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  • EARTH RESOURCES AND REMOTE SENSING  (1,945)
  • Physics  (1,517)
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  • 2005-2009
  • 1995-1999
  • 1980-1984  (1,348)
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  • 1983  (1,348)
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  • 1976  (1,421)
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  • 2005-2009
  • 1995-1999
  • 1980-1984  (1,348)
  • 1975-1979  (2,898)
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  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 11-27 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Fluorescence anisotropy decay experiments are described for polystyrene in various ethylacetate-tripropionin mixtures. Decay curve trends agree with the proposed theoretical autocorrelation function. Study of the effects of viscosity shows that the mean relaxation time varies according to a nonlinear law for low viscosities and that the relaxation time θ, reflecting the effects of the possible departures from the motions permitted by an ideal tetrahedral lattice, obeys a law of the type: θ = α + bη. Furthermore, the effects of the direction of the fluorophore transition moment are examined.
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  • 2
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1-10 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The scattering law S(k,w) for dilute polymer solutions is obtained from Kirkwood's diffusion equation via the projection operator technique. The width Ω(k) of S(k,w) is obtained for all k without replacing the Oseen tensor by its average (as is done in the Rouse-Zimm model) using the “spring-bead” model ignoring memory effects. For small (ka\documentclass{article}\pagestyle{empty}\begin{document}$ \sqrt N $ \end{document} ≪ 1) and large (ka ≫ 1) values of k we find Ω = 0.195 k2/β α η0 \documentclass{article}\pagestyle{empty}\begin{document}$ \sqrt N $ \end{document} and Ω = k2/βξ, respectively, indicating that the width is governed mainly by the viscosity η0 for small k values and by the friction coefficient ξ for large k values. For intermediate k values which are of importance in neutron scattering we find that in the Rouse limit Ω = k4a2/12βξ. When the hydrodynamic effects are included, Ω(k) becomes 0.055 k3/βη0. Using the Rouse-Zimm model, it is seen that the effect of pre-averaging the Oseen tensor is to underestimate the half-width Ω(k). The implications of the theoretical predictions for scattering experiments are discussed.
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  • 3
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 437-449 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The luminescence of 1,2-polybutadiene was measured during and following irradiation with 1.4-MeV electrons at 90 °K. Measured under isothermal conditions, the light intensity at first increases sharply on start-up of irradiation, and then reaches a plateau after several seconds. The equilibrium value was found to be linearly dependent on the dose rate employed. The postirradiation luminescence decay measured at 90°K follows second-order kinetics.The light emitted by the irradiated sample during warm-up to room temperature is characterized by the appearance of four intensity maxima at 118, 168, 223, and 261 °K. The first three peaks are attributable to the onset of local motion, whereas the peak at 223 °K is caused by the long-range motion occurring at the glass-to-rubber transition. A preirradiation of the polymer in vacuo causes an increase in these four peaks as well as the formation of a new maximum at 143 °K.Intermittent exposure of the irradiated sample to light of wavelengths λ 〉 450 nm causes the isothermal luminescence decay to be interrupted by a burst of light emitted by the sample during and shortly following the light exposure. This treatment also results in considerably reduced intensity maxima during warm-up to room temperature. An interpretation of the findings reported is given on the basis of reactions involving primary and secondary transient species produced during irradiation and on the molecular parameters of the polybutadiene.
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  • 4
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 401-414 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dynamic piezoelectric stress constant e*25 of drawn films of poly(γ-methyl D-glutamate) (PMDG) cast from solutions in α-helix-promoting solvents 1,2-dichloroethane (DCE) and chloroform and from the nonhelicogenic solvent dichloroacetic acid (DCA) was measured from -180°C to 200°C at 110 Hz. The drawn and annealed films cast from chloroform show a small peak for the real part of piezoelectric stress constant -e′25 in the temperature range of the mechanical α2-crystalline relaxation, which is caused by the distortion motion of the backbone chain of the α-helix. On the other hand, drawn films cast from DCE show the peak of the real part of the piezoelectric stress constant, whose magnitude decreases in the range of the mechanical α1-crystalline relaxation or the β-relaxation processes, which were previously ascribed, respectively, to mutual slipping of α-helices and to the micro-Brownian motion of disordered regions. Also, -e′25 becomes virtually zero near 180°C where the α2-relaxation is located. These results suggest that the polarization change induced by applied strain is caused by distortion of the backbone chains in the α-helix. Near 0°C, the temperature range of the side-chain mechanical relaxation, -e′25 exhibits a marked peak both for films cast from chloroform and from DCE. The maximum value of -e′25 and the orientation function of the α-helix axis are linearly related and extrapolation of -e′25,max to unit orientation function gives 1.3 × 104 cgs esu which corresponds to 2.4 Debye per residue. This value corresponds reasonably to the value of 3.71 Debye for the permanent dipole moment of NHCO bond if the correction for crystallinity is made. This result also indicates the piezoelectric properties of PMDG arise from distortion of the backbone chain of the α-helix induced by applied strain.
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  • 5
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 955-957 
    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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  • 6
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 941-954 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A mathematical model developed in an earlier paper describes the experimental x-ray profiles of equatorial nylon-6 reflections in terms of Pearson VII functions. The present paper deals with the physical aspects and interpretations of the interrelations of the parameters obtained and the relation between these parameters and the results of other types of measurements. It was found that the growth of the crystallites perpendicular to the chain axis is not isotropic, the strongest growth being in the direction of the hydrogen bonds. Growth and perfection of the crystallites are found to be highly correlated. Large crystals are related to short distances between the planes containing the hydrogen bonds and so to densely packed, i.e., perfect unit cells. This correlation forms the basis for the observed similarity between our quantification technique and the method of the crystal perfection index introduced by Statton. Curve resolution, however, makes the method better applicable for poorly crystallized samples. Comparison of the results with those of small-angle x-ray scattering gave a high degree of consistency with respect to the determined crystal size. In the literature mention is made of a relation between the dimensions and the melting point of the crystals; this relation is confirmed by comparing the appropriate x-ray parameters with DTA results of methoxymethylated nylon 6-yarns.Information about the γ-phase can be obtained from equatorial and meridional reflections. The expected relationship between the relevant peak areas was established. This reported evidence shows the physical validity of the parameters obtained using the Pearson VII model for the analytical description of x-ray reflections of nylon-6 yarns.
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  • 7
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1201-1209 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The glass-transition temperatures of a series of copolymers of ethyl acrylate and acrylic acid neutralized with various cations were investigated. It was found that a plot of Tg as a function of ion content, for every type of ion investigated here, gives an unusual sigmoidal curve, which can be correlated with the onset of the failure of time-temperature superposition in viscoelastic studies, as will be shown in a future publication. Also, all of the Tg versus concentration curves for the various counterions can be superposed if the plots are made against cq/a, where c is the metal acrylate content, q the cation charge, and a the distance between centers of charge. Furthermore, in one region of water content, a linear relation is obtained between the glass transition and the water content (in weight-%) independent of the ion concentration over wide ranges of ion content. Finally, above an ion concentration of 12 mole-%, the rate of change in Tg per water molecule per ion pair at constant ion content, (∂Tg/∂n)c is linear but with different slopes above and below two water molecules per ion pair.
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  • 8
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1087-1095 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The changes which take place on annealing rigid PVC in the vicinity of the glass transition have been followed by differential scanning calorimetry. The changes appear as an increase in the glass-transition temperature and a decrease in the enthalpy with time of annealing. For annealing at 75°C, the enthalpy after 50-100 hr approaches the value characteristic of the equilibrium liquid state. The results obtained for annealing at 65°C and 75°C are in accord with those expected for the relaxation of an amorphous material, and are at variance with those expected on the basis of crystallization taking place on annealing. The enthalpy relaxation process is characterized by a distribution of activation energies centered about 18.8 kcal mole-1, and seems to reflect a multiplicity of molecular processes.
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  • 9
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1149-1156 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The melt rheological behavior of an anionically polymerized styrene-butadiene-styrene (SBS) block copolymer sample (S: 7 × 103 and B: 43 × 103) was studied using a Weissenberg rheogoniometer. Highly non-Newtonian behavior, high viscosity and high elasticity, which are characteristics of ABA type block copolymers, were observed at 125°C, 140°C, and 150°C. The data at these temperatures superimposed well onto a master curve giving a constant flow activation energy. However, the data at 175°C indicated a marked change in the flow mechanism between 150°C and 175°C. At 175°C, the sample showed Newtonian behavior, negligible elasticity, and deviation from the master curve. These findings may be considered as an indication that the SBS block copolymer sample undergoes a structural change from a multiphase structure at low temperatures into a homogeneous structure at some temperature between 150°C and 175°C.
