of linear viscoelasticity.
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    Effect of diluents on poly(vinyl acetate) dynamics (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 211-221 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effect of diluents and temperature on segmental motion in poly(vinyl acetate) was investigated by both NMR and ESR spectroscopy. Three classes of diluents were studied: chloroform, a thermodynamically good solvent; water, a poor solvent which slightly swells the polymer and lowers its glass transition temperature; and decane, a nonsolvent so poor it does not appear to swell the polymer nor lower the calorimetric glass transition temperature. At all temperatures investigated each type of diluent increased the segmental motion of the polymer over that of the bulk sample. Under the conditions studied, 13C and 2H NMR and nitroxide spin-label ESR data gave similar views of segmental motion of the polymer, indicating that in this amorphous polymer the segmental motion of the polymer may be safely inferred from spin-label data.
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    Solution annealing of poly(TMPS) crystal mats (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 223-236 
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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(tetramethyl-p-silphenylene siloxane) crystal mats initially prepared from benzene/methanol (2:1 v/v), when annealed in small amounts of solvent undergo considerable thickening in the chain direction. When the crystals are annealed above their formation temperature, their physical properties change rapidly at first before reaching an asymptotic limit commensurate with annealing time and type of solvent. Changes in melting temperature, heat of fusion, small-angle x-ray spacing, and wide-angle x-ray scattering patterns have been monitored for three solvents of varying solvent power, ranging from very good to extremely poor. Upon solution annealing, the original crystals mats equilibrate to more stable dimensions compatible with their environment. The activation energy of crystal thickening in contact with a liquid is estimated to be about an order of magnitude lower than that deduced from dry annealing data. It appears that the crystal surface and the crystalline core of the crystals comprising the mats must participate in the measured severalfold increase in long period noted after annealing. The lower surface (or interfacial) energy of the liquid annealed mats compared to isothermally melt-crystallized polymer of similar molecular weight has a direct bearing on the polymer morphology and crystallinity.
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    Self-diffusion in polymer-solvent-solvent systems (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 459-469 
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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 ternary self-diffusion data of Ferguson and von Meerwall are analyzed using a generalized form of the free-volume theory of diffusion proposed by Vrentas and Duda. It is shown that the predicative capabilities of this form of the theory are satisfactory and comparable to those of the Fujita version. The lack of significant differences in the predictive capabilities of the two theories for the two ternary systems studied is explained in terms of the properties of the materials utilized. The data of Ferguson and von Meerwall are consistent with the hypothesis that the size of a polymer jumping unit is a fixed property of the polymer and that the jumping units for sufficiently large n-paraffins are smaller than the entire solvent molecule.
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    Birefringence of high-pressure injection-molded high-density polyethylene at 70.5 μm wavelength (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 471-474 
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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 newly constructed far-infrared laser interferometer was used to measure the birefringence of 1-mm-thick injection-molded high-density polyethylene test bars, manufactured at unusually high molding pressures. The long wavelength used, 70.5 μm, allowed nondestructive tests to be made, demonstrating the usefulness of far-infrared techniques for probing crystalline polymers. The birefringence was shown to increase with increasing molding pressure, supporting the belief that molecular orientation increases with increasing molding pressure. The tensile modulus was also measured and was found to increase linearly with molding pressure.
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    The drawing behavior of polyethylene copolymers (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 475-484 
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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 tensile drawing behavior of a range of selected polyethylene copolymers has been studied. Sheets were prepared by quenching molten polymer into cold water. Two-centimeter-gauge-length samples were then drawn in air at 75 or 115°C in an Instron tensile testing machine at a crosshead speed of 10 cm/min. It was found that even at the very low concentration of one side branch per 1000 carbon atoms there was a very marked effect on the strain hardening behavior and the maximum draw ratio that could be achieved. The reduction in draw ratio increased with increasing branch concentration, and long branches were more effective than short branches in limiting the draw ratios achieved. The similarity between these effects and the effects of increasing M̄w or radiation crosslinking is noteworthy. This suggests that even a very small concentration of branches can significantly reduces the moleculer motions required for the process of plastic deformation. The Young's modulus/draw ratio relationship follows a pattern virtually identical to that observed in the case of homopolymers.
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    Model calculations of the distribution function of molecular weight and chemical composition of binary statistical copolymers (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 501-517 
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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: Model calculations based on the kinetics of free-radical copolymerization were carried out for the distribution functions of molecular weight and chemical composition, and for heterogeneity parameters of statistical copolymers. The calculations were conducted so as to depict the dependence of the heterogeneity parameters on the degree of conversion and to make possible an estimate of the maximal heterogeneity of statistical copolymers at given monomer reactivity ratios and rate constants. A comparison of the results obtained with a critical analysis of the feasibility of the determination of heterogeneity parameters by light scattering has revealed that, for statistical co polymers, this method can in principle be used with satisfactory accuracy only with samples of high degree of conversion and high molecular weight. The frequently used approximation P = 0 cannot be applied with out careful verification.
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    Changes in superstructure of drawn isotactic polypropylene with annealing: A two-dimensional small-angle x-ray analysis (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 485-500 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Two-dimensional small-angle x-ray (SAXS) analysis is extended and applied to isotactic polypropylene cold-drawn and annealed near the melting point. The SAXS intensity down to very small angles is detected by a high-resolution point-collimation camera. The SAXS fiber pattern, exhibiting only one meridional reflection and continuous scattering on the equator, shows that the microparacrystallites (“bricks” of the macrolattice) are densely packed together laterally into finite extended layers. The drawing process increases the ultrafibrillar characteristics of the samples and annealing increases their lamellar character. Annealing is carried out at a temperature near the melting point with the ends of the samples fixed so that recrystallization under strain takes place. The volume crystallinity increases on annealing from 32 to 57%. The SAXS results are in good agreement with NMR results; nevertheless the ideal paracrystal model assumption is, in the present case, not quite consistent with the results.
