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  • 1985-1989
  • 1975-1979  (487)
  • 1970-1974
  • 1977  (487)
  • Physics  (487)
  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 109-125 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The Flory-Huggins formulation of the combinatorial entropy, supplemented with residual free energy, is applied locally to obtain the interfacial free energy and the concentration profile of polymer in the interface between two demixed polymer solution phases. Two choices were investigated for the residual free energy: a “regular solution” formulation and an empirical formulation of Koningsveld for polystyrene in cyclohexane. Asymptotic, analytical solutions of the equations near the critical solution point and solutions obtained by numerical calculations are given as a function of temperature for several molecular weights. At temperatures farther below the critical temperature the equations have no solutions. The reason for this is not entirely clear. The local formulation of the free energy used here is an improved version of a previous one, which gave wrong results for asymmetric systems (polymer in a low molecular weight solvent). This newer version is consistent with our theory of critical opalescence and gives a relation between the interface “thickness” and the correlation range of the concentration fluctuations. The calculated correlation ranges were in good accord with those found experimentally by Debye, Chu, and Woerman. That the newer version of our equations for an interface gives no acceptable solutions at lower temperatures could be caused by a “collapse” of a diffuse to a sharp interface as suggested by Nose.
    Additional Material: 7 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 173-191 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The four-center photopolymerization of five diolefinic compounds has been investigated by x-ray crystal analysis. A common packing feature is found for the photopolymerizable crystals and all polymers are three-dimensionally oriented. Topotaxies observed are classified according to the coincidence of space group and the three crystal axes, between monomer and polymer. The polymerization mechanism is discussed on the basis of the topotaxies and it is concluded that the polymerization is lattice controlled over the whole reaction process.
    Additional Material: 15 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 199-210 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It is well known that polycarbonate annealed at 80-130°C undergoes gradual changes in mechanical properties. Annealing below Tg (ca. 150°C) results in a decrease in impact resistance and an increase in strength. Polycarbonate has three single relaxation processes and some distributed relaxation processes in the temperature range between 100 and 250°K (the β transition region). The effect of thermal pretreatment on the relaxation has been investigated by the thermally stimulated discharge current technique. Partial heating, peak cleaning, and theoretical fitting have also been performed and the activation parameters associated with the relaxation processes have also been calculated to assist in the analysis of the relationship between effects of annealing and structural motions in polycarbonate.
    Additional Material: 9 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 211-226 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Oriented gels, obtained by high supercoolings of isotactic polystyrene solutions, exhibit unexpected “fiber-type” x-ray diffraction patterns. In particular a pronounced meridional reflection at a spacing of 0.51 nm, together with its successive orders, requires an extended, or nearly extended, chain conformation which appears irreconcilable with the stereochemistry of isotactic polystyrene. Furthermore, the value of 0.51 nm correlates directly with the axial projected repeat expected for two styrene monomer units. Two possible stereosequences merit atention: syndiotactic and syncephalic (head-to-head, tail-to-tail). In addition to the 0.51 nm meridional reflection, layer lines are observed with spacing 3.06 nm (6 × 0.51) which equate with 24 carbon-carbon bonds in the backbone. Cylindrically averaged Fourier transform calculations for the various models are compared with the observed x-ray results and the best fit is obtained for a 24/11 helix of isolactic polystyrene with the syncephalic stereosequence. This conclusion, however, clashes with the 13CNMR evidence which indicates that the polymer is essentially isotactic. The implications of these novel results in relation to gel crystallization are discussed.
    Additional Material: 7 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 239-245 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dynamic mechanical properties of four aromatic polyesters were measured at temperatures in the 78-540°K region at 103-104 cps. The polymers studied were: poly(1,3 phenylene isophthalate), poly(1,4 phenylene terephthalate), poly(4,4′ diphenylene isophthalate), and poly(4,4′ diphenylene terephthalate). All four polymers had β loss peaks at about 280°K. Distinct β* mechanical processes were found for the two terephthalate esters. Broad-line nuclear magnetic resonance measurements were carried out in the 150-440°K temperature range on the four polyesters mentioned above in addition to poly(4,4′ diphenylene 4,4′ biphenyl dicarboxylate). A change in NMR second moment takes place in the 190-330°K region, the magnitude of which is dependent on the polymer structure. The results are compared with those found for a series of aromatic polyamides and are discussed in terms of possible motional processes.
    Additional Material: 4 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 247-253 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The melting point of the 1:1 copolymer of ethylene and CO is 244°C. It falls rapidly as the percent CO is reduced indicating that the heat and entropy of fusion are 0.60 kcal and 1.15 e.u./mol of chain atoms, respectively. These are lower than the values for polyethylene. Dynamic mechanical measurements showed loss peaks at -100° and 25°C. The low temperature γ-relaxation which is also seen in dielectric data appears to be a local mode relaxation with an activation energy of about 12 kcal/mol. The room temperature relaxation is associated with a large decrease in the modulus and a large increase in the dielectric constant. It is probable that the low entropy of fusion is due in part to extensive motion in the crystal.
    Additional Material: 7 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 283-289 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetics of the quaternization of poly(4-vinyl pyridine) with 1-bromopropane in sulfolane has been studied in the temperature range 308-348°K with data points covering the whole conversion range. The results have been analyzed according to the neighbouring-group model with rate constants k0, k1, and k2 for reaction of pyridyl groups with zero, one, and two already reacted neighbors. Allowing for limiting reaction at about 95%, the experimental results substantiate the model with K = k1/k0 = 0.80 ± 0.03, and L = k2/k0 = 0.37 ± 0.03, which are independent of temperature. The temperature dependence of k0 values gives an activation energy of 66.22 ± 4.20 kJ mol-1. It is still not possible to decide whether steric or electrostatic factors are responsible for K and L values less than unity. Other systems are mentioned where side reactions occur.
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 303-320 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The design and operation of an automated light-scattering apparatus for studying structures in polymer films are described. The apparatus has angular resolution of 0.02 and 1.0° in radial and azimuthal angles, respectively. The radial scan can be made over the range of 0.5 (or less) to 90° and the azimuthal scan covers 180°. Time resolution is in the order of milliseconds. The operation, data collection, and reduction are fully automatic. Illustrative data on the crystallization of a low density polyethylene are described.
    Additional Material: 10 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 321-331 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Periodate oxidation of polysaccharides shows inhibitory neighbor effects due to hemiacetal formations. A second periodate oxidation may be performed after removal of all protecting hemiacetals formed in the first oxidation.We give the theoretical analysis of the kinetics of such repeated oxidations. For complete protection the oxidation limit of the second reaction, as function of the extent of the first oxidation, lies between 41.1 and 43.2%, in good agreement with experiments on alginate. For general protection effects we calculate the degree of oxidation and the mean sequence lengths of the three types of monomer units. Second-oxidation data, in contradistinction to first-oxidation results, allow separate determination of left-and right-hand inhibitory effects.
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  • 10
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 333-353 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Deformation bands formed at the yield point in tensile tests on oriented high-density polyethylene have been studied by optical microscopy and wide-angle x-ray (WAXS) diffraction. The observations of the rotation of the optical extinction direction are shown to obey a simple scheme proposed previously by us: the principal directions of the refractive index ellipsoid within the deformation bands are everywhere parallel to the principal axes of the plastic strain ellipsoid, zero strain referring to the isotropic state. This result is similar to that obtained previously for polyethylene terephthalate (PET) and polypropylene despite the much higher crystallinity obtained with polyethylene. Independent measurements of the molecular reorientation in the deformation bands made using wide-angle x-ray scattering broadly confirm the optical measurements. The results taken together suggest that the material within the band, whether crystalline or not, becomes realigned about the new direction of maximum elongation as if controlled by the deformation of an effective molecular network.
    Additional Material: 9 Ill.
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  • 11
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 403-416 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The free-volume theory describing diffusion in polymer-solvent systems is reexamined. Calculation of the specific free volume for such systems is discussed, and equations are presented for the determination of the self-diffusion coefficients of the polymer and the solvent. Conditions under which the mutual diffusion coefficient can be deduced solely from free-volume considerations are clarified, and a more general version of the free-volume diffusion theory proposed by Fujita is presented. The further restrictions needed for the theory of Fujita are discussed, and it is concluded that these additional restrictions are responsible for failures of the Fujita theory.
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  • 12
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 385-388 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 4 Ill.