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  • 10
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1161-1167 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A new crystalline form of isotactic poly(pentene-1) was obtained from dilute solution in amyl acetate. We have designated it as form III. The morphology and structure of isothermally crystallized samples were investigated by electron microscopy and electron and x-ray diffraction. This crystalline modification can be indexed on an orthorhombic unit cell (cell dimensions: a = 21.20 ± 0.05 Å, b = 11.48 ± 0.05 Å, c = 14.39 ± 0.05 Å (fiber axis) and probable space group P212121).
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  • 11
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1187-1199 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Glass-transition temperatures and phase separation have been studied in amorphous bisphenol-A polycarbonate plasticized with pentaerythritol tetranonanoate (PETN), trimellitic acid, tridecyloctyl ester (TMDO), and tritolyl phosphate. (TTP). Phase separations occur with partially compatible plasticizers like PETN or TMDO. With PETN, for compositions situated in the miscibility gap, the system is composed of a pure plasticizer phase and of a plasticized polymeric phase characterized by a transition temperature of 110°C. In the case of TMDO and additional phase separation occurs below 55°C and two plasticized polycarbonate phases are observed. In compositions falling in the region where the could point curve crosses the glass-transition diagram the phase separation may be delayed by quick cooling. TTP is completely compatible with polycarbonate and the variation of the glass-transition temperature follows a Gordon and Taylor equation.
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  • 12
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1235-1240 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An x-ray back-reflection rotating camera has been used to measure the lattice constant, thermal expansion, and compressibility in the polymer chain direction of a polydiacetylene, poly[bis(p-toluene sulfonate) of 2,4-hexadiyne 1,6-diol]. The thermal expansion coefficient of the polymer chain is small and positive (0.9 ± 0.2 × 10-6 °K-) at 300°K, but negative below about 70°K. Application of 3.43 kbar hydrostatic pressure at 299°K changed the unit cell dimension in the polymer chain direction by less than 10 ppm.
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  • 13
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1425-1431 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Persistence vectors a ≡ 〈r〉 are calculated for polypropylene, polystyrene, and poly(methyl methacrylate) chains as functions of chain length and stereochemical constitution. Differences between the progressions of a with chain length for these vinyl polymers are related to their conformational characteristics. The preferences of the syndiotactic chains for the tt dyad conformation are manifested most strikingly in the behavior of this vector.
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  • 14
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Solvent-cast films of blends of poly(∊-caprolactone) (PCL) with poly(vinyl chloride) (PVC) were examined by low-angle x-ray scattering and by small-angle light scattering. X-ray scattering from crystalline compositions were analyzed using the Tsvankin-Buchanan technique and led to values of the repeat period of the lamellar structure and the thickness of the crystalline and amorphous layers. With increasing content of PVC, the amorphous layer thickness increased sufficiently to accommodate the PVC, leading to values of the linear crystallinity consistent with macroscopic measurements by density and DSC techniques up to about 50% PVC by weight. Above this concentration, the lamellar structure no longer appeared to be volume filling. At high concentration of PCL, the polymer consisted of volume-filling spherulites containing the lamellar substructure. Spherulite sizes were measured by light scattering and absolute light scattering intensities were consistent with calculations based upon the degree of crystallinity and anisotropy of the spherulites. Compositions containing more than 60% PVC were amorphous. Low-angle x-ray scattering was interpreted in terms of the Debye-Bueche theory which leads to values for a correlation distance lc and the mean-square electron density fluctuation 〈η2〉 (which was also obtained from the invariant). By the method of Porod, the correlation distances were resolved into persistence lengths within the two phases, which were determined as a function of composition. The fluctuation 〈η2〉 was analyzed in terms of a two-phase model to show that its value was somewhat larger than would be obtained if the phases were composed of the pure components. It was not possible to uniquely determine their compositions. The data were consistent with the existence of a transition zone of the order of 30 Å thick between phases.
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  • 15
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1485-1493 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The universal calibration for gel permeation chromatography (GPC) has been applied to amylose and dextrans. The molecular weight distribution of amylose has been measured starting from known data on dextrans. The agreement found between the molecular weight averages resulting from GPC and those obtained by other methods justifies the procedure followed. The GPC measurements were performed with dimethylsulfoxide as the elution solvent and deactivated silica gel (Porasil) as the column-filling material.
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  • 16
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1495-1512 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Unoriented T-die flat films of nylon 6 and PET films annealed at 90°C were stretched in water at 80°C. Amorphous PET films were stretched in water at 65-75°C. Changes in the light scattering patterns from these samples upon stretching were investigated. One of the observed LS patterns from the stretched samples is the Hv eight-leaf pattern consisting of four lobes and streaks. In the nylon 6 and heat-treated PET showing this pattern, spherulitic patterns can be seen in polarization microscopy. The microscopic spherulitic superstructure may possibly be the factor responsible for producing the lobe-and-streak pattern. On the other hand, many microscopic eight-leaf patterns can be observed in amorphous unannealed PET showing the lobe-and-streak pattern. These microscopic patterns are due to retardation at stress concentrations around impurities and nuclei. The superstructure giving these microscopic patterns must be the origin of the lobe-and-streak pattern from unannealed PET. Another scattering pattern, the Vv cruciform pattern, was observed in both stretched nylon 6 and unannealed PET. This pattern is due to an orientation change across the slip lines observed under a polarizing microscope. It is noted (1) that the appearance of the slip lines in PET coincides with the occurrence of oriented crystallization on stretching, (2) that the lobe-and-streak pattern from PET in which orientation crystallization has taken place is fairly stable to heat treatment and does not disappear until just before melting, and (3) that the superstructures produced at low stretching seem to be deformed on further stretching, in accordance with affine deformation theory.
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  • 17
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1567-1573 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An Interesting kinetic effect in the environmental stress cracking (E.S.C.) of polyethylene has been observed, in which the liquid viscosity plays an important role. E.S.C. of a low density, high melt index polyethylene due to silicone oils has been studied using constant load creep experiments. For relatively low stresses, it has been found that the time to fracture is independent of the viscosity of the silicone oil, all other factors being approximately equal. However, at high stresses, the time to fracture increases with increasing viscosity for a given stress. This effect has been shown to be due to the relative ease with which the liquid penetrates a growing crack and thus always be at the crack front. Times to fracture for viscous liquids at high stresses are longer since crack propagation continues partially with and partially without liquid contact, fracture rate being much slower when not in the presence of the liquid.
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  • 18
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1591-1599 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dielectric β-relaxation in oriented poly(ethylene terephthalate) was investigated over wide ranges of frequency and temperature, with the electric field applied at inclinations of 0°, 45°, and 90° to the draw direction. Pronounced directional anisotropy is observed over the entire range of temperature and frequency. With the external field parallel to the draw direction the dielectric loss is considerably smaller than the value obtained with the field normal to the draw direction. The value obtained with the electric field at 45° to the draw direction is intermediate between the other two. On the other hand, the activation energy is largest for 0° inclination and smallest for 90° inclination. It is suggested that motions of the dipoles involve localized rocking of the molecular chain backbone, particularly when the external electric field is parallel to the chain direction.
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  • 19
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1659-1669 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dynamic mechanical properties of cold-compacted films of polyethylene prepared by γ-ray-induced polymerization in bulk at 30°C are discussed in connection with the fine structure. The cold-compacted films show a broad α-relaxation at a lower temperature than do single-crystal mats or melt-crystallized polymer. From the effects of annealing and swelling by carbon tetrachloride on the relaxation, it is concluded that the α-relaxation, like the α-relaxation in the single-crystal mats, originates from molecular motions within lamellar crystals. This is consistent with the finding that these films are composed of stacked small irregular lamellar crystals. The γ-relaxation is also similar to that in crystal mats.
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  • 20
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1641-1658 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The drawing behavior of a series of linear polyethylene homopolymers with weight-average molecular weight (M̄w) ranging from 67,800 to ∼3,500,000 and variable distribution (M̄w/M̄n = 5.1-20.9) has been studied. Sheets were prepared by two distinct routes: either by quenching the molten polymer into cold water or by slow cooling below the crystallization temperature (∼120°C) followed by quenching into cold water.When the samples (2 cm long) were drawn in air at 75°C using a crosshead speed of 10 cm/min it was found that for low M̄w polymers the initial thermal treatment has a dramatic effect on the rate at which the local deformation proceeds in the necked region. At high M̄w such effects are negligible. An important result was that comparatively high draw ratios (λ 〉 17) and correspondingly high Young's moduli could be obtained for a polymer with M̄w as high as 312,000. It is shown how some of the structural features of the initial materials (mainly studied by optical microscopy, small-angle x-ray scattering and low-frequency laser Raman spectroscopy) can be interpreted in terms of the molecular weight and molecular weight distribution of the polymers. Although crystallization and morphology can be important at low M̄w, it suggested that the concept of a molecular network which embraces both crystalline and noncrystalline material is more helpful in understanding the drawing behavior over the whole range of molecular weights.