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    Diffusion during the immersion precipitation process (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 519-524 
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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: 5 Ill.
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    Determination of relative rate constants of reactions on polymers from the triad distribution data (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 525-527 
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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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    Mechanical properties of electron-irradiated polysulfones (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 529-533 
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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: 5 Ill.
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    Elastic modulus of syntactic foams (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 535-535 
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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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    URL: http://dx.doi.org/10.1002/pol.1984.180220316
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    Isothermal melting behavior of poly(L-lactic acid) (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 537-542 
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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 isothermal melting behavior of poly(L-lactic acid) spherulites has been studied in order to understand the mechanism of melting using hot-stage microscopy. When the periphery of the spherulite melts or shrinks, the central portion undergoes thickening as a result of which the melting or shrinking rate is not linear. Annealing studies at 448 K reveal that there is an increase in melting temperature and heat of fusion with annealing time, suggesting an increase in lamellar thickness. The high activation energy (828 kJ/mol) obtained in this investigation suggests the highly complex nature of the melting process wherein both melting and thickening occur.
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    Crazing in polyethylene (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 543-559 
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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 tensile stress - strain curves of various types of polyethylene were compared from 77 to 298 K in nitrogen, isopentane, and the inert environment of helium at various strain rates. It was found that in general polyethylene crazes in a gas such as nitrogen at a temperature below 1.6 times its boiling point and in isopentane. Although the behavior of polyethylenes is similar to that of other polymers with regard to crazing in gases at low temperatures, they are in general less sensitive to the gas. The decrease in tensile strength of polyethylene in an environmental gas increases with crystallinity. The differences in the intrinsic low-temperature brittle fracture stress are attributed to differences in the density of tie molecules. The intrinsic yield point at room temperature showed the usual increase with increasing crystallinity, but all the polyethylenes have the same yield point below the γ transition temperature.
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    Creep behavior of ultrahigh-modulus polyethylene: Influence of draw ratio and polymer composition (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 561-575 
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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 creep behavior of ultrahigh-modulus polyethylene monofilaments has been studied over the temperature range 20-70°C. A wide range of samples was examined in an attempt to determine the influence of draw ratio, molecular weight, copolymerization, and crosslinking by γ irradiation Prior to drawing. Results are also presented for a solution-spun fiber. It is proposed that the permanent flow creep arises from a combination of two creep processes, one of which is associated with the crystalline regions of the oriented structure and the other with a molecular network.
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    Complex formation between enantiomeric polyesters (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 577-587 
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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 this study, three different polymers were blended: a racemic PMEPL (PMEPL-RAC) which consists of a random distribution of repeat units of R or S configurations, an isotactic PMEPL made of repeat units of S configuration [PMEPL-S(-)], and a second isotactic PMEPL made of repeat units of R configuration [PMEPL-R(+)]. The acronym PMEPL stands for poly[α-methyl-α-ethyl-βpropiolactone]. The racemic PMEPL is optically inactive but the isotactic PMEPLs are optically active. In the first part of this study, an equimolar mixture of PMEPL-S(-) and PMEPL-R(+) was made. This racemate mixture leads to the formation of stereocomplex between the two polymers which has a melting point roughly 40°C higher than those of the isotactic polymers. The racemate morphology is composed of large spherulites. In the second part of this study, binary blends of PMEPL-S(-) and PMEPL-R(+) were prepared with an excess of one of the isotactic PMEPLs. The stereocomplex is preferentially formed between the isotactic polymers and this complex controls almost entirely the morphology of the sample. The enthalpy of fusion of the stereocomplex in the binary blends can be predicted. however, the excess isotactic polymer is trapped between the lamellae of the spherulites of the stereocomplex and its crystallization is hindered by the high viscosity of the partially crystallized medium. In the third part of this study, ternary blends were prepared. It is shown that PMEPL-RAC does not from a complex with the isotactic polymers. The PMEPL-S(-)/PMEPL-R(+) stereocomplex is again preferentially formed and it controls the morphology of the sample. It decreases the degree of crystallinity of both the excess isotactic polymer and the PMEPL-RAC. This control of the morphology is effective even in samples in which the sterocomplex accounts for only 3% of the total weight of the blend.
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    The effects of morphology on 1H NMR spectra and relaxation in semicrystalline polyolefins (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 589-616 
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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 brief résumé is given of the role of structural heterogeneity, magnetic dipolar couplings, molecular structure, and molecular motion in determining the 1H NMR spectra and relaxation properties of heterogeneous solids such as semicrystalline polymers. Measurements of 1H spin-lattice relaxation in laboratory (T1) and rotating frames (T1ρθ) are reported for a number of solid polyolefin samples. These include solution-crystallized and melt-crystallized polyethylene, annealed and quenched isotactic polypropene, and isotactic polybut-1-ene. In addition, broad-line 1H spectra, both normal and partially (T1ρ90) relaxed, are reported for these materials as well as a number of pulsed NMR experiments having the philosophy of the so-called Goldman-Shen experiment. Spin-lattice relaxation (T1) for all samples is a single exponential process, whereas rotating-frame relaxation comprises three exponential processes both on-resonance (θ = 90°) and off-resonance at the magic angle (θ = 54.7°), with the latter generally being much slower. The spectra show clearly the existence of components having differing degrees of mobility and, with the exception of the solution-crystallized polyethylene, the partially (T1ρ90) relaxed spectra indicate a correlation between breadth of resonance line and magnitude of T1ρ. The Goldman-Shen-type experiments indicate a spin-diffusional transport of magnetization between the different spectral and (T1ρ90) components. A computer program has been used to simulate the NMR behavior of a three-region system comprising repeating units of infinite lamellae of different widths, each region having different intrinsic relaxation times and spin diffusion coefficients. The results demonstrate that the observed 1H NMR behavior of these samples can be interpreted in terms of this model and that, inter alia, the long-time T1ρ90 behavior reflects, qualitatively, the time taken for magnetization to diffuse a distance of the order of the dimensions of the region to which it corresponds.