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  • 13
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 847-861 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Models for the interpretation of magnetic relaxation in a randomly coiled macromolecule in dilute solution are considered. Expressions are given for the spin-lattice relaxation time and the nuclear Overhauser enhancement resulting from modulation of the dipole-dipole interaction by three specific independent and mutually competitive types of macromolecular motion. Overall molecular rotation is characterized by a single exponential correlation time and internal anisotropic rotation by the well-known Woessner theory. A simple description of backbone motion is presented based upon a three-bond crankshaft motion and the concept of limited coupling among backbone bonds. The resulting correlation function is numerically similar to that recently proposed by Valeur, Jarry, Gény, and Monnerie from a somewhat different standpoint. Representative calculations for appropriate ranges of the model parameters are made for a 13C nucleus relaxing by heteronuclear dipole-dipole interaction with a single 1H nucleus.
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  • 14
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 881-895 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dielectric measurements were made on some methyl methacrylate (MMA)-related polymers in dilute solution, in the frequency range of 1-150 MHz. Effects of the solvent viscosity upon the relaxation behavior were carefully examined. The dielectric relaxation of MMA-styrene copolymers with a high content of MMA units as well as that of the MMA-α-methylstyrene copolymer was little affected by the solvent viscosity. With the aid of Kramers'rate constant for small friction, it was found that their dipolar relaxation is very similar to that caused by the internal rotation of a flexible side-chain. On the other hand, MMA-styrene copolymer with a low content of MMA units showed a diffusion-controlled relaxation process, which can be interpreted in terms of Kramers' theory for large friction. In the latter case, the dipolar relaxation appears to reflect a molecular motion such as sweeping out solvent molecules. These results indicate that it is not the dipole itself but its environment, or rather the local molecular structure containing dipoles, that principally controls the relaxation process. On this basis, we propose a criterion, for quantitatively distinguishing the two relaxation mechanisms from each other.
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  • 15
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 1199-1210 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The influence of pressure on the thermal conductivity K of four vitreous poly(alkly methacrylate) polymers has been measured by steady state techniques. The measurements were made under pressures up to 2 kbar and over a temperature range between 173 and 300°K. For each member of the homologous series, K was found to increase with applied pressure. Shifts in thermal conductivity transition temperatures (attributed to glass transition phenomena) of 25, 26, and 16°C per kbar of applied pressure were observed for poly(methyl methacrylate), poly(ethyl methacrylate), and poly(n-isobutyl methacrylate).
    Additional Material: 7 Ill.
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  • 16
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 1283-1289 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The melting behavior of bisphenol-A polycarbonate samples plasticized by tritolyl phosphate (TTP), pentaerythritol tetranonanoate (PETN), and trimellitic acid-tridecyloctyl ester (TMDO) has been investigated and discussed on the basis of current theories. Using the Hoffman and Weeks approach modified for finite chain length, the variation of the equilibrium melting temperature has been determined as a function of the plasticizer concentration. Extrapolation of these data yields an equilibrium melting temperature of 317°C for the pure polycarbonate of infinite molecular weight. This figure greacly exceeds the value so far reported in previous publications. It is also shown that the compatibility of the plasticizer affects the melting temperature just as it controls the glass transition. The cryoscopic effect observed, however, is much more pronounced than anticipated on the basis of the Flory-Huggins theory.
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  • 17
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 1319-1327 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Differential scanning calorimetry (DSC) studies show that poly(ethylene oxide) (PEO) exhibits three transition regions below its melting point. The effects of annealing on the intensity and temperature of these transitions enable us to locate T 〈 Tg (Tγ) Tg, and Tα at about 130-140. 190-240, and 263-313°K, respectively. Our results argue for a small transition Tg (L) at 190-200°K with a second Tg (U) above 233°K, the temperature of which increases on annealing. The shape of DSC derivative curves reveals that T 〈 Tg and Tα are complex and suggests the possibility of two steps in these processes. In addition, a splitting of Tα is observed every time a multiple melting endotherm appears as a result of annealing. Up to three separate melting endotherms can be observed. One of them is related to the normal primary crystallization process. Its peak temperature increases linearly with the annealing temperature, yielding an extrapolated value for the equilibrium melting temperature T0m of 347°K as found before.
    Additional Material: 6 Ill.
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  • 18
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 1379-1395 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Fourier transform infrared spectroscopy has been used for the detection of thermally induced conformational changes in atactic poly(vinyl chloride) (PVC). Difference spectra emphasize changes in the distribution of gauche defects in the chains as functions of temperature and annealing. Specific bands in the ν(CCl) and δ(CH2) regions varied with inverse temperature, allowing a calculation of the activation energies of the rotamer species. Conformational changes were also detected in quenched PVC films as a result of annealing below the glass transition temperature, Tg.
    Additional Material: 14 Ill.
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  • 19
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 1409-1425 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Low-density polyethylene was modified by the inclusion of phosphonate ester pendent groups by using an oxidative chlorophosphonylation reaction followed by esterification of the polyethylene poly(phosphonyl chloride) with an alcohol. Two different types of phosphonate esters were prepared: dimethyl phosphonate from the reaction with methanol and a phosphonate graft copolymer from the reaction with hydroxy-terminated poly(ethylene oxide) (PEO). For the latter, oligomers with molecular weights of 350 and 750 were used. For each type of phosphonate, a series of polymers were prepared with pendent group concentrations ranging from 0 to 9.1 substituents per 100 carbon atoms. The modified polymers were characterized by infrared spectroscopy, differential scanning calorimetry, and by measurement of the tensile modulus. Infrared spectroscopy proved to be useful for determining if the polymer modification reaction resulted in entirely phosphonate ester pendent group substitutions or if unesterified phosphonic acid groups were also present. The polymers prepared in this investigation exhibited no infrared absorbances arising from phosphonic acid groups. The presence of phosphonate ester groups resulted in a decrease of crystallinity with increasing phosphonate concentration and with the exception of the polymers containing 9.1 PEO-phosphonate grafts per 100 carbon atoms, the effect of phosphonylation on the melting temperature of the polymers was consistent with Flory's theory for the melting point depression of random copolymers. The tensile modulus measured from a constant uniaxial elongation experiment decreased with increasing phosphonylation. The behavior of all three phosphonate series was identical and could be attributed to the effect of decreasing polymer crystallinity.
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  • 20
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 1475-1483 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The subject of this paper is the degree of crystallinity and annealing behavior of solution grown single crystals of isotactic polystyrene (IPS) in relation to the fold length, an enquiry which acquires special significance in view of the fact that previously the fold length had been found to be identical over a wide range of crystallization temperatures (Tc). It was found that both crystallinity and thermal stability increase with Tc even over the range of constant fold length thus invalidating the usual assumption that the fold length and crystal properties are uniquely correlated. Further, the crystallinity figures as measured by conventional calorimetry are very low (〈50% throughout) which by conventional ideas would require an unrealistically thick amorphous surface layer. However, the “linear crystallinity” (crystal core thickness as determined from x-ray linewidths) is much larger, commensurate with crystallinities in single crystals from other materials. It is suggested that this is the more relevant figure for the subdivision of the lamellas into crystal core and surface layer. The additional amorphous content being otherwise accommodated. Further, this “linear crystallinity” is broadly unaffected by fold length changes induced by heat annealing. The thermal stability (including annealing ability) of the crystals differs markedly whether Tc is above or below ∼60°C, a Tc value which is in the range where the fold length is constant, but corresponds to a maximum in the crystallization rate. Possible connections between crystallization conditions and the stability of the resulting crystals (fold length considerations apart) are pointed out.
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  • 21
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 1569-1583 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A framework for analysis of stress-induced diffusion is presented. Diffusion of macromolecules is considered to be driven by gradients of entropic potential arising from distortion of the molecular conformation by deformation, as well as by gradients of concentration of individual molecular weight species. Resulting concentration profiles in circular capillary flow have been calculated for a system containing a single macromolecular species. Significant variations in concentration with capillary radius are predicted at full development. Estimates of the dynamics of development of these profiles indicate that the length to diameter ratios needed to see a measurable effect are proportional to the Peclet number, which may be quite large for macromolecular fluids depending on the geometry and flow velocity of the system. This effect may have implications in the rheology, chromatography, and technological uses of macromolecular fluids.