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  • 21
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1693-1700 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Spin-lattice relaxation times (T1) for methyl, methylene, and methine carbons in an amorphous polypropylene have been measured as a function of temperature from 46 to 138°C. The carbons from isotactic sequences characteristically exhibited the longest T1's of those observed. The T1 differences increased with temperature with the largest difference occuring for methine carbons where a 32% difference was observed. Activation energies were determined for the motional processes affecting T1's for isotactic and syndiotactic sequences with essentially no dependence upon configuration noted.
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  • 22
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1903-1907 
    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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  • 23
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1913-1916 
    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 14 (1976), S. 1921-1929 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In evaluating molecular orientation by dynamic infrared techniques, it is shown, subject to certain restrictions, that an extensional mechanism plays an important role in the measured orientation. Dichroic measurements can indicate a change in segmental orientation without any change occurring in the chain axis orientation. Extensional orientation was evaluated for a general helical molecule in terms of singular and coupled vibrational modes. Significant orientation changes can occur by the extensional mechanism, the sign and magnitude of which depend on the components of the transition moment vector.
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  • 25
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1801-1812 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A method is proposed for calculating the activation energy over the entire temperature range from relaxation measurements at two frequencies as a function of temperature by taking into account the entire experimental curve. The method is independent of the distribution of relaxation times, but assumes the validity of the time-temperature superposition principle.
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1871-1875 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The γ and δ relaxations of polystyrene (PS) are rendered more active dielectrically by sorbed oxygen. This effect, coupled with comparative work on molecularly similar systems has led to the assignment of the γ relaxation to a rotational libration of the phenyl ring in PS. Specific interactions of the pendant phenyl ring with molecular oxygen to induce off-axis dipole moments in the phenyl moiety is proposed. It is concluded that this interaction is strong enough to influence the dielectric relaxation strength of other relaxations in PS. It is further concluded that because of the interactions occuring in aromatic polymers containing sorbed oxygen, care must be taken to exclude oxygen or to vary its content, in order that intrinsic motions in the polymer system can be studied.
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1909-1912 
    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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  • 28
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1917-1919 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
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  • 29
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 2105-2108 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Physics
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  • 30
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 2109-2112 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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  • 31
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 2119-2128 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polystyrene networks prepared by anionic polymerization have been characterized by small-angle neutron scattering. Two kinds of systems have been examined:(A) networks with labelled branch points allowing characterization of the spatial distribution of crosslinking points; (B) networks containing a low proportion of chains labelled with perdeuterated polystyrene in order to characterize the conformation of individual elastic chains of the polymeric network. The dependence of the results on swelling and uniaxial extension is discussed.
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  • 32
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 2129-2136 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Relaxation of birefringence and stress in simple extension has been studied for polyisobutylene at -26.0°C and 25.0°C for extension ratios ranging from about 1.2 to 2.0. The dependence of both the stress and birefringence on the extension ratio, for a given time, is well described by equations of the Mooney-Rivlin form. The Mooney-Rivlin treatment of the birefringence experiments was found to reinforce but not add to information available from the stress-relaxation experiments alone. At 25.0°C, the stress-optical coefficient is found to be stress dependent. Possible explanations of this behavior are discussed. An experiment is also reported in which the birefringence is observed under zero stress immediately after cutting a strained sample. The zero stress birefringence is believed to be due to regions of stress-induced crystallization taking a finite time to melt after the stress is removed.
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  • 33
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 2195-2209 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The lateral swelling, changes in length and tensile stress-strain curve of reconstituted collagen hollow fibers, crosslinked with uv irradiation, were measured as a function of the pH and ionic strength of their aqueous environment. From pH 5 to pH 10 the lateral swelling and length are constant; at lower and higher pH the lateral swelling increases rapidly while the fiber shrinks in length. Corresponding to these changes, a pronounced toe develops in the stress-strain curve and extends to a higher strain in more acid (or basic) media. This toe is attributed to the straightening of a microcrimp in the collagen fibrils; the microcrimp is accentuated by the repulsion between the charged fibrils in acid or basic media. Direct small-angle x-ray evidence of these microcrimp structure changes at low pH is presented. Increasing the ionic strength of an acid solution by adding NaCl decreases the lateral swelling, increases the length, and decreases the extent of the toe on the stress-strain curve. These changes result from an increased screening of the charge on neighboring fibrils at higher ionic strengths thus decreasing the repulsion between fibrils and the resulting microcrimp. Although the zigzag elastica model of the crimp developed by Diamant et al. [Proc. Roy. Soc., Ser. B, 180, 293 (1972)] provides a good empirical fit to the stress-strain data, it is shown to be inappropriate where the crimp results from repulsive forces between fibrils. A new model taking these forces into account is developed and is shown to be in reasonable agreement with the experimental results.
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  • 34
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 2231-2240 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The mean-square dipole moments of poly(ethylene oxide) and poly(hexamethylene oxide) chains have been determined from dielectric constant measurements on dilute solutions of the polymers in benzene. The values obtained are in good agreement with those predccted using the rotational isomeric state models for these chains. In addition, the unperturbed dimensions of poly(hexamethylene oxide) have been calculated as a function of molecular weight, using the isomeric state theory.
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  • 35
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 2253-2257 
    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 phase transformation are treated for heterogeneous nucleation, where all nuclei are simultaneously initiated, and where initiation follows first-order kinetcs. The phase transformation curves are sigmoid. For simultaneous initiation in two dimensions, a(t)/(1 - a(t)) ∝ t2. For first-order initiation, we have, approximately, a(t)/(1 - a(t)) ∝ t2.85, and v(t)/(1 - v(t)) ∝ t3.74.
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  • 36
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 2241-2251 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Cloud-point curves have been determined for aqueous solutions of poly(ethylene oxide) (PEO) at several concentrations for a variety of inorganic salts (sulfates, carbonates, nitrates, and chlorides). From these, theta conditions have been determined. The resulting dependences of the critical temperature θ (mostly between 300 and 360°K) on the molar concentrations (or ionic strengths) of the salts in solution cannot wholly be summarized in sequences of ion effects. The major findings are that sulfates and carbonates are much more effective in reducing θ than the chlorides and nitrates at the same concentrations. The trends found depend on salt concentration, i.e., certain plots of the data cross over, but they broadly agree with those found for comparable systems by other workers. Exceptional are the chlorides of Group II and LiCl which show minima when θ is plotted against molar salt concentration. While interpretations based on solvent structure-breaking are not adequate, there are similarities in behavior with the structure-breaking attributes of the ions based on independent studies (infrared). The results are briefly discussed in terms of current postulates: a more detailed discussion will accompany further experimental studies on these systems.
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  • 37
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 2273-2284 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Six 6,10-ionenes with different counterions were prepared by ion exchange reactions in aqueous solutions. The counterions were Br, I, CIO4, BF4, SCN, and B(C6H5)4. The dynamic mechanical properties of these polymers were investigated by use of a torsional braid analyser. Three relaxations α (25-140°C), β (-30-0°C), and γ (-140-120°C) were observed at the frequencies of 0.3-0.8 Hz. The temperature of the α and β relaxations were largely dependent on the size of counterions, but those of the γ relaxations had little variation. The effects of electrostatic forces in the polymers on each relaxation was discussed. The influence of absorbed water on the α, β, and γ relaxations was examined. The absorbed water in the polymers greatly depressed the temperature of the α relaxations and this phenomenon was interpreted to be the result of the specific hydration on ionic portions.
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  • 38
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 2291-2311 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Small-angle and wide-angle x-ray scattering measurements, using a position-sensitive detector, were made during melt-crystallization of linear polyethylenes and PEO-PS-PEO triblock copolymer. The scattering measurements indicated that the triblock copolymer grew by the enlargement of regions in which lamellae are regularly stacked. During primary crystallization at higher temperatures similar behavior is observed in two linear polyethylenes. At lower temperatures, changes in the shape of small-angle scattering curves during the primary stage of crystallization indicate that amorphous gaps within the lamellar stacking become filled in. During secondary crystallization at higher temperatures new crystallites appear to grow between those formed in the primary stage. Concurrent decrease of the overall scattered intensity leads to the conclusion that secondary crystallization has two components: crystallization of new lamellae behind the spherulite growth front and the thickening of existing lamellae.
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  • 39
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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.
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    Keywords: Physics ; Polymer and Materials Science
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    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.