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    Correction factors for sizing weakly anisotropic transparent fibers using light scattering (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 647-653 
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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: Correction factors defined as the ratio of the true size parameter and the size parameter deduced from Fraunhofer diffraction theory are presented for weakly anisotropic transparent fibers. These correction factors enable the Fraunhofer diffraction approximation to be used for sizing weakly anisotropic fibers from light-scattering measurements. Fibers in the diameter range 4-50 μm and refractive index range 1.45-1.56 are considered. It is shown that for fibers having birefringence -0.005 ≤ Δm ≤ 0.01, the diameters may be obtained to within 9% accuracy if the fiber diameter lies between 4 and 50 μm.
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    Viscometric behavior of mesomorphic ethyl cellulose solution in chloroform (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 637-646 
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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 simple modification of the viscometer used to determine the viscosity of concentrated solutions is described which permits the ready measurement of viscosity versus shear rate behavior above room temperature. Basic experimental viscometry was performed on the ethyl cellulose-chloroform system using a B-type (Brookfield-like) rotating-cylinder viscometer. Data are compared with theoretical predictions. The flow curves exhibit yield stress at low shear rate. The yield stress is dependent on concentration and temperature. The viscosity versus concentration curves show typical mesomorphic behavior. The concentration dependences of viscosity and yield stress are similar. The critical concentration increases with temperature. In the single-phase region (isotropic or anisotropic state) the viscosity decreases with temperature and the apparent activation energy (Ea) for flow is positive, but in the biphasic range the viscosity increases with temperature and Ea is negative. The experimental results for the critical concentration appear to agree with Flory's theory of rodlike molecules when the ratio of persistence length to diameter of the chain is taken as the aspect ratio.
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    Study of ordered structures of syndiotactic poly(methyl methacrylate) in solution and in the solid state (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 617-635 
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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: From analysis of infrared spectra it was found that in syndiotactic (s) poly(methyl methacrylate) (PMMA) in solution, long s sequences contain an increased population of diads with a skeletal conformation tt (in the staggered approximation). Self-aggregation of s-PMMA in solution leads to a further increase of the fraction of long s sequences in the extended chain conformation, and to an ordering of easter groups. When solid s-PMMA is isolated from a solution in which it exists in the aggregated state, these characteristics are preserved in the solid. The polymer appears partially crystalline by x-ray scattering, and it exhibits fibrillar morphology under the electron microscope. Ordered structures of s-PMMA melt at temperatures about 150°C, while the presence of residual solvent decreases the temperature of melting. Solid s-PMMA obtained from solutions in which aggregation of the polymer does not take place, like s-PMMA which did not come into contact with solvent, contains a higher proportion of syndiotactic diads with a skeletal conformation tg; these samples are amorphous and morphologically structureless. Analogies between the structure of ordered s-PMMA and the structure of the PMMA stereocomplex are also discussed.
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    NMR study of polyethylene crystallization kinetics under high pressure (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 655-667 
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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: Crystallization of polyethylene under hydrostatic pressures of 1-4.5 kbar is directly observed using pulsed proton NMR. The rate of growth of extended-chain polyethylene crystals is measured over this pressure range and to a maximum temperature of 227°C. The observed crystallization isotherms are superimposable on a log time scale; this implies a consistent mechanism for extended-chain growth over this pressure range. Avrami coefficients for high-pressure extended-chain crystallization are determined to be 1.3-1.7. A decrease of crystal nucleus surface free energies with increasing pressure is indicated. Findings are consistent with Wunderlich's model of initial folded-chain crystallization followed immediately by chain extension. Future applications of this NMR technique are briefly considered.
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    High-temperature phases of poly(p-xylylene) (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 669-679 
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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 crystal structure of poly(p-xylylene), as polymerized, is the α form. This transforms irreversibly to the β from by annealing or drawing. To clarify the mechanism of this transition, structural changes of the α and β crystals were examined with a high-temperature stage in the electron microscope. Two high-temperature phases, β1 and β2, were found and their structures were analyzed. In these structures lattice distortions due to rotational and translational motions of chains are in troduced, especially in the β2 form. The α → β transition is induced through such a disordered phase. The statistical arrangement of a molecule in the β-form unit cell results from freezing the disorder in the high-temperature phases.
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    URL: http://dx.doi.org/10.1002/pol.1984.180220410
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    Structural relaxation in amorphous polymersThis paper was part of a presentation at the 7th International Conference on Thermal Analysis, Kingston, Ontario, Canada, August 23-27, 1982. (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 699-706 
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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 theoretical calculation based on the general solution of a multi-ordering-parameter model is found to be in good agreement with the measured volume relaxation of poly(vinyl acetate). This suggests that a limiting equilibrium state is eventually reached, which may resolve the disagreement between the behavior of the model and experiments discussed in the literature. In addition, the asymmetric character of the isothermal response and memory effect is satisfactorily calculated from the same basic equation. The distribution function and the temperature-structure dependence of relaxation times are discussed.