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  • 22
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 1675-1683 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The thermal behavior of films of amorphous silk fibroin in the random-coil conformation has been investigated in the temperature range 25-220°C by differential scanning calorimetry (DSC), thermal expansion, dynamic mechanical measurements, x-ray diffraction, and infrared spectroscopy. As the temperature is raised, water is lost up to about 100°C. Intramolecular and intermolecular hydrogen bonds are broken between 150 and 180°C. The glass transition is observed at 173°C by DSC. The random-coil→β-form transition accompanied by reformation of hydrogen bonds takes place above 180°C. Thermally induced crystallization to the β-form crystals starts at about 190°C.
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  • 23
    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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  • 24
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 1905-1912 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Etching of extended-chain crystals of polyethylene is shown to permit separation of the polycrystalline aggregate into single crystals. The single crystals are analyzed by density, molecular weight (lamellar crystal thickness), melting temperature, birefringence, superheating, and linear melting rate determination. The linear melting rate depends linearly on superheating and can be described by simple rate theory.
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  • 25
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 1885-1903 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The regularity bands of isotactic polystyrene are determined using Fourier transform infrared spectroscopy to digitally substract the spectrum of a quenched sample from that of an annealed sample. Crystallization-sensitive bands in the Raman spectrum are identified by comparison of the spectra of annealed and quenched samples. The normal modes of isotactic polystyrene are calculated using force fields determined for saturated hydrocarbons and alkyl benzenes. A good fit between observed and calculated frequencies is obtained. It is evident from this study that the complex behavior of certain bands in the spectrum is due to a mixing of phenyl and skeletal vibrations.
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  • 26
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 1937-1951 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dilute solution properties of linear (SI)3 six-block copolymers of styrene and isoprene are compared to those of random, two-block, and three-block copolymers of the same system. All the copolymers were prepared with sec-butyllithium in benzene. The microstructure of the polyisoprene blocks is close to that of homopolyisoprene prepared under the same conditions. In contrast, the random copolymer shows a larger amount of trans-1,4 isoprene units. The intrinsic viscosities of the copolymers in methylisobutyl ketone, a poor solvent for both polystyrene and polyisoprene, and in toluene, a good solvent for both homopolymers, are examined on the basis of the Fox-Flory relation for homopolymers. All the copolymers behave similarly in each solvent. In methylisobutyl ketone, the viscosity results indicate a random coil conformation with a small expansion owing to the extra repulsive interactions between the dissimilar units. In all cases, the heterocontact repulsive interactions are small and can be characterized by an interaction parameter χab close to 0.025. In toluene, the perturbation caused by the heterocontacts becomes negligible and the expansion factor αη can be predicted from a weighted average of those of the parent homopolymers of the same molecular weight as the copolymer.
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  • 27
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 1967-1982 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The intensity of the water-induced γ relaxation (see ref. 1) in crosslinked polyester networks in creases rapidly at low water concentrations (0 to 0.5% by weight). At higher water concentrations (0.5 to 3.0%) the intensity of the γ relaxation approaches a constant value. The shift of the relaxation peak to lower temperatures shows a similar pattern of behavior. These results have been related to the fraction of water involved in the relaxation and the changing nature of the relaxation sites with the increase in water concentration. The important role that fumarate units play in the γ relaxation has also been confirmed; however, the chemical nature of the relaxing unit appears to be more complex than was originally considered. Two models are proposed for this behavior.
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  • 28
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 2027-2031 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 3 Ill.
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  • 29
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 2037-2038 
    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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  • 30
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 2055-2056 
    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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  • 31
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 2051-2053 
    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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  • 32
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 1011-1027 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Information on molecular conformations inside polyethylene lamellas following high pressure treatments is obtained by comparing observed and predicted length distributions of nitrated samples. Three types of conformation are inferred. The commonest is that molecules are folded with chain ends included in lamellas, except that ends are not turned in by less than ∼600 Å from a surface. This situation accounts in detail for the previously observed agreement between the number fracture-surface distribution of crystal thicknesses and the gel permeation chromatography (GPC) weight distribution following nitration. The second conformation, found especially for samples of low polydispersity, is also of folded molecules but with chain ends excluded from lamellas. This particular case justifies rigorously the initial assumption of folding. Finally there are examples where the molecular length distribution is substantially lower than the crystal thickness distribution, implying that molecular length is not the upper limit of crystal thickness and that molecules can be fully extended inside lamellas.
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  • 33
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 1029-1036 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Conditions that affect the conformation of poly(β-benzyl L-aspartate) in films have been studied. A slow transition from the left-handed to the right-handed α-helical form is observed under certain conditions in half-dried film cast from chloroform solutions and after exposure of amorphous films of the left-handed β-helical form to chloroform vapor. This transition is caused by adsorption of moisture. Thermal transitions of these films were examined by differential scanning calorimetry and infrared spectroscopy. The right-handed α-helices change to left-handed ω-helices around 140°C, and sharp exothermic peak is observed in this region for some films.
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  • 34
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 1077-1088 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Ultrahigh molecular weight polyethylene has been crystallized at various pressures (0-330 MN m-2) to material of a wide range of specific gravities (0.928-0.967). Tensile measurements illustrate that the properties of these materials are dependent on specific gravity (sg), in that the yield stress increases linearly with sg. Low sg (0.928-0.944) materials exhibit higher yields stress than low molecular weight materials of the same sg but the opposite is true for higher sg material. Low sg material also extends uniformly after yielding while above a sg of 0.944 necking becomes more marked. Orientation hardening is observed with all these materials above 200% extension and is more marked than with low molecular weight polymers. Differential scanning calorimetry (DSC) analysis of the pressure crystallized materials indicate that in the range 200-400 MN m-2 two phases are present, i.e., chain-folded and chain-extended lamellas. Increasing or decreasing the pressure changes the crystalline component to chain-extended or chain-folded morphologies, respectively. The reorganization of the crystalline components on drawing is discussed.
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  • 35
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 1121-1126 
    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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  • 36
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 1177-1188 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A fiber composite model of highly drawn polyethylene is presented. Quantitative predictions and calculations are made using shear-lag theory. The drawing process is shown to occur in two stages, a neck and a postneck taper. It is shown that there is an empirical linear relationship, with a high correlation, between the parameter x in shear-lag theory (which involves the aspect ratio of the reinforcing elements and the square root of the ratio of matrix shear modulus to the Young's modulus of the reinforcing elements) and the 3/2 power of the taper draw ratio. It is concluded that crystalline fibrils (the reinforcing elements) deform homogeneously during the secondary, taper drawing process. The increase in aspect ratio resulting from this homogeneous deformation is held to be responsible for the increase in tensile modulus owing to the increased efficiency of the fibrils as reinforcing elements. The model is also used to explain the self-hardening process exhibited by these fibers and, using measurements of density of hardened fibers, to predict that immediately after the neck the aspect (length to diameter) ratio of the crystalline reinforcing elements is ca. 2 and that the shear modulus of the matrix material in as-drawn fibers is ∼103N/m2 and does not change significantly during the taper-drawing process.
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  • 37
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 1619-1626 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polydioxolan samples crystallized between 25 and 35°C present two optical phases when viewed on the polarizing microscope. These phases, termed central and external phases, form a spherulite. It is shown in this paper that the central phase of the two-phase spherulite melts at about 63°C, and is made of modification III crystals. The external portion of the two-phase spherulites melts at a lower temperature, around 59°C, and is composed of modification II crystals. Differential scanning calorimeter (DSC) melting curves, photomicrographs, and x-ray results are presented to prove these assertions.
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  • 38
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 1655-1661 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Doubly oriented specimens with a single texture can be obtained by unidirectional rolling of a sheet of low-density polyethylene. Swelling of the oriented samples with liquid biphenyl and in situ crystallization of the biphenyl give indirect information about the morphology of the polymer. In such samples, annealed a few degrees below the melting temperature, the orientation of the biphenyl crystals is a consequence of the interaction of the two crystalline lattices. The (001) biphenyl planes are parallel to the (h01) limiting planes of the lamellar polymer crystals. Theoretical considerations show that the epitaxial conditions are best fulfilled when the limiting planes of the lamellas are parallel to (201) planes. The experimental value of h is 3.
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  • 39
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 1697-1706 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The fine texture and molecular motion in rolled (draw ratios λ = 2, λ = 5), cold-drawn (λ = 6), and hot-drawn (λ = 6), linear polyethylene (Sholex 6050) films were studied by small-angle x-ray scattering, wide-line nuclear magnetic resonance (NMR), and dynamic viscoelastic measurements. NMR spectra of the rolled (λ = 5) and cold-drawn samples show a small narrow component at room temperature. For these cold-deformed samples, a gradual decrease in the second moment is observed well below the α relaxation temperature and a new relaxation appears in the same temperature region in the logarithmic decrement versus temperature. This relaxation is absent in the original and hot-drawn samples. It is concluded that the new relaxation arises from molecular motion in intermediate regions where molecular chains are less mobile than in the amorphous state.