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  • 41
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 103-108 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Polystyrenes lightly substituted with either tertiary amine groups or nitrophenol groups have been allowed to interact in concentrated t-butylbenzene solution and in bulk polymer. Above the glass transition temperature a temperature dependent equilibrium is achieved in the bulk polymer between the two substituents and the amine salt of the phenol. The degree of association found is considerably greater in the bulk polymer than in solution. The results show that much interpenetration of the polymer occurs, and the results are discussed in terms of models of the bulk amorphous state of the polymer.
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  • 42
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    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.
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  • 43
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 97-102 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Raman depolarization ratio measurements (ρ) have been made for 20% polydimethylsiloxane (PDMS) solutions in benzene and 10% Polystyrene (PS) solutions in cyclohexane over the temperature range 20 〉 T 〉 200°C. The bands studied were the 2907 cm-1 methyl stretch in PDMS and the 1002 cm-1 ring breathing mode in PS. The measured ρ are related to rotational isomeric state populations and a qualitative picture of the polymer conformation changes over much of their miscible ranges is described. Measurements of ρ for PDMS gum over the temperature ranges 20 〈 T 〈 200°C have been obtained and the upper theta temperature has been determined to be 171 ± 3°C for PDMS/benzene. Quantitative information about the variation of the polymer solvent interaction parameter χ can in principle be obtained.
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 137-144 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Preferential solvation and intrinsic viscosity measurements are reported for three systems: polystyrene + benzene + methanol, polystyrene + carbon tetrachloride + methanol, and poly(2-vinylpyridine) + ethanol + cyclohexane. Plots of the coefficient of preferential solvation λ′ as a function of variation of the segment density Δρ for a given ternary system, give a single curve for a large range of molecular weight and solvent mixture composition. This correlation between λ′ and Δρ is verified in previously published data.
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  • 45
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    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.
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  • 46
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    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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  • 47
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 523-540 
    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 of a study on eutectic solidification of the quasi binary system of unfractionated isotactic polypropylene and the dentritic growing diluent pentacrythrityl tetrabromide. This system was characterized by a eutectic-type experimental phase diagram with a eutectic composition of 68% (w/w) of polypropylene. The eutectic temperature was found to depend on kinetics, and was established by differential scanning calorimetry to be 122 and 102°C at a cooling rate of 0.5 and 32°C/min, respectively. A remarkeable nucleating effect of the primary diluent crystals was observed in the solidification of diluted polypropylene solutions. Here the eutectic horizontal was located at a temperature which was 15°C higher than in the eutectic solutions exceeding the temperature at which the pure polymer crystallized from the melt by 8°C. The eutectic microstructures produced were found to depend on the rate of solidification, which was varied by pulling the polypropylene solutions through a fixed temperature gradient of 3°C/mm at different speeds ranging from 0.2 to 80 mm/hr. At rates lower than 3 mm/hr the polymer and the diluent crystallized simultaneously from the eutectic solution in a uncoupled mode of growth, forming a coarse structure of diluent crystals and isotactic polypropylene spherulites with dimensions of about 0.1 mm. At higher speeds the simultaneous crystallization of the macromolecules and solvent molecules proceeded in a co-operative manner with a nonplanar growth front. A rodlike eutectic microstructure was produced, in which diluent rods, lined up in the growth direction, were dispersed in a polypropylene matrix. The lateral dimension λ1 of these rods were found to depend on the growth rate R in the following way: λ12 R = 10-9 mm3/sec, and ranged from 0.3 to 1.0 μm. This was in accord with values calculated by using the current theory of rod eutectic growth of Jackson and Hunt.
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  • 48
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 605-616 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Molecular motions in a series of linear aliphatic polyesters [poly(ethylene adipate), poly(ethylene sebacate), poly(hexamethylene sebacate), and poly(decamethylene 1,16-hexadecanedicarboxylate)] were studied by dielectric measurements. Two loss maxima were observed for each polymer in the temperature range from -196 to about 60°C and in the frequency range from 110 to 105 Hz. The loss maxima of these polyesters, lying between -17 and -38°C at 110 Hz (β-relaxation), are due to the micro-Brownian motions of amorphous main chains. It was found that these β-relaxations are well described by the WLF equation. The loss maxima in the range from -88 to -109°C at 110 Hz (γ-relaxation), are attributed both to local mode motions of main chains in the amorphous region and to motions of the polar groups involved at the chain ends. For the β-relaxation, no simple relation between the methylene sequence length and the loss peak temperature was found. Furthermore, as the methylene sequence length decreased, the effective dipole moment of the polyesters increased gradually. These facts were explained in terms of interchain dipole attraction.
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 641-656 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Samples of isotactic polypropylene (PP) were zone-solidified in temperature gradients up to 300°C/cm at growth rates down to 3 μm/min. Oriented α-type spherulites were obtained only by nucleation. While β nucleation is extremely rare, the β phase is easily initiated by growth transformations along the oriented α front. Since the β phase was found to grow considerably faster than the α phase, the α-to-β transformation points diverge across the sample, interrupting growth of the oriented α fibrils. This causes subsequent nucleation to yield teardrop-shaped α spherulites.Differential scanning calorimetry (DSC) studies of zone-solidified PP show the β-phase to be favored by slow growth rates, high temperature gradients, and large degrees of superheat in the melt - all of which tend to suppress nucleation. Differential thermograms of largely β-PP obtained at a heating rate of 1°C/min show the actual melting and recrystallization of the β spherulites into the α form.
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 683-692 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A theory has been developed to explain the jump in the relative modulus of filled polymers near the glass transition temperature Tg and the subsequent decrease in relative modulus at temperatures above the glass transition temperature. The theory is based upon the concept that there are some particle-particle contacts in doublets and in agglomerates containing a larger number of particles. Below Tg motion of particles at the contact points is possible because of the high modulus of the polymer. At Tg particle-particle motion mostly ceases because of the low modulus of the polymer. At higher temperatures, the mismatch in the coefficients of expansion allows some motion to occur at points of contact and slippage may occur at the polymer-particle interfaces, so the modulus decreases. It is shown theoretically and experimentally that both the elastic modulus and the mechanical damping depend upon the nature of the surface of the particles.
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 715-722 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A model is proposed for the electrical polarization that causes the orientation and, hence, the electric birefringence of a suspension containing single crystals of a poly(ethylene oxide)-polystyrene diblock copolymer or a poly(ethylene oxide) homopolymer. It serves to describe how an electric dipole moment lying in the plane of the single crystal can be induced by protons migrating in poly-(ethylene oxide). The resulting Kerr effect is calculated up to saturating fields, and the observed dispersion of the polarization in high frequency fields is explained as a space charge relaxation phenomenon. The estimated relaxation time agrees satisfactorily with published experimental data.
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  • 52
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 733-748 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Human transferrin was examined by analytical density gradient equilibrium centrifugation using a short liquid column and employing an iodinated organic gradient salt. Favorable conditions of low pressure and relatively low ionic strength could therefore be obtained. The short liquid column also permitted the layering of extra salt solution above the protein solution in a liquid equalization stage of each experiment. In this stage the amount of preferentially bound water was determined by measurement of solvation arising from the dissolution of the protein which had been added to the centrifuge cell as freeze-dried material. Since schlieren optics were employed, the refractive index of the macromolecular component in the mixed solution had to be known. This quantity was determined from the refractive index difference of the solvent/solution boundary at the liquid equalization stage of each experiment or, alternatively, by regression analysis of the equilibrium data. The new regression method yielded an anhydrous molecular weight of 78,000 daltons which is the same as the value obtained by the classical density gradient equilibrium method performed under the same conditions. Control experiments showed that the analytical ultracentrifuge cell cannot be regarded as a closed, inert system.
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 767-772 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We propose a new method for the investigation of molecular motion in polymeric solids. In a mechanical step-function experiment, we thermally stimulate the response to a constant stress. The high resolving power of this technique permits detailed study of the complex retardation modes observed in polymers. As an example, we consider the thermally stimulated creep of low density polyethylene. The experimental resolution of the thermally stimulated creep spectra shows the existence of elementary processes well fitted by the assumption of single retardation times.
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  • 54
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 795-804 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A simple method of measuring the solubility of gases in polymers at elevated temperatures and high gas pressures is described by direct weighing of the sample after cooling to ambient temperatures. Changes in gas content during cooling which would cause errors are largely prevented by nucleating bubbles throughout the samples immediately prior to cooling, with the effect of making the internal partial pressure of gas equal to the external pressure while the polymer is soft and thus preventing gas flux to or from the sample. Results are given for the solubility of nitrogen in branched polyethylene in the temperature range 130-190°C at gas pressures up to 1,030 bar. A kink in the solubility isotherm at temperatures just above the normal crystalline melting point is believed to be caused by a pressure shift of the melting point. Comparison of the results with previous work by Lundberg et al. suggests a systematic error in the latter which reduced the apparent solubility at higher pressures.