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    Fourier-transform infrared studies of polypropylene during mechanical deformation (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 681-698 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Quantitative Fourier-transform infrared (FTIR) measurements of frequency shifts Δν and absorbance profile asymmetry are reported for various polypropylene samples as a function of uniaxial stress σ. Generally, it was found that the frequency shift coefficient αχ, defined by Δν = αχσ, depended on stress rate \documentclass{article}\pagestyle{empty}\begin{document}$\dot \sigma$\end{document}, draw ratio, λ, molecular orientation f, tensile modulus E, and annealing conditions. With annealing, αχ decreased with increasing shrinkage in the case of highly oriented isotactic PP. The αχ values for the “helix bands” were less affected than those for the “liquid bands.” With increasing \documentclass{article}\pagestyle{empty}\begin{document}$\dot \sigma$\end{document}, generally αχ increased to an apparent asymptotic limit. With increasing λ, f, or E, αχ also increased from αχ ≃ 0 for λ = 1 (spherulitic) to maximum values for highly oriented isotactic PP. The observed variations in αχ can be interpreted in terms of the changes in the peak position and shape of the nonuniform molecular stress distribution. Analogous behavior with x-ray diffraction peaks obtained for polymers under stress is discussed.
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    Sorption and diffusion of toluene in highly oriented polypropylene (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 707-719 
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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 sorption and diffusion of toluene vapor at 30°C in polypropylene with draw ratios from 1 to 18 have been studied. Drawing leads to the transformation of the initially spherulitic material into the fibrous structure, with many taut tie molecules lying mainly on the outer boundary of the microfibrils. The free volume and hence the sorption sites are thereby reduced, and the microfibrils become less and permeable as the draw ratio increases. As a result, the equilibrium concentration and the zero-concentration diffusion coefficient drop by factors of 4 and 30, respectively. The diffusion coefficient increases exponentially with toluene concentration but the concentration dependence becomes weaker with increasing draw ratio, indicating that the severely constrained chain segments in the drawn samples have much less freedom to mix with penetrant molecules. Annealing relaxes the tie molecules and thus restores the sorption and diffusion properties to values corresponding to completely relaxed amorphous component, i.e., to values even higher than those of the undrawn but quenched material.
    Additional Material: 11 Ill.
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    Polypropylene spherulite morphology and growth rate changes in blends with low-density polyethylene (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 739-747 
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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: Morphological studies of isotactic polypropylene/low-density polyethlene blends revealed that the shape, size, and orientation of LDPE occlusions remain undisturbed during the crystallization of IPP spherulites. On the other hand, LDPE occlusions introduce large changes in the internal structure of IPP spherulites. It was found that many new boundaries similar to those between spherulites are fromed when the crystallizing front passes the LDPE occlusion. Dead-ended boundaries with soft LDPE occlusions at the ends give rise to an improvement of the impact properties. It was shown that LDPE obstacles do not influence significantly the IPP spherulite growth rate in thin films or in the bulk.
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    Anisotropic swelling of doubly oriented nylon-11 with a lamellar structure (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 749-758 
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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: Rolled smaples of nylon-11 annealed in formic acid (90%) at 80°C remain doubly oriented and have the same allotropic form as filter mats of single crystals. the basal planes of the crystals are parallel to (00l) planes. the long spacing is larger than in filter mats. Experimental swelling results obtained on such samples are discussed on the basis of two extreme models, the lamellar and the switchboard models. The long spacing dy and the length of the sample (along 0Y) change reversibly by the same proportion during swelling. Insertion of solvent between lamellae is invoked to explain such changes of dimension. As linear swelling ratios computed from macroscopic dimensions and SAXS measurements can reach 100%, lamellar crystals are only bonded by a few chains. The large increase of the SAXS intensity observed when annealed doubly oriented samples of nylon-11 are wetted with allylic alcohol cannot be explained on the basis of the switchboard model but only with a three-phase lamellar model. These three phases are the crystalline phase, the fold region, and a dilute solution of polymer in the swelling agent.
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    The dynamic relaxation behavior of poly(acetoxyethl methacrylate) and poly(pivaloyloxyethyl methacrylate) (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 773-775 
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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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    Hard-segment polymorphism in MDI/diol-based polyurethane elastomers (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 759-772 
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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 analyses of methylene-bis(4)phenyl isocynate(MDI)/diol/poly(tetramethylene adipate) polyurethane elastomers prepared using hexanediol (HDO), butanediol (BDO), and propanediol (PDO) point to the development of a second crystalline structure in the hard segments as a result of thermal elongation and annealing. The HDO polymer crystallizes initially in the fully extended conformation, but a second crystal structure, a contracted form, develops with stretching and annealing at 130°C. In contrast, the BDO and PDO polymers crystallize initially in contracted conformation, but fully extended forms develop as a result of elongation and annealing. Only a contracted conformation has been seen so far in hard segments prepared using ethylene glycol (EDO) as the chain extender. These results correlate very well with DSC data for the same polymers. The development of the new crystal structures is accompanied by the appearance of new hard-segment melting peaks in the DSC traces. For the HDO polymer, the new peak for the contracted form appears at a higher temperature than that for the original extended form; for the BDO and PDO polymers the new peaks for the extended forms appear at lower temperatures than those for the contracted forms. Only a single peak is seen for the EDO polymer, for which only one crystal structure has been detected for the hard segments. These results indicate that the development of polymorphic crystal structures must be taken into account in interpreting the multiple melting phenomena seen for the hard domains in polyurethane elastomers.