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  • 40
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 1745-1756 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Starting with Kirkwood's Fokker-Planck equation for the polymer configuration-space distribution function and using the Zwanzig-Mori projection operator technique we have calculated the scattering law S(q,w) for a freely jointed model polymer chain in a dilute solution. When memory effects are neglected, the theory predicts a Lorentzian for S(q,w) with a halfwidth Ω(q), which we have determined as a function of the momentum transfer q for all values of q. The results are compared with recent neutron scattering experiments on deuterated polytetrahydrofuran and polystyrene in dilute solution in CS2. It is found that the observed q dependence of Ω(q) is represented satisfactorily by the present theory with a bond length b of about 6.3 Å for polystyrene and 3.8 Å for polytetrahydrofuran, and a friction coefficient ζ = 4πη0b where η0 is the viscosity of the solvent.
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  • 41
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 2047-2049 
    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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  • 42
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 2057-2064 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It is proposed that the mobility of sufficiently long molecules undergoing translational diffusion through solid polyethylene is significantly reduced by tie molecules and fixed entanglements within the interlamellar regions of the matrix. The effect on the diffusion coefficient both of diffusant molecular length and of the host matrix morphology is considered, and a semiquantitative relation between them obtained. This indicates that the mobility of long diffusants is higher in polyethylene which has been cooled slowly from the melt than it is in quenched polyethylene, in marked contrast to the behavior of gaseous and other small diffusants.
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  • 43
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 2095-2101 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Molecular motions of hydrophobic-hydrophilic water-soluble block copolymers in solution were investigated by high-resolution proton magnetic resonance (NMR). Samples studied include block copolymers of polystyrene-poly(ethylene oxide), polybutadiene-poly(ethylene oxide), and poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide). NMR measurements were carried out varying molecular weight, temperature, and solvent composition. For AB copolymers of polystyrene and poly(ethylene oxide), two peaks caused by the phenyl protons of low-molecular-weight (M̄n = 3,300) copolymer were clearly resolved in D2O at 100°C, but the phenyl proton peaks of high-molecular-weight (M̄n = 13,500 and 36,000) copolymers were too broad to observe in the same solvent, even at 100°C. It is concluded that polystyrene blocks are more mobile in low-molecular-weight copolymer in water than in high-molecular-weight copolymer in the same solvent because the molecular weight of the polystyrene block of the low-molecular-weight copolymer is itself small. In the mixed solvent D2O and deuterated tetrahydrofuran (THF-d8), two peaks caused by the phenyl protons of the high-molecular-weight (M̄n = 36,000) copolymer were clearly resolved at 67°C. It is thought that the molecular motions of the polystyrene blocks are activated by the interaction between these blocks and THF in the mixed solvent.
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  • 44
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 379-384 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The photoelectret charge in the aluminum-poly(vinylcarbazole) (PVK) conducting-glass (NESA), sandwich cell configuration has been observed to decrease with voltage above some critical voltage, depending on the intensity of illumination. This critical voltage corresponds to the value at which a time-independent photocurrent is observed and also to the “knee-point” voltage in the current voltage plot. The results are explained on the basis of field-assisted detrapping setting in at high field.
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  • 45
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 441-453 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A method is presented for anticipating condition under which anomalous diffusion effects can be expected for amorphous polymer-solvent systems. The diffusion process is characterized by a dimensionless group called the diffusion Deborah number, and a method for calculating this dimensionless number is presented. Deborah number diagrams are constructed for the unsteady diffusion of ethylbenzene and polystyrene in thin films, and observed diffusion phenomena are discussed on the basis of these diagrams.
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  • 46
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 455-464 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Mechanical relaxation at hypersonic frequencies is measured using Brillouin spectroscopy for polyisobutylene, atactic polypropylene, polydimethyl siloxane, and polyvinyl acetate. The temperatures of maximum loss determined in the gigahertz range are compared to the published transitions maps for the above polymers. It is found that the hypersonic relaxation data fall on an extrapolation of the secondary main chain glass-rubber relaxation line above the region where the primary and secondary lines merge.
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  • 47
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 485-499 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Thermally stimulated discharge has been used in the past to diagnose and estimate the magnitude of electrical polarization in polymers. Nevertheless, molecular characterization of operative phenomena by this technique alone is often a difficult task. In the present work, infrared attenuated total reflection spectroscopy has been used to investigate the origin of thermally stimulated discharge currents near 200°C in externally unpolarized films of polyacrylonitrile (PAN). Spectroscopic analysis of thermally degraded films reveals some unsaturation of the PAN backbone and possibly the generation of cyanide ions. Opposite surfaces in a solvent-cast film give different spectra, indicating a gradient in chemical degradation products across the film thickness. Data suggest that nonuniform generation of charged species and unsaturated bonds gives rise to internal potentials in PAN. The origin of thermally stimulated currents in PAN near 200°C is thus believed to be associated with the onset of chemical degradation.
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  • 48
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 579-582 
    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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  • 49
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 593-603 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Ethylene solubility in low-density polyethylene has been measured using the piezoelectric sorption method from 0 to 69 atm at 126, 140, and 155°C. The measured solubility data indicate lower ethylene solubility in polyethylene at a given temperature and pressure than a previously published extrapolation of infinite-dilution results. The data are interpreted using the Flory-Huggins solution theory.
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  • 50
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 627-639 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dc conductivity of crystallizable poly(phenylacetylene), made in the presence of ferric acetylacetonate and triethylaluminum, and its dependence on time, temperature, pressure, and crystallinity was determined. A decrease in conductivity upon annealing is probably attributable to an irreversible conformational transformation of the polymer. There is also a reversible decrease in conductivity upon compression which, under some conditions, corresponds to a volume of activation as high as 70 cm3/mole. Upon complexing with iodine the conductivity is increased by several orders of magnitude and activation energies and volumes are greatly reduced, even at iodine concentrations as low as 1.6 mole % iodine per monomer unit. Although an identification of unpaired spins with the charge carriers is probably not justified, defect states, whose presence is demonstrated by electron spin resonance, may play a major role in the charge transport process. The strong reversible decrease of the conductivity with an increase in pressure is plausible, if intermolecular charge transport is the rate-controlling step, an interpretation consistent with the large increase in conductivity upon complexing with small amounts of iodine.
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  • 51
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 657-674 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We propose a new model for the Lamb-Matheson-Philippoff (LMP) increment in the dynamical viscosity of polystyrene solutions. The crucial difference between the new model and the currently accepted models is that our model predicts that at least a large part of the LMP increment relaxes at a particular frequency, whereas the conventional models predict a nonrelaxing increment. In order to derive our model, we reformulate the internal viscosity (IV) concept, for a fluid undergoing shear, in such a way that the shear filed appears explicitly in the IV resistance. Since the derivation of this IV model is nonrigorous and produces a result which may be surprising, we rederive the dynamical viscosity using a correlation function technique, into which the flow field does not enter explicitly. We show that our model predicts the principal experimental results on the LMP increment as well as the conventional models do, but that our model gives a result which is more in line with current thinking (i.e., that the increment might be expected to undergo relaxation). We also show that our model accurately predicts an “anomalous” result obtained recently on the viscoelastic absorption spectrum of poly(propylene glycol) melts, the description of which is quite outside the scope of the Rouse-Zimm model or the currently accepted IV model.
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  • 52
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 703-714 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The solid-state thermal polymerization of 2,4-hexadiyne-1, 6-diol has been studied by a variety of methods. Pure monomer heated under vacuum or in an inert gas atmosphere is found to polymerize readily, unlike material heated in air. X-ray diffraction reveals that samples anneal during polymerization. Initially, a long chain polymer is formed, but above 20% conversion a less perfect product is obtained. Measurements suggest a complex molecular rearrangement during the nonideal phase of polymerization. Possible models for this process are discussed.