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  • 55
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 837-846 
    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 and the heat of fusion were measured by differential scanning calorimetry (DSC) as a function of draw ratio for linear polyethylene. Both the melting point and the heat of fusion increased with an increase in draw ratio. The plot of the heat of fusion against the melting point was approximately linear. The linear relation is explained theoretically using the assumption that the increases in the melting point and the heat of fusion are due to the orientation of the amorphous phase caused by drawing. The excess free energy of the amorphous phase derived from the orientation increases the melting point, and the amorphous phase absorbs heat for its randomization at the melting point. Hence for drawn samples having an oriented amorphous phase not only the crystal phase but also the amorphous phase contribute to the heat of fusion.
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  • 56
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 907-914 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Although hydrogen gas is about tenfold more soluble in hot-filtered mats of polyethylene (PE) single crystals (SC) than in bulk linear PE, we found that no hydrogen solubility at all could be measured in freeze-dried SC. Despite this, hydrogen gas still exerts a catalytic effect on alkyl radical decay on both the fast and slow first-order decay reactions in the freeze-dried samples. Above 40°C the first-order decay constants of the slowly decaying component decrease with increasing fold period.
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  • 57
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 955-967 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It has been previously shown that when rigid poly(vinyl chloride) is extended by fully necking the test-piece, subsequent fracture takes place by a novel mechanism. Surface crazes grow into “diamond” -shaped cavities which slowly expand while retaining their shape. We have now found that this new mechanism is of general applicability to a wide range of plastics which fracture after yielding. Examples are given from polycarbonate, poly(ether sulfone), and poly(methyl methacrylate) broken at elevated temperatures. The form of the diamond cavity is determined by the continuation of plastic deformation in the whole test-piece while the diamond grows bigger. After fracture a characteristic cavity is left behind on the fracture surface which demarcates the zone of slow growth. At a given point, which is generally easily observable on the fracture surface, the crack speeds up. This change is believed to correspond to a situation where enough elastic energy is available to propagate a crack. It is favored, not only by the increase in size of the diamond in the test-piece but also by an increase in the average energy stored per unit volume of material.
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  • 58
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 987-993 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Thermoluminescence of poly(methyl methacrylate) (PMMA) irradiated with x rays, has been studied in the temperature range 100 to 460°K. Two glow peaks with maxima at 136 and 368°K have been observed. These are analyzed by three methods and the results are compared. Both curves obey second order kinetics and correspond to activation energies of 0.17 and 0.88 eV, respectively. It is possible to identify the centers responsible for the two peaks by correlation with electron spin resonance and optical data obtained for the same samples irradiated under the same conditions. Spectral studies of the emission show that the low temperature peak has its maximum at 365 nm while the high temperature peak has its maximum at 480 nm.
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  • 59
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 1037-1040 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effect of particle size on glass transition temperatures is discussed. The phenomenon is treated in terms of Ehrenfest second-order thermodynamics and in addition related to free volume concepts. Consistent formulas are obtained and the order of magnitude of the effect is estimated.
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 1067-1075 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The differential scanning calorimetry (DSC) melting curves of drawn nylon 6 were studied from the standpoint of reorganization of the crystals during the heating process. A new method was presented to obtain the DSC curve associated with the growth and melting of the original crystals, and that with the recrystallization and final melting process, separately. The results obtained show that, in the case of a heating rate of 10°C/min, the original crystals in the sample start perfecting themselves at temperatures far below their initial melting temperature and melt out below 222°C, recrystallization starts at about 210°C, and the newly emerged crystals melt out at 228°C. The superposition of two such constructed DSC curves reproduces the observed DSC curve well. Therefore, the double melting peaks of the sample are considered to be the result of superposition of three processes which occur successively during heating; perfection of the original crystals, melting of the perfected crystals concurrently with recrystallization, and melting of the recrystallized crystals.
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 1129-1142 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effect of molecular weight heterogeneity on the second virial coefficient A2 in good solvents is studied for binary mixtures of monodisperse poly(α-methylstyrenes). It is concluded that A2 for polymer mixtures passes through a maximum with variation of the mixing ration. From comparison with the data, it is concluded that no available theory quantitatively explains both the molecular weight dependence of A2 of monodisperse polymer and the variation of A2 of mixtures with the mixing ratio. The interpenetration function for two polymer coils with different molecular weights is discussed on the assumption that the thermodynamic interaction between two polymer coils in good solvents can be approximated by a hard-sphere model.
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 1267-1281 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The anisotropy of thermal conduction in a spherulite is calculated for a two-phase model. The problem of the temperature distribution due to cooling of a spherulite suddenly heated at one point is solved. An analytical result is given and isothermal contours are calculated for wide ranges of thermal conduction anisotropy and cooling time. Experiments with spot-heated isotactic polypropylene (i-PP) and isotactic polystyrene (i-PS) spherulites were conducted using a laser pulse and a needle as heat sources. The isotherms were recorded using a thin coating of a heat-sensitive indicator substance, and then by comparison with theoretical isotherm patterns the heat conduction anisotropy of a PP spherulite was estimated. Additional measurements of heat conduction coefficients of at least two polymer films characterized by different crystallinity permit calculation of the thermal conductivity of the amorphous phase, and the conductivities of single crystals along chains and perpendicular to the chains. The results show that the heat is transferred mainly along the primary bonds of polymer chains. However, the morphology of sperulites and lamellas plays an important role.
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 1315-1317 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 1339-1345 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Raman depolarization (ρ) measurements have been made over the temperature range 20 〉 T 〉 60°C for solutions of poly(dimethyl siloxane) (mol wt 7.7 × 104 and 2.0 × 104) for several concentrations up to 100%. The band studied was the highly polarized methyl stretch at 2907 cm-1. Computer calculations of the probability pt of a rotational isomer being trans allow the ρ values to be related to ΔG, the free energy of mixing. ΔG is plotted as a function of concentration and minima are observed at 60 ± 3% (mol wt = 7.7 × 104) and 70 ± 3% (mol wt = 2 × 104).
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 1397-1407 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dielectric constants have been determined for a fraction of poly(diethylene terephthalate) in benzene at several temperatures. The data indicate that the dipole moment ratio 〈μ2〉/Nm2 is somewhat higher than that of poly(ethylene oxide), and its temperature coefficient is in the vicinity of zero. Both the dipole ratio and its temperature coefficient are in very good agreement with those predicted by the rotational isomeric state theory. Using this theory, the unperturbed dimensions of poly(diethylene terephthalate) were calculated and it was found that (〈r2〉/M)∞ = 0.80 Å2 (g mol wt)-1, a value intermediate between those of poly(ethylene oxide) (0.57) and poly(ethylene terephthalate) (1.05).
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 1451-1473 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Monomer distributions and number-average sequence lengths are determined from 13C nuclear magnetic resonance (NMR) data for 1,4- and 1,2-butadiene additions and styrene additions in a series of four hydrogenated butadiene-styrene copolymers. The monomer distribution is expressed in terms of the six unique days from which it is possible to calculate the number-average sequence length of each monomer type. Carbon-13 NMR spectral assignments are given and the techniques for making the assignments are discussed. The method presented could, in principle, be applied to any copolymer or terpolymer. Limitations that are encountered in the analysis of hydrogenated butadiene-styrene copolymers high in 1,2 additions are discussed.
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 1507-1520 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A differential scanning calorimeter (DSC) was used to study the melting behavior of drawn nylon 6 yarns which were prevented from shrinking during heating. The DSC curves exhibit a single melting peak at a higher temperature instead of the double peaks which, as reported previously, were observed in the unconstrained state. The curve is explained quantitatively in terms of the perfecting of the original crystals followed by monotonic melting of these crystals during heating. The single peak results from the absence of the partial melting-recrystallization process which plays an important role in the appearance of double peaks. The temperature of the melting peak for the constrained sample increases linearly with draw ratio, and is unaffected by drawing temperature and by annealing at constant length after drawing. The elevation of the melting temperature is discussed on the basis of the entropy effects predicted theoretically by Zachmann. Thermal analysis of constrained samples has proved to be useful for detecting oriented crystals which coexist with unoriented ones.