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    Crazing and shear deformation in crosslinked polystyrene (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 721-737 
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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: Thin films of polystyrene (PS) are bonded to copper grids and crosslinked with electron irradiation. When the films are strained in tension regions of local plastic deformation, either crazed or plane stress deformation zones (DZs), nucleate and grow from dust particles. the nature of the local deformation, as well as the local extension ration λ, is determined by transmission electron microscopy. The behavior of the PS glass is consistent with its being a network of molecular strands of total density v = vE + vX, where vE is the entangled strand density inferred from melt elasticity measurements of uncrosslinked PS and vX is the density of crosslinked strands determined from the ratio of the applied electron dose to the electron dose for gelation. when v is less than 4 × 1025 m-3 (〈1.3vE), only crazes are observed whose microstructure is similar to those in uncrosslinked PS. As v increases from 4 × 1025 to 8 × 1025 m-3 (from 1.3vE to 2.5vE) shear deformation begins to compete with crazing. As v increases above 8 × 1025 m-3, only shear DZs are observed, the strain in which becomes progressively more diffuse as v increases. The λ in the crazes and DZs correlate well with λmax, the maximum extension ratio of a strand in a network of density v computed using the Porod×Kratky model. For crazes ln(λ) ≃ 0.9 ln(λmax) and for DZs ln(λ) ≃ 0.55 ln(λmax). The strain at which crack nucleation is first observed increases as v increases from 〈5% in uncrosslinked PS with v = 3.3 × 1025 m-3 to 〉20% in PS with v = 33 × 1025 m-3 (v = 10vE); crosslinking to still higher crosslink densities, e.g., v = 14vE, results in cracks which propagate in a catastrophic manner at low applied strains. An optimum v thus exists, one not too high to suppress local shear ductility but high enough to suppress crazes which can act as crack nucleation sites. these results are compared with previous results on a variety of linear homopolymers, copolymers, and polymer blends that are characterized by a wide range of v (v = vE). The transitions from crazing to crazing plus shear and from crazing plus shear to shear only take place at almost identical values of v. In addition the correlation between λ in the crazes and DZs and λmax for a single network strand is the same for both classes of polymers. This agreement implies that chain scission is the major mechanism by which strands in the entanglement network are removed in forming fibril surfaces. Craze suppression, by either increasing v in the crosslinked polymer or vE in the uncrosslinked ones, is due to the extra energy required to break more main-chain bonds to form these surfaces.
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    The effect of microstructure and molecular weight on the refractive index increment of polybutadiene in cyclohexane (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 777-779 
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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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    Microstructural rearrangement during heat treatment of drawn nylon 66 fiberAccepted for publication November 23, 1984 (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 781-792 
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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 nylon 66 fibers were drawn and subsequently heat treated isothermally and quenched. The heat-treated fibers were then examined by wide-and small-angle x-ray scattering (WAXS and SAXS), by differential scanning calorimetry (DSC), and by static mechanical testing. These measurements allow one to follow microstructural changes taking place during the course of the heat treatment. WAXS results show that as the treatment progresses, the crystallites become both more perfect and more disoriented with respect to the fiber axis. SAXS results show crystallite thickening. DSC results show that the melting point increases, goes through a maximum, and then decreases as the heat treatment progresses. The tensile modulus decreases with time to an asymptotic level. The changes in crystallite perfection and thickness occur more rapidly than do the changes in crystallite orientation, modulus, and melting point. A model is proposed whereby the two time frames are related to intracrystalline and intercrystalline processes, respectively.
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    A spectroscopic study to interpret the increased piezoelectric effect at high temperature in poly(vinylidene fluoride) (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 827-834 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Spectroscopic experiments were carried out to directly measure the electric-field-induced microstructural changes in PVF2 at high temperature (65°C). We found, in comparison with roomtemperature measurements, that the reduction of the coercive field is directly related to faster dipolar orientation at this temperature. Furthermore, the α to β or δ phase transformation can take place at a much faster rate and lower field strength than has been previously reported either theoretically experimentally.
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    Properties of crystallized trans 1,4-polyisoprene (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 793-803 
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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: Stirrer crystallization of a trans-1,4-polyisoprene fraction(M̄n = 3 × 105) was carried out from n-butyl acetate and from n-heptane solutions (2% w/v). Fibrous crystals in the ß form were obtained at temperatures of 46-48°C in the two solvents, respectively. At 36-46°C from n-butyl acetate and 25-35°C from n-heptane lamellar crystallization took place leading predominantly to the α form. Melting endotherms and densities for various samples were obtained. The maximum TENDO for α was 74°C and for ß 79°C and the maximum weight fraction crystallinity for ß was 0.78. The stability of performed α nuclei in n-butyl acetate and n-heptane using a fraction with M̄n = 2.5 × 105 was monitored as a function of temperature. The dissolution temperature of fibrous ß-TPI with the maximum TENDO was measured in 13 liquids and the results analyzed in terms of the Flory-Huggins parameter. The heats of fusion for the α and ß forms, obtained by extrapolation of heat of fusion versus change in specific volume, were found to be 8.0 and 10 kJ mol-1, respectively. The pressure coefficients of the melting temperature were calculated to be 38 and 43 K kbar-1 and the fold-surface free energies recalculated to be 42 ± 1 and 53 ± 1 erg cm-2 for the α and ß forms, respectively. The number of monomer units per average noncrystalline chain traverse for the most crystalline fibrous ß-TPI was estimated at 36.