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  • 53
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 757-759 
    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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  • 54
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The temperature dependence of the conformational transition from a compact to expanded-coil form of the alternating copolymer of maleic acid with styrene in aqueous 0.03M NaCl solution was studied at 15 to 40°C by pH titration, optical titration, and calorimetric measurements. The pH titration curve scarcely changed with temperature. The degree of dissociation of primary carboxyl groups in the copolymer at the midpoint of the conformational transition, determined by the optical titration, was almost independent of temperature. The standard enthalpy change of the transition at 25°C estimated from the calorimetric data was 0.363 kcal/mole, which may mean that the difference between the standard free energy changes of the transition at 20°C and 40°C does not exceed experimental error. The enthalpy change agrees well with the heat of transfer of benzene from the hydrophobic to the aqueous medium, and thus the compact form of the copolymer is considered to be stabilized by the hydrophobic interaction between the phenyl residues in the interior of the molecule.
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  • 55
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 787-793 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The crystallite size distribution and lattice distortion in the [100] direction in hot-rolled high-density polyethylenes have been obtained by the analysis of the 200 x-ray line profile, using a Fourier transform technique. In the early stage of rolling (roll ratio 〈6) crystallite orientation is accompanied by breakup of crystallites due to intracrystallite slip, whereas in the heavily rolled stage (roll ratio ≧6) deformation proceeds through intercrystallite slip without degradation of crystallites. No marked change in lattice distortion can be found on hot-rolling, at least up to a roll ratio of 8. This shows that the lattice distortion in the rolled sample relaxes to the same extent as in the original lattice when the sample is processed in the crystalline relaxation (αc) region.
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  • 56
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 821-836 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The broad-line proton NMR spectra of melt-crystallized samples of polyethylene covering a very wide range in molecular weight have been analyzed in terms of contributions from three components: (1) a crystalline region with crystals of orthorhombic form; (2) a noncrystalline region with liquid-like character which produces a Lorentzian contribution to the spectrum; and (3) an intermediate region in which the rotation of methylene groups about C - C bonds is partly hindered. The relative mass fractions as well as the character of these components depend greatly on the molecular weight. Samples of low molecular weight (e.g., ≤30,000) are predominantly composed of lamellar crystalline regions with a minor amount of interfacial regions and no liquid-like interzonal regions. As the molecular weight increases beyond 45,000, an interzonal region with a liquid-like character associated with a higher molecular mobility is produced. Above a molecular weight of 100,000, this liquid-like character becomes pronounced with an increase in molecular mobility in the interfacial region.
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  • 57
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 863-872 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A review of the experimental evidence for phenyl group rotation in various polystyrenes and improvements in the interpretation of spin relaxation data for dilute solutions of randomly coiled polymers led to a new calculation of the correlation time for phenyl group rotation from nuclear magnetic resonance (NMR) data. Both 13C and 19F NMR data were reconsidered by using a model which includes motional modulation of the dipole-dipole interaction by overall rotatory diffusion, backbone rearrangements, and internal anisotropic rotation. The choice of a twofold potential to characterize local resistance to internal phenyl group rotation strongly influences the estimate of the rate of phenyl group rotation. The magnetic resonance data are found to be consistent with a correlation time for phenyl group rotation which is one to six times longer than the average correlation time for backbone rearrangement.
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  • 58
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 897-906 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The x-ray pole-figure technique has been applied to the study of orientation in Valonia cellulose. It is found that the maximum of the orientation distribution of the (220) poles of crystallites in Valonia cell walls is precisely normal to the cell wall surface, and the pole population is denser in the longitudinal direction than in the transverse direction. The orientation is interpreted as a typical uniplanar-axial orientation after Heffelfinger and Burton's classification: a uniplanar orientation in (220), and two types of uniaxial orientation in the (220) and (400) planes based on the unit cell parameters for Valonia cellulose. The degree of biaxial orientation of the (220), (220), and (400) plane normals as well as three principal crystallographic axes are shown by Desper's equilateral triangle plots.
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  • 59
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 945-954 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Mechanisms of photocarrier generation in poly(ethylene terephthalate) (PET) have been investigated. In the wavelength range of λ ≦320 nm, the photocurrent spectra correspond closely with the optical absorption spectra of PET and the assignment of the absorption peaks revealed that photocarriers are generated through ππ* excitations. In the wavelength range from 320 to 400 nm, photocarriers are injected from metal electrodes. The threshold energies for Al and Cu electrodes are 2.87 and 2.94 eV, respectively, indicating the presence of surface states. The simplified model gives the density of the surface states as 1.7 × 1014 cm-2 eV-1.
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  • 60
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 969-979 
    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 presented which makes possible the calculation of the dielectric parameters for a distributed dipole relaxation from thermostimulated depolarization current (TDC) data. The theory is applicable to dielectrics which obey the time-temperature superposition principle, i.e., for thermorheologically simple materials. The shift factor, the activation energy, the dielectric relaxation strength, the density of the isothermal displacement current, and the distribution function of relaxation times of the β relaxation in poly(methyl methacrylate) are calculated. The TDC investigations were carried out over the temperature range of -136 to 90°C. The values for the activation energy U = 26.4 kcal/mole and the dielectric relaxation strength Δ∊β = 2 are in good agreement with values obtained from dynamic measurements. A criterion for checking the validity of the time-temperature superposition principle by TDC is suggested.
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  • 61
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 995-1009 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Chain extensions above 1000 Å have been measured in two independent ways for various linear polyethylenes which had either been annealed in or crystallized into the high-pressure hexagonal phase. The distributions of fold-stem lengths measured from fracture-surface statistics and by gel permeation chromatography (GPC) molecular weight analysis of nitrated polymer agree reasonably well both in shape and position. Thinner lamellas, contributing to separate low melting peaks are, however, generally not recorded in fracture surfaces. The best agreement between the two measures, in their averages and overall distributions, is when the GPC weight distribution is compared with the number fracture-surface histogram. This is explicable in terms of the details of nitration.
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  • 62
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 1055-1066 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The micromechanism of the fatigue process in highly oriented nylon 6 fibers is discussed on the basis of changes in mechanical and structural properties during fatiguing. Experimental results show that the fatigue process can be divided into two stages. The characteristic features in the initial period are increases in breaking strength, long period, and molecular orientation, and a reduction in dye penetration. In the second period, after about 500 cycles, breaking strength and orientation decrease slightly, and the long period, permanent strain, and dye penetration increase with duration of fatiguing. It is demonstrated that the structural changes mainly occur in the amorphous regions of the fiber structure. The structural and mechanical changes in the initial period lead to the conclusion that the initial cyclic strain causes strain hardening caused by extended tie chains which do not rupture. A combination of load bearing by tie chains and sliding motion of the fibrillar elements can explain the progressive degradation of the fiber during the second stage of fatiguing.
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  • 63
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 1089-1100 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Binary mixtures of a linear polyester (poly(∊-caprolactone)) and a crystallizable monomer (trioxane) have been investigated by means of differential scanning calorimetry and optical and electron microscopy. The phase diagram indicates the existence of a eutectic at a temperature TmE = 314°K and for a polymer volume fraction φ2E = 0.70, values close to those predicated by the Flory-Huggins theory (using χ = 0.3). Microscopic studies reveal unusual morphologies: (1) In hypoeutectic mixtures, at room temperature, the solvent crystallizes as highly ramified or branched needles. When the remaining melt reaches the eutectic composition, transcrystallization of the polymer is induced by the epitaxial deposition (as established by electron diffraction) of polycaprolactone on the existing trioxane crystals, and leads to highly ordered structures. (2) In hypereutectic mixtures a predominantly spherulitic texture is observed. Blends of trioxane and several other linear polyesters are found to exhibit similar behavior.
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  • 64
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 1117-1120 
    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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  • 65
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 1163-1175 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The method of sedimentation equilibrium was used to obtain values of the thermodynamic interaction coefficient χ as a function of concentration. Five samples of polystyrene with molecular weights ranging from 36,000 to 1,750,000 were studied in benzene over the concentration range up to the volume fraction equal to 0.03. The experimental data were used to test the theory of Koningsveld et al. (Macromolecules, 7, 73, 1974). This theory predicts that the interaction term in the free enthalpy of mixing may be split into one term common for all molecular weights and another term, which depends on molecular weight and vanishes exponentially at high concentrations. It is concluded that the functional form proposed by the theory gives a fair description of experimental data. However, the phenomenological coefficients obtained from the experiment differ significantly from the values predicted by the theory.