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1241-1255 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Fibers were drawn from polymers of octadecyl acrylate, octadecyl methacrylate, N-octadecylacrylamide, and a series of N-substituted acrylamides with a second amide group in the side chain as well as from copolymers of octadecyl and methyl esters of acrylic and methacrylic acid. Wide-angle and small-angle x-ray diffraction patterns were recorded for these materials. The interpretation of the characteristic difference between the behavior of the polycrylates and polymethacrylates, as proposed by Platé and his collaborators, is found to be inconsistent with a number of features of the experimental evidence. In the case of poly(octadecyl methacrylate) the data allow the estimation of two parameters of the electron density distribution in the side-chain crystallites. With polyacrylamide derivatives, a second amide group in the side chain is found to destabilize the side chain crystallites. The bahavior of the copolymers is very complex and exhibits, in one case, evidence for a long periodicity parallel to the fiber axis.
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1287-1295 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Hydrophobic-hydrophilic block copolymers were prepared by “living” anionic polymerization. They consist of polystyrene and poly(ethylene oxide) blocks, and are soluble in water. Their interfacial properties were investigated, employing aqueous solutions. The block copolymers lowered the surface tension of water in analogy with the low molecular weight surfactants such as sodium lauryl sulfate and heptaethylene oxide n-dodecyl ether. Their aqueous solutions exhibited solubilization properties differing from those of polyethylene glycol. Therefore, it is thought that the polystyrene blocks produce solubilization phenomena. In samples of the same styrene content, the precipitation temperature of a high molecular weight copolymer in water was lower than that of a low molecular weight copolymer at the same concentration in the same solvent. The surface tension and precipitation temperature of aqueous solutions seem to be influenced by molecular weight and composition.
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1317-1324 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A weak acid gel (carboxylmethyldextran) was titrated with sodium hydroxide while equilibrated with a solution sodium poly(vinyl sulfate), a salt of a strong acid polyelectrolyte.It was found that the quantity \documentclass{article}\pagestyle{empty}\begin{document}$$ S = {\rm pH} - {\rm pNa} + \log (V/V_0) $$\end{document} in which V/V0 is the volume of gel relative to its volume in acid form in pure water, is independent of the concentration Cp of the polyelectrolyte solution and of the relative volume of gel.The relation \documentclass{article}\pagestyle{empty}\begin{document}$$ S - \log \left({\frac{{\alpha ^2}}{{1 - \alpha}}} \right) = {\rm pK'} + \log \gamma _{{\rm Na}}^{\rm g} + \log (v/V_0) $$\end{document} where α is the degree of ionization, pK′ is the apparent pK of the gel, γnAG is the activity coefficient of the counterion in the gel phase, and v is the number of ionizable groups, is found to be constant for all values of Cp and for 0.1 〈 α 〈 0.9. These results can be extended to highly crosslinked ionexchange resins.
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 1647-1654 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The infrared spectra of polyethylene single crystals suspended in liquid are reported and compared to dried mats of the same material. In order to observe the polyethylene bands, liquids with partial windows in complementary regions of the spectra were chosen. Any remaining bands of the suspending media were removed by substraction of the spectrum of the pure liquid. The crystalline bands of suspended polyethylene are much sharper than those of the dried material, indicating a decrease in lateral crystalline order upon drying. Drying also results in a change in the type and distribution of conformations associated with amorphous and fold structures, as determined by the observed frequencies of the methylene wagging mode.
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    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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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 1757-1767 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: From glass transition Tg measurements on isotactic polystyrene (IPS)-poly(2,6-dimethyl phenylene oxide) (PPO) blends, it was concluded that thoroughly annealed, freeze-dried samples, or samples evaporated from solution at high temperature, are homogeneous. Without annealing, the freeze-dried blends show two to three Tg's characteristic of the presence of different phases. The overall crystallization rate of these samples is much higher than that observed with annealed samples. The presence of dissolved PPO in annealed samples reduces the overall crystallization rate and the spherulitic growth rate, compared to IPS. The melting behavior of the blends is influenced by the extent of mixing of both polymers. Without annealing, isothermally crystallized, freeze-dried blends show the same melting behavior as IPS (i.e., multiple melting). In homogeneous annealed samples the rate of reorganization is strongly reduced and multiple melting only occurs at low scanning rate (e.g., 1°C/min). This behavior is influenced by the crystallization temperature and by the composition of the blends. The addition of PPO has no influence on the relation between melting point and crystallization temperature and the same equilibrium melting point is found by extrapolation.
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 1837-1861 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Energy-deformation characteristics for the primary T, S, and U conformational units of tie molecules were obtained from the analysis of data generated from a constrained minimization algorithm. Energy-deformation profiles (covering the range from compact equilibrium defect structures to the fully extended chain) are reported for the S0 and S1 members of the Sλ family and for the U00 member of the Umn family. Estimates of the energy content V0 and the elastic modulus E were obtained from the computed energy-deformation data in the vicinity of the equilibrium Structure - S0 → {60°, 180°, -60°}, V0S0 = 1.7 kcal/mole, ES0 = 60 kcal/cm3 [250 × 1010 dyn/cm2];S1 → {60°, 180°, 180°, 180°, -60°}: V0S0 = 1.7 kcal/mole, ES1 = 25 kcal/cm3 [100 × 1010 dyn/cm2]; and U00 → {60°, 180°, 60°, 180°, 60°}: V0U00 = 2.7 kcal/mole, EU00 = 80 kcal/cm3 [340 × 1010 dyn/cm2]. Although the elastic modulus of the U00 unit is comparable to the elastic modulus of the fully extended chain, the highenergy content of this unit (V0 = 2.7 Kcal/mole) prohibits a significant population and thereby mitigates an appreciable reinforcing effect from this rigid unit. A model for a surrogate force constant is introduced to generalize the results from this study to any member of the Sλ or Umn family as well as any combination of Sλ and Umn units. This generalization provides a basis for estimating the deformation characteristics of tie molecules comprised of various populations of these primary conformational building blocks.
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 1913-1925 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Ultraviolet and Fourier-transform infrared spectroscopy are used to characterize the chain conformation of 2,6-dimethyl poly(phenylene oxide) (2MPPO) in compatible 2MPPO-polystyrene (PS) blends. Blending with PS increases the intramolecular energy of the 2MPPO. Atactic PS induces a greater distortion from the minimum energy conformation of 2MPPO than isotactic PS. The dispersion interaction between the phenyl ring of PS and the phenylene ring of 2MPPO is found to be quite strong. These large intermolecular forces are thought to supercede the increase in 2MPPO conformational energy and to be responsible for the blend compatibility.
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 1967-1982 
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    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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    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
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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
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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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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 2087-2093 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Interactions of water-soluble AB block copolymers of polystyrene and poly(ethylene oxide) with sodium lauryl sulfate (SLS) in aqueous solution were investigated by high-resolution proton magnetic resonance (NMR). The viscosity in aqueous SLS solution was also measured. From the NMR results in D2O, it appears that molecular motions of the polystyrene blocks of the copolymer in aqueous solution are activated by interaction between the polystyrene blocks and the added SLS. From solution viscosity, on the other hand, it is apparent that a complex is formed between the copolymer and SLS and that it exhibits typical polyelectrolyte properties. The polyelectrolyte character is attributable largely to intrachain repulsions between like charges of the SLS anions adsorbed on the poly(ethylene oxide) blocks of the copolymers since the polystyrene blocks are insoluble in water and the styrene content is less than 10%.
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 2127-2142 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Spin-lattice 1H and 13C nuclear magnetic relaxation (NMR) times T1 have been measured for solutions of polystyrene in hexachlorobutadiene at two different frequencies. Some nuclear Overhauser enhancements and linewidths have also been determined. At 15 and 25 MHz the relaxation times T1 of the ortho and meta carbons show two different dependences on temperature. These measurements indicate internal motion of phenyl groups around the Cα - Cpara axis. A single isotropic correlation time is inadequate to explain the relaxation data for the para carbon. Use of a diamond-lattice motional model reveals that segmental reorientation of the chain backbone of polystyrene can be described in terms of two correlation times, ρ characterizing the three-bond motion process, and θ reflecting either isotropic motions of subchains or departure from an ideal lattice. Data on low-molecular-weight polystyrene indicate the participation of overall rotatory diffusion in the relaxation process. This motion is no longer efficient in high-molecular-weight polymers, where relaxation is due to segmental reorientation.