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    Polymer fibers drawn to the limitPresented at IUPAC 28th Macromolecular Symposium, Amherst, MA, 1982. (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 805-826 
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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 orientational drawing of polymers is known to be terminated because of sample rupture. The limiting draw ratio λlim reached may be different (either large or small) depending on the polymer and the actual drawing conditions. The purpose of the present work is to identify the change of supermolecular structure of polymer fibers which results in the termination of orientational drawing. Small-and wide-angle x-ray diffraction were used to study the variation of geometrical parameters of this structure with increasing draw ratio λ. The geometrical parameters discussed are the dispersions (fluctuation) of long periods and of longitudinal sizes of crystalline as well as amorphous regions. In this study we used fibers of poly(vinyl alcohol), poly(ε-caprolactam), polyoxymethylene, and poly(4,4′-diphenyloxide) pyromellitimide. It is found that the long period dispersion of these polymers, drawn under different conditions, increases to approximately the same value for different samples drawn to the limit, this relative standard deviation δL of long periods being 0.30-0.40. It is also found that the crystallite size dispersion does not increase with increasing λ; the increase of λL is due to increasing dispersion of the amorphous region lengths. For poly(vinyl alcohol) fibers drawn to the limit under different conditions and which have different λlim, the relative standard deviation of the sizes of amorphous regions δA turned out to be about the same (ca. 0.60). The latter evidence gives grounds to suggest that the rupture of polymers under drawing is associated with reaching a high degree of amorphous region size dispersion. In those regions which are considerably below the average size there probably will appear local overstress and molecular ruptures because the relative deformation of these regions is much larger than that of the adjacent regions in the cross section of the sample.
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    Thermal expansion and Grüneisen parameters of isotropic and oriented polyethylene (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 835-846 
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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 expansion coefficients α of three isotropic samples (crystallinity v = 0.42-0.8) and one oriented sample (v = 0.8, draw ratio 11) of polyethylene have been measured between 2 and 100 K. Together with our previous measurements at high temperatures, these data provide general patterns for the crystallinity and orientation dependence over a wide temperature range. α varies only slightly with crystallinity from 50 to 120 K, but at higher and lower temperatures, it increases significantly with decreasing crystallinity. The increase at high temperature arises from segmental motion in the amorphous regions, while the large increase near 5 K is similar to that observed in many glasses. The tranverse expansion coefficient of the oriented sample is 40-100% higher than the values for isotropic polyethylene, but the axial expansion coefficient is much smaller and is negative over the entire temperature range. The values of these coefficients are quite close to those for the polyethylene crystal, a feature readily understood in terms of existing models. However, as a result of the much larger elastic anisotropy of the crystal, the Grüneisen parameters (especially the axial Grüneisen parameters) of these two types of polyethylene have rather different values.
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    Theory of the rod-to-coil transition in polydiacetylene (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 847-852 
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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 is proposed for the rod to coil transition in polydiacetylene 4BCMU and related polymers which is based on the hypothesis that the high-temperature (yellow) phase consists predominantly of the cis structure, while the low-temperature (red) phase is trans. Because the occurrence of a cis-trans interface is energetically costly, the correlation length for either isomer remains long and the transition is sharp, much like the helix-coil transition in the theory of Zimm and Bragg. The transition is driven by the higher entropy of the cis isomer, which is free to coil, unlike the trans or butatriene forms. The theory gives excellent agreement with optical absorption measurements and is consistent with all other experimental data for this system.
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    Concentration dependence of the first cumulant for partially labeled chains in dilute solutions (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 853-862 
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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 use Zimm's single-contact approximation to investigate the concentration dependence of the first cumulant for partially labeled chains in dilute solutions. This approximation allows us to express interchain properties (such as the interference part of the generalized mobility) in terms of static structure factors, which are then modeled using a Gaussian chain model. We present numerical results for three specific labeling sequences.
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    Temperature dependence of the thermal expansivity of polymer crystals: Linear chain model (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 979-991 
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    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A linear chain model is used to calculate the thermal expansivities of polymer crystals from room temperature down to liquid-helium temperature. Because of restraint by strong covalent forces, vibrations along the chains give a negligible contribution. Vibrations transverse to the chains cause the length projected along the chain direction to decrease. The expansivity along the chain direction, αc∥ is therefore negative, and has temperature dependence characterized by the low Debye temperature of transverse vibrations. These vibrations, through a cubic term in the interchain van der Waals potential, also cause a positive expansivity, αc⊥ perpendicular to the chain direction. The theoretical predictions for αc∥ and αc⊥ agree quite well with experimental data over the wide temperature range under consideration.
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    On the lateral size of shish crystals (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 993-999 
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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 lateral sizes of shish crystals crystallized from high-molecular-weight isotactic polystyrene and different blends with atactic polystyrene were examined with the help of transmission electron microscopy. It is found that the lateral sizes of shish crystals decrease with increasing content of the noncrystallizable aPS. A model accounting for the observation is proposed.
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    Random-coil configurations of aromatic polyesters: Stress-optical behavior of poly(diethylene glycol terephthalate)Author proofs received March 26, 1984 (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 917-929 
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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 behaviour of an elastomeric network of poly(diethylene glycol terephthalate) (PDET) was measured over a wide range of elongation ratios α (up to 5) and temperatures (293-353K). No evidence of strain -induced crystallization was found;on the contrary, the plot of birefringence versus stress exhibits negative deviations from linearity at values of α over 2.6. Values of the optical configuration parameter Δα of the order of 20 × 10-24cm3 with relative temperature coefficients of -1.1 × 10-3K-1 were found for the unswollen sample. The introduction of tricresylphosphate as diluent roughly doubles the birefringence of the network, presumably because of an increase in intermolecular interactions. Theoretical calculations carried out with the RIS model give values of Δα about one order of magnitude smaller than the experimental ones and temperature coefficients of about 4.1 × 10-3K-1. No reasonable modification of conformational energies or contributions to the anisotropic part of the polarizability tensor would achieve agreement between theory and experiments. The discrepancy between theoretical and experimental results may be qualitatively explained by intermolecular interactions.