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  • 66
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 1189-1198 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Previous work on the small-angle light scattering of polyethylene films, to determine the supermolecular structure, has been continued. One of the main efforts has been the study of a binary mixture whose low molecular weight component forms well defined spherulites and whose high molecular weight component yields a poorly defined rod-like morphology. The addition of the high molecular weight fraction causes a progressive deterioration of the initial spherulitic morphology; a relatively small amount of the high molecular weight species causes a major decrease in the spherulitic size. However, there are no indications of any spherulitic structures when the weight fraction of the high molecular weight species is 0.5 or greater. The isothermal crystallization of a fraction M = 6.6 × 105 was also studied. Spherulites were formed at low crystallization temperatures while at the higher crystallization temperatures the morphology became nondistinct. Preliminary studies with solvents indicate that high molecular fractions, which do not form spherulites when crystallized in the pure state, do so when crystallized from highly swollen solutions.
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  • 67
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 1261-1266 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Thermoluminescence of irradiated polystyrene has been studied in the temperature range 100 to 440°K. Three glow peaks with maximum at 160, 221, and 378°K have been observed. These peaks are analyzed by different methods and the activation energies which were obtained are compared. The activation energies are found to be 0.22, 0.48, and 1.45 eV for the peaks with maxima at 160, 221, and 378°K, respectively. Second-order kinetics is appropriate to all these cases. The glow peaks are attributed to the decay of the free radicals formed on irradiation and subsequent thermal stimulation. The peak with the maximum at 160°K is attributed to electron trapping by the carbonyl groups or peroxy radicals formed on irradiation. The curve with the peak at 221°K is attributed to the cyclohexadienyl radical, and the curve with the peak at 378°K is attributed to the chain radical —CH2—C (C6H5)—CH2—. The centers responsible for the observed thermoluminescence are identified by correlation with electron spin resonance (ESR) data obtained on the same samples.
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  • 68
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 1291-1308 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An unusual crystalline aggregate, which is toroidal in shape, has been formed at the entrance region to capillary dies during the high-pressure extrusion of poly(ethylene terephthalate) melts in an Instron capillary rheometer. The toroidal remnant was discovered in capillary dies removed from the rheometer after the occurrence of oscillating flow. Detailed observations of the rheological factors involved in the formation of the crystalline toroid were made. Examination of recovered entrance plugs disclosed that the crystalline toroid was a hard, stagnant zone which throttled the bulk flow of polymer melt into the capillary during the extrusion experiments. Hot-stage optical microscopy, differential scanning calorimetry, and wide-angle x-ray techniques were used to initiate a structural study of the crystalline toroid. The toroid contained clusters of fibrous crystals which persisted to high temperatures. The fibrous clusters were randomly oriented in a matrix polymer which melted normally. Based upon the rheological and structural evidence, a mechanism of crystalline toroid formation is proposed.
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  • 69
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 1347-1361 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The spin-lattice relaxation time and the nuclear Overhauser enhancement (NOE) of 19F nuclei in dilute solutions of poly(p-fluorostyrene) and poly(m-fluorostyrene) were measured as a function of molecular weight, concentration, temperature, solvent, and field strength. Models for local motion of the chain backbone based on independent internal rotations or on one-dimensional defect diffusion failed to provide a quantitative description of both T1 and the NOE. A model based on three-bond crankshaft motions and a cutoff of coupling along the backbone gives a consistent account of these results as well as 13C nuclear magnetic resonance (NMR) relaxation data on polystyrene from the literature. The model provides a finite set of exponential correlation times to describe local motion, the center of the distribution lying in the nanosecond region for dilute solutions of polystyrenes in normal solvents. The apparent activation energy for the backbone motion obtained from the temperature dependence of the average correlation time based on NMR data is about 20 kJ mole-1. The local correlation times based on NMR are appreciably shorter than those determined by dielectric relaxation. This discrepancy points to the existence of several different local motions which make different contributions depending upon the experimental technique employed.
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  • 70
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 1427-1434 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Samples of ultradrawn high density polyethylene were studied by thermomechanical analysis. The purpose was to study the dimensional changes in polyethylene morphologies of extreme orientation. Dimensional changes were measured from -140 to +70°C with a precision of better than 1%. A negative thermal expansion coefficient was observed along the length (c axis) of the fibers containing the polyethylene morphologies of extreme orientation. A change in negative coefficient is observed between -35 and -45°C. The sign and magnitude of the expansion coefficient confirm, along with other evidence, the existence of extended chain structures in these morphologies. A series-parallel model has been developed for the ultradrawn polyethylenes to describe the dimensional changes with temperature.
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  • 71
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 1501-1505 
    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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  • 72
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 1521-1536 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The steric factors σ of homopolymers of ethyl, n-butyl, and n-octyl methacrylate, of equimolar random and alternating copolymers of these monomers with styrene, and of polystyrene, were determined by measuring intrinsic viscosities in a good solvent (butanone, 25°C) and extrapolating the data thus obtained to zero molecular weight of the polymer. For all comonomeric pairs under investigation, the σ2 of an equimolar random copolymer and, particularly, of an alternating copolymer, is higher than the arithmetic mean (σ2A + σ2B)/2 of the σ2 values of the parent homopolymers. The positive deviation from the linear dependence of σ2 on the copolymer composition, expressed as an increment of σ2, is proportional to the mole fraction of alternating dyads in the copolymer chain with in the limits of experimental error. The effect of copolymer microstructure on the unperturbed dimensions of the chains has been compared for equimolar copolymers of styrene with methyl, ethyl, n-butyl, and n-octyl methacrylate by using a relative increment ξ defined as the ratio of σ2 of the alternating copolymer to (σ2A + σ2B)/2. The dependence of ξ on the number of carbon atoms in the alcohol substituent of the methacrylate component of the copolymer seems to exhibit a maximum for ethyl methacrylate.
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  • 73
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 1585-1600 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The thermodynamic theory of bulk ABA copolymers developed by Leary and Williams is extended to copolymer-solvent systems. Free energy expressions are derived for five hypothetical phase-separated morphologies and evaluated specifically for a polymer with approximately 25% of the A component. The separation temperature, Ts, at which a given morphology will be in equilibrium with a homogeneous mixture, is also evaluated. The major result is the prediction of the Ts(φS) depression, where φs is the solvent fraction. Depression is maximized when δS is equidistant between δA and δB, but becomes rapidly less when δS is outside the δA-δB range. Morphological favoritism is independent of φS and δS (model does not apply to preferential precipitation), with a planar microstructure being favored along with microstructures containing domains of B in continuous A for the 25% A polymer.
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  • 74
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 1627-1639 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Bromine has been randomly substituted in the 3 or 6 position of the pendant carbazole group of poly(N-vinylcarbazole) using N-bromosuccinimide in chlorobenzene solution. X-ray diffraction indicated that this substitution interferes with the interchain interactions in the amorphous polymer eliminating the unusual degree of chain parallelism and destroying the ability to crystallize. Charge carrier photogeneration and mobility measurements show that holes are still the majority carrier in the bromine-substituted polymer but both generation and mobility are substantially reduced compared to the unsubstituted polymer. It has not been possible to separate the influence of pendant group electronic structure from that of bulk chain conformation in this modification of the polymer photoconductive properties.
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  • 75
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 1663-1674 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The relationship of birefringence to stress in an amorphous polymer was studied, with emphasis on conditions of high stress and rapid cooling. The latter (nonisothermal) conditions are important in connection with studies of polymer processing operations. Polystyrene was pulled at a constant elongation rate (0.075 to 2 sec-1 in the present and related work) under both isothermal conditions (in the range 120 to 157°C) and nonisothermal conditions (with cooling rates in the range 0.6 to 1.7°C/sec). Generally we conclude that stress in proportional to birefringence under a wide range of conditions, except that a nonlinear regime appears at stresses higher than about 107 dyn/cm2. In this regime, stress increases more rapidly with deformation than does birefringence.
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  • 76
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 1721-1738 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Various methods of solving the dynamical equation for defect polymers are discussed. It is shown that the Green's function (GF) can be conveniently used to reduce the order of the characteristic equation to the number of the degrees of freedom of a repeat unit in the case when the perturbation caused by each of the defects is localized within it. In the general case, the order of the reduced determinant depends on the range of the interaction forces between the defect unit and the regular chain.For a polymer chain containing one or two defect units, the Green's function method allows us to obtain the exact solution of the dynamical equation, while for a high concentration of randomly distributed defect units various approximation methods can be used. As a possible approach to the solution of the latter problem we suggest using either one of the versions of the perturbation theory (the dilute limit, the coherent potential approximation) or the cluster approximation.