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  • 82
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    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 2185-2199 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Biaxial and uniaxial tensile stress relaxation tests were made on square sheet specimens of styrene butadiene rubber (SBR), mounted in a universal biaxial tester within a temperature-controlled box, with the object of studying the effect of temperature on the strain energy function. The stress relaxation responses, usually for times up to 10 min, were obtained for various degrees of biaxiality, various extension ratios, and various temperatures within the limits of +25 to -45°C. The results indicated that if the Valanis-Landel representation of the strain energy function \documentclass{article}\pagestyle{empty}\begin{document}$ W = \sum\nolimits_{i = 1}^3 {w\left( {\lambda _i } \right)} $\end{document} is adopted, then time and strain are factorizable over the indicated temperature range, with time and temperature being related in the usual fashion. That is, changing the temperature does not affect the form of w(λi) but only that of G(t/αT), the temperature-dependent relaxation modulus, aT being the regular Williams-Landel-Ferry (WLF) shift factor. The results verify the Valanis-Landel theory for various combinations of biaxiality
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  • 83
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1891-1901 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A nonisothermal creep experiment has been analyzed to ascertain its suitability for determining the temperature dependence of low activation energy viscoelastic processes in elastomers far above Tg. The nonisothermal method was employed to determine the activation energy for creep near 35°C in a lightly crosslinked cis-1,4 polybutadiene elastomer at small strains within the linear viscoelastic region, and at various large deformations up to rupture. The observed activation energy was essentially independent of the level of strain, and the value of ΔHa (∼11 kcal/mole) determined via the nonisothermal creep method was in good agreement with the result (∼12 kcal/mole) obtained via time-temperature superposition of isothermal linear viscoelastic creep data. The nonisothermal data allowed for an estimate of the volume of the “flow unit” associated with the controlling viscoelastic creep mechanism, attributed here to slippage of entanglements within the lightly crosslinked network.
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  • 84
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1877-1890 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dielectric relaxation and Brillouin scattering are jointly used in studying molecular relaxation in poly(propylene oxide) (PPO) and its solutions in methylcyclohexane. The dielectric method was applied to the more concentrated (100%, 80%, 60%, by volume) solutions over a wide temperature and frequency range (30 Hz to 8 GHz) in order that the variation in activation energy characteristic of a glass-forming substance could be delineated. The present work extends previous work on the undiluted polymer to higher frequencies so that range of 12 decades in the dielectric loss maximum fmax as a function of temperature is now available. The “Antoine” equation is found to represent the behavior of log fmax, of the bulk concentrated solutions very well. The more dilute (40%, 20%) solutions were studied only in the high-frequency (GHz) region since phase separation occurred at low temperatures. Both the temperature and dilution effects were interpreted in terms of free-volume theory. Brillouin scattering spectra were obtained at several scattering angles and a wide range of temperatures. A maximum in the curve of hypersonic attenuation versus temperature was observed in each polymer solution. The attenuation maximum shifts toward lower temperature upon dilution, in agreement with the dielectric relaxation result. The Brillouin scattering follows different activation parameters and evidences a more rapid process than does the dielectric relaxation. It is speculated that it monitors a secondary or subglass relaxation, due perhaps, to damped torsional oscillations.
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  • 85
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 165-171 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The preparation of chloroprene-methyl methacrylate copolymers in the presence of Lewis acids (Et1.5AlCl1.5) in hydrocarbon solvent and the effect of Lewis acids concentration on copolymer composition are described. 13C NMR spectra were obtained on these copolymers. In samples of high MMA content, tactic placements of MMA were observed as well as several different kinds of sequences for chloroprene and MMA. In samples of low MMA content, no tactic placements of MMA were found but several different kinds of chloroprene sequences were observed. From the analysis of the 13C NMR spectra of the different copolymers examined, it is apparent that all the various kinds of chloroprene sequences in these copolymers can be determined.
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  • 86
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 187-210 
    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 made of the crosslinking of linear polyethylene in solution. Networks containing a low number of trapped entanglements and elastically ineffective chain ends were prepared by crosslinking high molecular weight linear polyethylene in 1,2,4-trichlorobenzene solutions with dicumyl peroxide at 120°C. No syneresis was observed during crosslinking except at high peroxide concentrations. The networks were characterized by swelling measurements, infrared spectroscopy, and differential scanning calorimetry. The crosslinking efficiency, calculated from swelling, was found to be proportional to the square of the polymer volume fraction. The proportionality constant was 0.8, indicating close to unit efficiency for undiluted polymer.Chemical modification of the polyethylene chains by attachment of peroxide and solvent fragments was of the order of one foreign unit per elastically active network chain, depending on peroxide and polymer concentration. Sol-gel analysis indicated that no chain scission occurred. These results are shown to be consistent with a “cage” mechanism for crosslinking. The possible topological consequence of this mechanism, preferential crosslinking of entanglements, is discussed. The concentration of trapped entanglements was also found to be proportional to the square of the polymer volume fraction. The proportionality constant corresponds to a molecular weight between entanglements of 4000 for the undiluted polymer, which is close to the value of 4200 found for networks prepared from the undiluted polymer. Since the results obtained are based mainly on the use of the swelling equation, different aspects of the applicability of this equation for the evaluation of the crosslinking process are discussed. As regards the reference dimensions, which should be known for a quantitative application of the elastic theory, the results strongly support the use of the dimensions of the network chains after completion of crosslinking.
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  • 87
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 251-262 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Isolated spherulites of poly(methyl D-glutamate) (PMDG) were nucleated in bromoform. The morphology of these spherulites was investigated by SEM and photographic small-angle light scattering (SALS). From the SALS patterns, the development and growth of the spherulites could be noted. Films of PMDG cast from bromoform solution were found to be partially spherulitic. The mechanical properties of these films, prepared by different procedures, were compared with the general behavior of PMDG films cast from chloroform, the latter of which does not contain spherulitic texture.
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  • 88
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 299-308 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Data are presented to show that two correlations of viscosity-concentration data are useful representations for data over wide ranges of molecular weight and up to at least moderately high concentrations for both good and fair solvents. Low molecular weight polymer solutions (below the critical entanglement molecular weight Mc) generally have higher viscosities than predicted by the correlations.One correlation is ηsp/c[η] versus k′[η], where ηsp is specific viscosity, c is polymer concentration, [η] is intrinsic viscosity, and k′ is the Huggins constant. A standard curve for good solvent systems has been defined up to k′[η]c ≍ 3. It can also be used for fair solvents up to k′[η]c ≍ 1.25· low estimates are obtained at higher values.A simpler and more useful correlation is ηR versus c[η], where ηR is relative viscosity. Fair solvent viscosities can be predicted from the good solvent curve up to c[η] ≍ 3, above which estimates are low. Poor solvent data can also be correlated as ηR versus c[η] for molecular weights below 1 to 2 × 105.
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  • 89
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 317-322 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: X-ray line broadening measurements were used to determine the apparent “mosaic block” sizes of randomly oriented polyethylene and polyoxymethylene single crystals. Both dried-down and uncollapsed crystals were examined. PE lamellae were grown at 80, 85, and 90°C by isothermal crystallization from a 0.1% solution in xylene. POM crystals were grown at 125°C by self seeding from an 0.05% solution of the polymer in o-dichlorobenzene. A given preparation was split into two parts. One part was dried down in the usual manner, the other was exchanged to paraffin oil and the crystals never permitted to dry down. Previously reported studies used dried-down crystals and gave crystallite sizes of approximately 300 Å. More recently, using electron microscopy, it has been postulated that PE single crystals are free of “mosaic block” over regions of several thousand angstroms. It is evident from this present study that crystallite sizes in uncollapsed lamellae are significantly larger than those observed for the same crystals dried down. In the case of uncollapsed lamellae, one can explain the observed crystallite sizes solely on the basis of chain obliquity rather than by invoking the “mosaic block” model. It has also been determined that there is an upper limit to the crystallite sizes that can be observed in PE and POM crystals using wide-angle x-ray techniques. This limit may account for discrepancies between x-ray and electron diffraction.
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  • 90
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 323-342 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The morphology and thermal behavior of trans-1,4-polybutadiene single crystals prepared from dilute solutions in n-heptane have been investigated by electron microscopy, wide-angle and low-angle x-ray diffraction, and differential scanning calorimetry. The thickness of the single crystals of trans-1,4-PBD is much greater, for the same undercooling, than that of other linear polymers. From the calorimetric study, convincing evidence of the presence, in the single crystals, of crystalline blocks of form 1 with two different thermodynamic stabilities is obtained and the relative amounts are calculated. From thermodynamic considerations we find a value of 75°C for the equilibrium transition temperature between forms 1 and 2, 139°C for the equilibrium melting temperature of form 2, and 31.2 erg/cm2 for the fold-surface free energy of modification 2.
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  • 91
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 343-352 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Complete and partial alcoholyses of ethylene-vinyl acetate (E-VA) copolymers yield ethylene-vinyl alcohol (E-VOH) copolymers and ethylene-vinyl acetate-vinyl alcohol (E-VA-VOH) terpolymers, respectively. From the 220-MHz proton NMR spectra of E-VOH copolymers the stereoregular and chemical sequence distributions of the comonomers can be readily determined. Partially hydrolyzed E-VA polymers were acetylated with perdeuterated acetic anhydride. The monomer distributions in the terpolymers were then quantitatively determined by examining the proton spectra of the derived products. It was found that alcoholysis of E-VA polymers occurs preferentially at VA units which have neighboring VA groups.