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    Oriented polyolefin laminates: A refractometry and infrared studyIssued as NRCC Report No. 22828. (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 1011-1027 
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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 polypropylene-copolymer laminates produced by biaxial orientation in the 120-155°C range has been characterized by refractometry and infrared (IR) spectroscopy. The copolymer was a random ethylene-propylene resin and the IR techniques included tilted-film transmission as well as internal reflection, both using polarized radiation. The IR techniques yielded spectra corresponding to the machine, transverse, and through directions. Similarly, the refractometry gave refractive indices of both components of each laminate along all three axes. Results from the three techniques were compared and contrasted and the validity of the calculated internal reflectance spectra discussed. Practical methods to estimate the source and extent of errors in the latter technique from false radiation and contact problems were explored.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.180220607
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    Theoretical models for diffusion in glassy polymers. II (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 1001-1009 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The author refines and generalizes a model for diffusion in glassy polymers which he previously introduced. The model unifies many diverse observations by explicity formulating the common property of a glassy polymer in all its various modes, namely the finite relaxation time due to its slow response to changing conditions. An integral approximation method is used to study the motion of the penetrant front and the glass-gel interface and a useful polynomial approximation method is introduced for use in special simple situations.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.180220606
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    Effects of polymer chain disentanglement on NMR properties. II. 13C magnetic relaxation in polystyrene (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 957-978 
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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 transverse magnetic relaxation of 13Cα nuclei has been studied in concentrated solutions of polystyrene. The magnetic relaxation rate was measured as a function of molecular weight at several temperatures (313,318, and 323 K) and at several concentrations (0.53, 0.43, and 0.34 g/cm3). The spin-system response of these nuclei in natural abundance exhibits a characteristic evolution from pseudosolid properties to liquidlike one, induced by decreasing the molecular weight of polymer molecules. This evolution is analogous to that already observed in protons attached to polyisobutylene or polydimethylsiloxane chains; it is assumed to be induced by an increase of the disentanglement rate of polymer chains. The spin-system response may be considered as reflecting single-chain magnetic properties, because of the low concentration of 13CCα nuclei, although all chains are in dynamic interaction with one another. The NMR disentanglement transition is interpreted in terms of a two-step motional averaging effect involving submolecules. A numerical analysis of NMR properties is given using a model of polymer chain relaxation based on a multiple-mode relaxation process, characterized by (i)a terminal relaxation time τv1 depending upon M3, the molecular weight, and approximately proportional to the polymer concentration C (like the reptation time); (ii)a relaxation-time spectrum analogous to a Rouse spectrum; (iii)a terminal relaxation time τv1 = 2.5 × 10-2s for M = 2.5 × 105, C = 0.53 g/cm3 in carbon tetrachloride at 313 K.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.180220603
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  • 90
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    The volume structural relaxation theory for amorphous polymers (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 1041-1059 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An interpolation model of density fluctuations in amorphous bulk polymers is suggested for the explanation of some peculiarities of structural relaxation of amorphous polymers volume. The main peculiarities of the model are (i) its account of the influence of fluctuations in the region where the WLF theory is true (the region of large fluctuations); (ii) its account of small fluctuations in the region where the dissipation mechanism appears to be considerably different from that in the region of large fluctuations; and (iii) its joining of the solutions of the resulting kinetic equations in the crossover region. On the basis of the suggested model we have obtained an equation of the Fokker-Plank type for the distribution function for density fluctuations with nontrivial boundary conditions for large fluctuations, and a quasistatic solution for small ones. These equations are analyzed and numerically solved in the isothermal regime. The results show that the theory corresponds to the WLF theory at temperatures much higher than Tg and that memory effects are found in the Tg region. In addition, preliminary estimates show that near Tg an extreme form of temperature dependence on activation energy is observed. All these facts agree qualitatively with experiment.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1984.180220609
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  • 91
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    Crystalline order and melting behavior of isotactic polypropylene (α form) (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 1029-1039 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Samples of isotactic polypropylene in the α form may have different degrees of order in the up and down positioning of the chains. By suitable programming of the crystallization history of unoriented samples it is possible to show, from DSC and WAXS data, that a strict correlation exists between the melting behavior and the degree of ordering of the chains. The process of ordering at annealing temperatures above 150°C may lead to a “continuum” of modifications of the α form from less ordered to highly ordered ones; correspondingly we observe an increase in the melting point by as much as 15°C.
    Additional Material: 10 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1984.180220608
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  • 92
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    PCILO conformational energy calculation of model poly(vinyl chloride) molecules (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 1097-1104 
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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 quantum-chemical PCILO method is applied to models for poly(vinyl chloride) molecules. Calculations of conformational energies were carried out on 2,4-dichloropentanes. The values and the positions of the energy minima are determined and compared with results of other authors.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1984.180220612
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  • 93
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    Selective permeation of CO2 and CH4 through kaptonRegistered trademark, E.I. Du Point Company. polyimide: Effects of penetrant competition and gas-phase nonideality (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 1061-1084 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Sorption isotherms for pure CO2 and pure CH4 in Kapton H® polymide films at 60°C are reported for pressures up to 20 atm and are analyzed in terms of the dual-mode sorption model. An experimental scheme for the measurement of steady-state permeabilities of both pure and mixed gas feeds is described. Permeabilities of Kapton to the individual components at 60°C are presented for a mixture comprised of 32.2% CO2 in CH4 as functions of feed pressure up to 590 psi (absolute). The permeabilities for the individual penetrants in the mixed feed are lower than the respective purecomponent values at the corresponding partial pressures. Furthermore, the permeabilities of both penetrants drop as the feed pressure is increased at constant composition. The dual-mobility transport model used to analyze the data postulates that the observed pressure and composition dependence of the permeabilities is due to competition between penetrants for a limited microvoid sorption capacity in the glassy polymer. It is demonstrated that in addition to flux depressions due to dual-mode effects, nonideality of the gas phase must be accounted for to explain the substantial flux depressions observed for the CO2/CH4 mixtured used in this study.