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  • 77
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 1707-1719 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The telechelic polybutadiene-methacrylic acid copolymer (Hycar CTB) containing 2 mole percent acid and neutralized (5-100%) by alkali ions, Na+, K+, and Cs+, has been studied by small-angle x-ray scattering. Salt groups form clusters, and the average value of the radii of gyration is approximately 8 Å; this value seems to be independent of the nature of the cation and the degree of neutralization. The existence of a low-angle maximum in the scattering intensity gives evidence of a mean distance of 80 Å between clusters in the fully neutralized sample. This distance increases slightly with a decreasing degree of neutralization. A more precise analysis of the small-angle scattering curve gives further information on the cluster structure: the ionic groups may form small bilayer disks while the polymer chains maintain a regular distance of 80 Å between the disks.
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  • 78
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 1779-1789 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Extruded, injection-molded, unoriented crystallized specimens and capillary rheometer efflux strands of commercially stabilized polypropylene without nucleating agents were examined by optical microscopy and x-ray diffraction to determine the conditions for β-form crystallization as a function of the distance from the surface and of the shear rate at commercial processing conditions. Results demonstrate that at all “cooling conditions” ΔT = Tm - Tb (defined as the melt temperature Tm minus the bath temperature Tb) effects of strain flow initiate nucleation of β-form crystals. The shear rate is demonstrated to be important for β-form crystallization. A critical average threshold value for the shear rate of approximately 3 × 102 sec-1 has to be exceeded. The β modification is mostly connected with type-III spherulites and partly to row structures, and it is observed at processing conditions in oriented structures only.
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  • 79
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 1805-1835 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The geometrical constraints acting on sections of tie molecules in noncrystalline regions severely limit the number and type of available polymer chain conformations. It is shown that these constraints induce explicit correlations in the rotations about the backbone bonds. These correlated rotations, in turn, specify distinct structural conversion paths which define the molecular mechanisms underlying the deformation response of tie molecules. Application of these constraining relationships to highly oriented polyethylene shows that the kink and jog structures of tie molecules can be decomposed into combinations of three primary conformational building blocks. Each of the basic conformational subunits follow an explicit set of dihedral angle correlations and, consequently, imparts specific characteristics to the composite structure of tie molecules. It is proposed that the composite response characteristics of tie molecules can be described as linear combinations of the response characteristics of these three primary conformational subunits.
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  • 80
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 1953-1966 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The low-temperature γ′ relaxation was found to originate in the diol units of a variety of crosslinked polyesters. The results were explained in terms of Boyer's Crankshaft model. As the polyester concentration in the networks increased, the γ′ relaxation shifted to higher temperatures and the intensity of the relaxation increased but not as rapidly as the diol concentration. This behaviour was interpreted in terms of an interaction of the relaxing species with the surrounding matrix.
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  • 81
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 1989-1998 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Anodic growths on tungsten electrodes as a result of an applied electrostatic field with an atmosphere of benzonitrile (from about 5 × 10-4 to 10-5 torr) are studied as a function of many parameters. In order to observe the growth phenomena at high resolution in situ, the experiments were performed in an electron microscope. The growth rate of the dendrites is found to be irregular; an expression for dependence on the electric field is proposed to explain the evolution of needle length versus time t: \documentclass{article}\pagestyle{empty}\begin{document}$$ l(t) = l_M [1 - \exp ( - at)] $$\end{document} The mechanism of branching is also discussed.
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  • 82
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 2039-2045 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 4 Ill.
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  • 83
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 2065-2074 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The diffusion coefficient for two diffusants of the type n-(CH2)NX is measured, where N ≃ 25, 45 and X is a suitable label; the matrix is linear polyethylene cooled at two widely differing rates from the melt. The measuring technique used is a recently developed one based on infrared microdensitometry. The results indicate that these diffusants diffuse faster in the slowly cooled matrix, in marked contrast to the behavior of gaseous diffusants. They are in agreement with the predictions of the model developed in a previous paper (part I), in which the constraints imposed by interlamellar tie molecules on long diffusants were shown to be important.
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  • 84
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 2103-2111 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dichroism of the 889, 1364, and 3063 cm-1 infrared absorption bands of glassy, amorphous polycarbonate has been measured as a function of the strain in the range 0 to 2% at 23°C. The data obtained for these three bands superpose rather well over this strain range. Negligible dichroism is observed up to about 0.6% strain; above this level, the dichroic ratio increases in an approximately linear manner. Independent mechanical data, obtained under comparable conditions of time-scale and temperature, are cited which show that a transition from approximately linear to marked non-linear viscoelastic behavior occurs with glassy polycarbonate in the range 0.7 to 1.0% strain. The coincidence on the strain axis of a relatively abrupt increase in optical absorption anisotropy with a distinct change in Young's modulus is discussed in terms of a recent molecular theory of deformation of glassy polymers. It is suggested that the data are consistent with the view that the transition from linear to nonlinear viscoelastic behavior in glassy polycarbonate is marked by the onset of significant rotation around backbone bonds.
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  • 85
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 2213-2225 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: This paper reports the first measurements of macromolecular segmental relaxation times by phosphorescence depolarization. Steady-state phosphorescence polarization experiments were performed on samples of poly(methyl acrylate) incorporating 0.5 wt % copolymerized acenaphthylene or 1-vinyl naphthalene as phosphorescent probes over the temperature range 77 to 310°K. Depolarization of phosphorescence occurs with the onset of segmental motion of the polymer at ca. 278°K. Motion of either probe is characterized by an activation energy of 195 (±5) kJ mole-1, which is in fair agreement with the mean value of 230 kJ mole-1 estimated for the segmental relaxation of poly(methyl acrylate) by dielectric and mechanical relaxation techniques. Transient depolarization measurements confirm the absence of probe motion below the glass transition temperature. Phosphorescence intensity and triplet state lifetime data are capable of detection of a second transition in the polymer in accord with observations using more conventional techniques.
    Additional Material: 6 Ill.
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  • 86
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 2255-2267 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: For a nondraining polymer coil in the vicinity of the theta temperature the cube of the viscosity expansion factor αη may be expanded in powers of the excluded-volume parameter z as αη3 = 1 + C1z + C2z2 + ···. No exact values of the coefficients C1, C2, ···, are as yet known. This paper aims at evaluating C1 by the Kirkwood-Riseman formalism of polymer hydrodynamics with no mathematical approximation. The analysis gives C1 = 1.29, which is much smaller than 1.55 derived on the basis of the same formalism by Kurata and Yamakawa. The approximations used by these authors are discussed by comparison of their analysis with the present one. The first-order excluded-volume effect on the translational friction factor is also evaluated in the same way as for the intrinsic viscosity, and the result is shown to agree quite closely with the exact value determined by Stockmayer and Albrecht.
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  • 87
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 2277-2280 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 3 Ill.
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  • 88
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 1-9 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The autocorrelation function of orientations, derived for the model of conformational jumps in a chain described in a tetrahedral lattice, has been tentatively applied to dielectric relaxation data. The complex dielectric relaxation of polymers can be interpreted by the aid of only two relaxation processes. In the case of poly(p-chlorostyrene) in solution, the characteristic times that we have calculated agree favorably with the fluorescence-depolarization results. The model has been shown to be consistent with the empirical decay function exp[- (t/τ)β] proposed by Williams.
    Additional Material: 5 Ill.
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  • 89
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A study has been conducted on the solid-state extrusion of three semicrystalline polymers:poly-propylene (PP), poly(vinylidene fluoride) (PVDF), and high-density polyethylene (HDPE). HDPE has been extruded in continuous lengths with area reductions up to 25× at temperatures substantially below the melting region. Such extrusion has been identified as a solid-state process, since measurements of the temperature of the polymer during extrusion indicate the absence of significant heating due to deformation. In contrast, continuous lengths of PP and PVDF could not be obtained substantially below their melting temperatures, indicating that crystallization during extrusion is an important process for these polymers. Under severe extrusion conditions (low temperatures, high area reductions. etc.), all three polymers failed within the tapered region of the extrusion die. Two modes of failure have been identified, brittle fracture and, surprisingly, necking. Grid-line distortion patterns and a highly simplified upper-bound plasticity analysis both indicate that shear deformations are a major factor during high-stress extrusion.
    Additional Material: 5 Ill.