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  • 92
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 353-365 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The small-angle x-ray scattering (SAXS) from quenched and annealed rigid polyvinyl chloride (PVC) has been measured using a Bonse-Hart system. After correcting for absorption, background, and beam divergence, the scattering has been placed on an absolute basis using a standard silica suspension as a reference. The scattering from annealed (6 days at 75°C) and unannealed PVC was identical within experimental error, varying with scattering angle in a manner similar to the SAXS from other amorphous polymers. The intensity decreases rapidly with increasing scattering angle over the ranges from 20 sec to 20 min. Beyond 20 min the intensity is fairly constant, decreasing only slightly with increasing angle. At the largest angles of measurement (in the range of 120 min), the measured intensity is close to the value calculated for thermal density fluctuations frozen-in at the glass transition.The angular variation of intensity is well described by the scattering from heterogeneities of various sizes and concentrations superimposed on the scattering from thermal density fluctuations. These heterogeneities range in radius from 50 to 4500 Å and, assuming the crystalline excess density, the total concentration of heterogeneities is less than 0.5%. The mean-square fluctuation in density, determined from the measured intensity invariant, is also consistent with such a distribution of heterogeneities.The present SAXS results on rigid PVC are inconsistent with the presence of nodular features as representative of the bulk polymer. Rather, it is suggested that they are associated with surface effects. It is further suggested that previously indicated volume fractions of crystallinity in rigid PVC (generally in the range of 5-12%) are incorrect, and that the model of a three-dimensional network of crystallites used to explain the rheological behavior of this material should be re-examined.
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  • 93
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 427-435 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The crystal structure of poly(m-phenyulene isophthalamide) was determined by x-ray analysis. The triclinic cell, with a = 5.27 Å, b = 5.25 Å, c (fiber axis) = 11.3 Å, α = 111.5°, β = 111.4° and γ = 88.0° and space group P1, contains one monomeric unit. The crystal density is 1.47 g/cc. The molecules in the crystal are contracted by 1 Å per monomeric unit from the fully extended conformation, and the planes of the benzene rings and adjacent amide groups make angles of about 30°. The crystal is composed of molecular chains connected by N—H···O hydrogen bonds along the a and b axes forming a “jungle gym” network structure. The low tensile modulus of this polymer as compared with that of poly(p-phenylene terephthalamide) is attributed to the contracted molecular conformation.
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  • 94
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 521-529 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Raman spectroscopy has been used to analyze the characteristics of the crystal-crystal phase transition of trans-1,4-polybutadiene. The low- and high-temperature structures were found to coexist at the transition. The Raman spectra obtained at high temperature can be understood on the basis of the change in chain conformation associated with the phase transition.
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  • 95
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    Keywords: Physics ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Relaxation of stress and birefringence in simple extension has been studied for two samples of 1,2-polybutadiene with 95% and 88% vinyl content and weight-average molecular weight 1.9 and 2.9 × 105, respectively. The extension ratio, λ, ranged from 1.14 to 2.08, temperatures from 0 to 15°C, and times, reduced to 0°C, up to 3 × 105 sec. The stress-optical coefficient C was negative and positive, respectively, for the two samples, the difference being attributable to opposite signs and very different magnitudes of the contributions of the 1,2 and 1,4 moieties to the birefringence. For each polymer, C was independent of time but increased (algebraically) with temperature. For one polymer a very minor dependence of C on λ was observed. At any instant of time, the dependence of both stress and birefringence on λ could be described by equations of the Mooney-Rivlin form with coefficients C1,C2 and B1,B2, respectively. At short times the contributions of the C1 and C2 terms to the stress and of the B1 and B2 terms to the birefringence are roughly equal. With increasing time, C1 and B1 decrease gradually while C2 and B2 remain constant over several decades in time. Finally, C2 and B2 decrease rather rapidly. A tentative interpretation of these phenomena in terms of motions of entanglements is given.
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  • 96
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 759-768 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Experimental data on styrene-acrylonitrile (St-AN), and styrene-methyl methacrylate (St-MMA) copolymers reported in Part I of this series are tested by “two-parameter” theoretical relations. The Fox-Flory (F-F) parameter K is estimated using the F-F, Stockmayer-Fixman (S-F), and Inagaki-Ptitsyn (I-P) equations. In general, the K values obtained by the F-F equation are low for the three St-AN copolymer samples in the systems studied while the values obtained from S-F and I-P equations agree within the limits of experimental error. Values of K obtained from Kurata-Stockmayer (K-S) equation for sample SA1 agree with values obtained by the S-F and I-P equations. The specific solvent effect on the K values is discussed. Values of the unperturbed dimension r̄02/M̄w, calculated from the K values estimated from the S-F equation and from the homopolymer data are compared. Except in one case, the calculated r̄02/M̄w values from homopolymer data are low in comparison with the values obtained from experimental data, which shows that the presence of the repulsive interactions between unlike monomer units brings about an expansion of copolymer molecule. The effect of composition on the steric factor σ values is discussed. The long-range interaction parameter B, the excess interaction parameters ΔBAB, and χAB are calculated. The effects of composition and solvent on these parameters are discussed.
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  • 97
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 821-831 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The possible explanations for the temperature-induced reversible changes in long spacing in polymers are reviewed. The observation of particularly large changes in certain irradiated samples of oriented low-density polyethylene is reported. By combining these results with those obtained by DSC and other means it is concluded that the spacing changes are caused by partial melting of small lamellae within the lamellar stacks which alters the mean periodicity. The requirement of an irregular lattice explains why the effect is observed primarily in bulk samples and especially in materials which contain intrinsic irregularities.
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  • 98
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 861-867 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A technique is described which enabled exceptionally thin sections of rubbery material to be cut for electron microscopy, and applied to samples of polystyrene-polybutadiene-polystyrene (SBS) copolymers which contain the segregated S phase in the form of cylinders arranged in a regular hexagonal macrolattice throughout the macroscopic specimen, with center to center distance of 300 Å. The technique consisted of sectioning the material hardened by a combination of osmic acid treatment and cooling with liquid air. By this method longitudinal sections containing single layer S rods could be obtained as verified by appropriate tilting tests. Such sections enabled the viewing of single cylinders without overlap which in turn enables the study of the structure of individual cylinders and the effect of various treatments on this structure. Examples quoted include the yielding or breaking of individual cylinders on longitudinal deformation of the macroscopic sample relating to our mechanical studies to be reported elsewhere. The technique also enabled sectioning in the swollen state of samples which are not sectionable other wise and this leads to the recognition of new structures and results in an overall improvement of image quality even when the thinness itself is not the prime requirement.
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  • 99
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 879-895 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Metal-insulator-semiconductor (MIS) techniques were used to show that 86-210 nm thick plasma-polymerized tetrafluoroethylene films on silicon stored only negative charge (electron acceptors). This property persisted at a reduced level when a 7 nm thick inner layer of hydrolyzed γ-aminopropyltriethoxysilane was combined with an outer layer of plasma-polymerized tetrafluoroethylene. The dispersion force contribution to the surface energy, γds, for the fluorocarbon films was found to be 6 mJ/m2 (erg/cm2) which is comparable with the lowest values found in the literature. X-ray photoelectron spectroscopy (XPS) revealed a substantial content of —CF3 groups in the fluorocarbon films. This finding coupled with the reported effects of noncrystallinity, crosslinking, and branching on the surface energies of fluorocarbon systems were used to explain the low surface energy and electrophilicity of the plasma-deposited poly(tetrafluoroethylene)s.
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  • 100
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 913-920 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A simple treatment based on continuum mechanics shows that weak interlamellar forces in crystalline n-alkanes should result in a characteristic upward shift of the frequencies of the longitudinal acoustical (LA) modes, which is independent of the chain length and decreases inversely with the mode order. A raman spectroscopic determination of the LA mode frequencies of a series of different n-alkanes confirms the theoretical conclusion and permits a derivation of a force constant characteristic of the interlamellar forces. The discussion results in a new formula valid for the LA mode frequencies of the orthorhombic n-alkanes in the acoustical limit and yields a new determination of the limiting elastic modulus Ec of crystalline polyethylene. The value obtained, Ec = 2.9 × 1012 dyne/cm2, is markedly smaller than the value derived by Schaufele and Shimanouchi neglecting the influence of the interlamellar forces on the LA mode frequencies.
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