    Additional Material: 16 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.180220610
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    A small-angle X-ray scattering study of an aromatic polyimide (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 1105-1117 
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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 morphology of isotropic films of poly[N,N'-bis(phenoxyphenyl)-pyromellitimide] was investigated by means of small-angle x-ray scattering. A significantly different morphology was found to develop in these films as compared to that in films possessing as in-plane molecular orientation. It was found that morphology could be described by a damped periodic modulation in the electron density characteristic of a chain segment aggregation. An increase in the initial imidization temperature resulted in an overall increase in the lateral packing of the chains and a reduction in the amplitude of the density modulation. Evidence was also found for segmental aggregation in the precursor polyamic acid which contained up to 35% solvent.
    Additional Material: 8 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1984.180220613
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    Mechanical relaxations and moduli of oriented nylon 66 and nylon 6 (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 1173-1191 
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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 mechanical relaxations of dry and wet nylon 66 and nylon 6 with draw ratios λ = 1-3 have been studied from -180 to 160°C and in the frequency range of 1 Hz to 10 MHz. The five independent elastic moduli C11, C12, C13, C33, and C44 have also been determined by an ultrasonic method at 10 MHz. Wide-angle x-ray diffraction and birefringence measurements reveal that the crystalline orientation rises sharply at low λ and becomes saturated near λ = 3; the amorphous orientation function increases continuously, reaching values of 0.3-0.5 at λ = 3. The alignment of molecular chains and the presence of taut tie molecules in the amorphous regions lead to a lowering of segmental mobility, thereby reducing the magnitude and increasing the peak temperature and activation energy of the α relaxation. Water absorption weakens the interchain bonding and so gives rise to effects opposite to those of drawing. At low temperature, the development of mechanical anisotropy is largely determined by the overall chain orientation, with the c-shear mechanism contributing a small additional effect. However, above the α relaxation, where the amorphous region is rubbery, the stiffening effect of taut tie molecules becomes dominant and leads to increases in all moduli.
    Additional Material: 21 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1984.180220703
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    Interpretation of the moduli of trifunctional model elastomers of polydimethylsiloxane (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 1201-1210 
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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 survey is made of published experimental values of the elongation moduli of trifunctional model networks of polydimethylsiloxane [—Si(CH3)2O—]. The results thus obtained are interpreted in light of recent molecular theories of rubberlike elasticity, particularly with regard to predicted values of the modulus, the degree of nonaffineness of the deformation, the relevance of the network sol fraction, and the efficiency and possible importance of the trapping of interchain entanglements. The most important result of this study is the conclusion that it is not necessary to invoke equilibrium contributions from interchain entanglements in order to interpret the experimental results presently available in the literature.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.180220705
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    Fourier-transform infrared studies of the thermal degradation of isotopically labeled polyacrylonitriles (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 1211-1222 
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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(d3-acrylonitrile), poly(1-13C-acrylonitrile), poly(15N-acrylonitrile), and 18O2 have been used to assign the infrared spectra of the thermal degradation products of polyacrylonitrile. Isotopic data and elemental analyses show that the degradation products can be made free of oxygen. The infrared data suggest that the reaction proceeds sequentially from imines to fused pyridine-dihydropyridine moieties.
    Additional Material: 8 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1984.180220706
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    Enhanced electrical conductivity of poly(ethylene terephthalate) implanted with fluorine ions (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 1349-1352 
    Details
    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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.180220717
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    X-ray diffraction by liquid-crystalline copolymers prepared from 4-hydroxybenzoic acid and 2-hydroxy-6-naphthoic acid: A one-dimensional paracrystalline model (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 1343-1347 
    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.1984.180220716
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    Effects of copolymer composition on the formation of ionic species, hydrogen evolution, and free-radical reaction in γ-irradiated styrene-butadiene random and block copolymers (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 22 (1984), S. 1313-1329 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Block and random copolymers of butadiene and styrene as well as polybutadiene and polystyrene homopolymers have been investigated with respect to formation of trapped electrons, contribution of ionic species to crosslinking, and hydrogen gas evolution due to γ radiation. The decay kinetics of the disubstituted benzyl radical has also been studied. The yields of electron trapping G(e-) are measured. The G(e-) increase linearly with increased polystyrene content in block polymers, while in random copolymer a deviation from a linear relation is observed. The contribution of ionic reactions to crosslinking is about 25-35% of the total crosslinking yield. Hydrogen production in block copolymers is approximately a linear function of the weight-fraction additivity of the yield of hydrogen formation in polystyrene and polybutadiene homopolymers. Energy transfer from butadiene units to styrene units in random copolymers resulted in a deviation from such an additivity relation. The decay of the disubstituted benzyl free radical in block copolymers is a second-order reaction. In random copolymer, the decay is best interpreted in terms of equation based on a second-order decay mechanism of a fraction of the free radicals decaying in the presence of other nondecaying free radicals.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.180220714
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