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  • 90
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 59-69 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polyurethanes are block copolymers composed of hard and soft segments which often undergo microphase separation with the resultant formation of hard and soft domains. The nuclear-magnetic-free induction decay of such systems is shown to consist of a fast Gaussian component corresponding to glassy domains and a slow exponential component corresponding to rubbery domains. Thus, by being sensitive to the microscopic mobility of a material, nuclear magnetic resonance (NMR) has the potential to determine when a polyurethane has separated into domains and the relative amounts of material in each domain. After annealing the free-induction decay of a linear polyurethane showed a distribution of relaxation times indicating that mixing of the domains had taken place and a continuum of compositions exist in the material. The free-induction decay of a cross-linked polyurethane was unaffected by annealing, confirming the results of an earlier study.
    Additional Material: 7 Ill.
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  • 91
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 85-95 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Gel permeation chromatography (GPC) combined with on-line flow time measurements have been applied to the analysis of branching in polymers. Three sets of branched polymers were examined: polybutadienes lightly crosslinked by high energy radiation, a styrene-divinyl benzene copolymer and several of its fractions, and polyvinyl acetates branched by polymer transfer reactions during polymerization. The reduction in intrinsic viscosity due to branching was determined for each GPC fraction of the polybutadiene samples. The branching frequency in these fractions was known from other information, so the results were used to establish a relationship between viscosity ratio G and the theoretical size ratio g. This relationship was then used to calculate the distribution of branching and Mw in the styrene copolymers and the polyvinyl acetates. The results were compared with independent information on these polymers. The agreement was generally good.
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  • 92
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 279-282 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Adiabatic compressibility measurements are reported on solutions in hydrocarbon solvents of a low Mw high ethylene content, and of both high and low Mw low ethylene content ethylene-propylene copolymers. In all solutions the observed adiabatic compressibility was lower than the solvent value by an increment which was a function of the solvent type. Comparison of the data for a high and low molecular weight sample of the same copolymer indicates no molecular weight effects. Changes in the composition of the copolymer, as indicated by NMR spectroscopy, have only a slight effect on the adiabatic compressibility. The dominant feature of these studies is the apparent correlation of the chain length of the alkane solvent with the decrement in the compressibility.
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  • 93
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 263-277 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Acoustic absorption and adiabatic compressibility measurements are reported on solutions of polystyrene (Mn = 89,000) in toluene and cyclohexane. The data in toluene cover a temperature range from 293 to 343°K and a concentration range of 10-400 Kg m-3 (1-40 wt%). The dependence of acoustic absorption on concentration was found to be linear up to 100 kg m-3, which corresponds to the concentration at which polymer-polymer interactions cause significant changes in the specific viscosity-concentration relationship. Up to 200 kg m-3 the data could be fitted to computations based on an artificial separation of the dispersion into contributions from viscoelastic and segmental processes, using parameters obtained from a study of narrow molecular weight distribution samples at 25 kg m-3. However, neither approach was capable of describing dispersions in the 300, 400 kg m-3 solutions. The modification of the relaxation spectrum observed at the highest concentrations is ascribed to volume and entropy changes associated with alterations of the local environment around a segment of the polymer chain. These changes have their origin in interchain penetration and polymer-polymer contacts, and indicate that ‘entanglement’ is primarily entropic in effect.The adiabatic compressibility exhibited similar deviations from a simple concentration dependence, and allowed estimation of an incompressible volume increment associated with polymer-polymer interactions in the high-concentration entangled matrix. However, the adiabatic compressibilities of solutions of polystyrene, 10-15 kg m-3, in cyclohexane showed no deviations from simple behavior in the region of the theta temperature. Measurements of the adiabatic compressibility of polystyrene in mixtures of cyclohexane-toluene have been used to obtain the relative magnitude of solvent and polymer contributions to the excess compressibility.
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  • 94
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 355-369 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Crystallization during polymerization of polydiphenylsilylene has been accomplished. Best results are obtained by initial thermal polymerization to the amorphous macromolecule. The macromolecules are then decomposed and repolymerized by sublimation. Macroscopic extended-chain single crystals are produced. The polymer crystals, once molten, will not recrystallize. Their initial characterization is described using infrared, Raman, ultraviolet, and nuclear magnetic resonance spectroscopy. X-ray and thermal analysis data are also given.
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  • 95
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 371-378 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Samples of the alkoxyphosphazene polymer [P(OCH3)2—N—]x and the aryloxyphosphazene polymer [P(OC6H5)(O-p-C6H4C2H5)—N—]x were crosslinked using γ-radiation. The resulting elastomeric networks were characterized, in elongation, with regard to both their stress-strain relationships and their stress-temperature (“thermoelastic”) properties. Values of the ratio 2C2/2C1 of Mooney-Rivlin constants used to characterize the stress-strain isotherms were found to be similar to those of other elastomeric networks of comparable degree of crosslinking. The thermoelastic data show the energetic component of the retractive force to be positive for the alkoxy polymer, but negative for the aryloxy polymer. Although it is not difficult to suggest a possible molecular explanation for some of these thermoelastic results, a definitive interpretation would require reliable information on the conformational characteristics of the skeletal bonds in the polyphosphazene chain.
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  • 96
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 417-439 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A new free-volume theory is combined with the thermodynamic theory of Flory and the entanglement theory of Bueche to provide a means of predicting the temperature, concentration, and molecular weight dependence of mutual-diffusion coefficients in amorphous polymer-solvent systems. The predictions of the theory are compared with actual data for the ethylbenzene-polystyrene system.
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  • 97
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 477-483 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The problem of a polyelectrolyte near the rod limit is formulated incorporating both the short-range stiffness of the backbone (the “wormlike chain”) and the electrostatic interaction between segments taken as a Debye-Húckel potential. By the use of a physically valid approximation an expression is derived for the mean-square extension length of a short polyelectrolyte chain. Some remarks are made on the relationship between the electrostatic interaction and the usual excluded-volume problem for polymer solutions.
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  • 98
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 541-554 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The thermally stimulated current (TSC) technique has been used to perform a detailed study of the complex relaxation modes observed in poly-L-proline II. Each mechanism has been resolved into elementary processes, each well described by using the assumption of a single relaxation time following an Arrhenius equation. This resolution allows us to predict the complex dielectric constant for temperatures between 77 and 400°K and frequencies between 10-6 and 104 Hz. In the range where experimental results are available, the predicted energy losses are in very good agreement with those measured by DC transient experiments, the pendulum technique without contacting electrodes, and the AC bridge. We discuss the probable origin of the various relaxation modes. The relaxation observed at the highest temperature may be attributed to electrons trapped at the boundaries between paracrystalline and crystalline regions. From the changes in the relaxations caused by bound water, we conclude that there are two types of water interacting with the macromolecular substrate. With increasing water content, the relaxation modes observed may first be due to water tightly bound between two carbonyl groups of adjacent chains and second, to increased stiffness of the poly-L-proline chain from more mobile water.
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  • 99
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Light scattering from polybutene-1 films prepared by tubular extrusion was studied in order to investigate its crystalline superstructure and the deformation mechanism. Analysis of the light-scattering patterns together with electron micrographs, indicate the existence of sheaflike crystalline superstructures. The sheaves are aligned nearly side by side with their axes preferentially oriented perpendicular to the machine direction. The Hv scattering patterns exhibit a “butterfly” appearance. Analysis of the patterns in terms of scattering and azimuthal angles at which the scattering intensity is a maximum yields information on the size and shape of the sheaflike texture. The information should be of importance in studies of anisotropic crystal growth caused by molecular orientation in the melt and of the deformation mechanism of the texture. The deformation behavior should be representative of that of different parts of spherulites, at least qualitatively; the deformation of the texture along the machine and transverse directions corresponds to deformation of equatorial and meridional regions of a spherulite, respectively.
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  • 100
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 617-626 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Changes in scintillation efficiency during formation of plastic scintillator compositions have been studied. The separate roles of energy transfer and solute fluorescence efficiencies in the determination of the observed luminescence output of the systems were elucidated. Bis-1,4-2-(5-phenyloxazolyl)benzene(POPOP); 1,1′,4,4′-tetraphenylbutadiene(TPB), and 9-methyl anthracene (MAN) were employed as scintillator solutes. The increased scintillation yield of polymerizing solutions of POPOP is primarily a consequence of increased energy transfer efficiency from solvent to solute. Solutions of TPB exhibit enormous increases in luminescence output upon formation of polymers. The major contributor to the overall effect is the great enhancement of the fluorescence efficiency of TPB which occurs when the microviscosity of the medium is increased. MAN solutions exhibit a decreasing luminescence yield upon polymerization despite increasing energy transfer efficiency. Structural rearrangements of the fluor, consequent upon involvement in the polymerization kinetic chain, are responsible for the decreased scintillation efficiency.
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