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  • Physics  (966)
  • 1980-1984
  • 1970-1974  (966)
  • 1930-1934
  • 1974  (486)
  • 1973  (480)
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  • 1980-1984
  • 1970-1974  (966)
  • 1930-1934
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  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 1005-1011 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We have outlined a theory which considers the durability of adhesive joints in the presence of a hostile environment. The approach is basically the Griffith theory modified for the presence of liquids. Two main conditions for spontaneous delamination of a composite appear to be immiscibility of the liquid in the environment with the members of the composite and complete interaction of the liquid (in a surface-chemical sense) with one or more members of the composite. In the absence of chemisorption and interdiffusion in an A-B composite, we find that (σfL/σf)2 = WABL/WAB, where σf is the critical stress to failure, WAB is the work of adhesion, and the superscript L refers to the presence of a liquid phase. When the liquid (L) interacts, in a surface-chemical sense, with the composite, we have WAB 〉 WABL, and σfL 〈 σf. To illustrate the main features of the theory, composites are prepared whose interfacial tensions have been modified by the presence of an adsorbed monolayer of a fatty acid. In this instance, the interfacial tensions are changed so that WAB ≈ WABL and σfL ≈ σf. The composite then becomes more stable under an applied stress in the presence of an environment of high relative humidity.
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  • 2
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 1023-1045 
    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) patterns of a number of linear polyethylene (PE) and polyoxymethylene (POM) samples have been measured and compared to the intensity functions of one-dimensional paracrystalline lattices. It was found that the ratio of the angular positions of the second and first scattering maxima (θ2/θ1) is generally less than or equal to 2.0, implying that the paracrystalline lattice statistics are symmetric or moderately skewed to larger periods. The Bragg spacing (“long period”) of such samples is within 3% of the identity period of the macrolattice. With quenched POM the ratio θ2/θ1 is substantially larger than 2.0, which indicates either extremely asymmetric lattice statistics or coexisting structures within the material. From consideration of the reduced widths of the first scattering maxima, it was found that some broadening is present in addition to that from the paracrystallinity. This excess broadening could result from a finite lattice length of ∼1000 Å. The need for careful experimental technique for obtaining the actual position of the scattering maximum is emphasized. In addition, it is demonstrated that the scattering curve and the correlation function of the system yield essentially the same apparent structural periods.
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  • 3
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 1111-1116 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The polymerization of p-xylylene was followed with a newly designed differential thermal analysis system at temperatures between -196°C and -20°C. It was found that at the lower temperatures the monomer condenses first to the crystalline monomer before simultaneous polymerization and crystallization. At the higher temperatures, polymerization and crystallization are successive. The data are in agreement with the morphology and crystal structure data derived in Part I of this series of papers on crystallization during polymerization of poly-p-xylylene.
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  • 4
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 1077-1089 
    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 nylon 12 prepared by polymerization of dodecalactam has been determined by x-ray diffraction. Nylon 12 fiber exhibits only the γ form as its stable crystal structure. The unit cell of nylon 12 was determined with the aid of the x-ray diffraction pattern of a doubly oriented specimen. The unit cell is monoclinic with a = 9.38 Å, b = 32.2 Å (fiber axis), c = 4.87 Å and β = 121.5° and contains four repeating monomer units. The chain is planar zigzag for the most part but is twisted at the position of amide groups, forming hydrogen bonds between neighboring parallel chains. The chain conformation is similar to that of the γ form of nylon 6 proposed by Arimoto. It was deduced from the calculations that there are two chain conformations statistically coexistent according to the direction of twisting. In each conformation, hydrogen bonds are formed between parallel chains to make pleated sheetlike structures. The sheets are nearly parallel to (200) and in the sheet the directions of the neighboring chains are antiparallel, as is the case with nylon 6.
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  • 5
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 1091-1109 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Three different polyolefins, a linear polyethylene, an isotactic polypropylene, and an isotactic polybutene-1, were melt-spun into filaments. The degree of orientation of the filaments was measured by polarized-light microscopy, x-ray diffraction, and a retraction technique, and the results were then related to the melt-draw ratio. The increase in the elastic deformation ratio of polymer chains by spin-stretching, estimated by thermal retraction at a temperature above Tm, was monotonic with respect to the melt-draw ratio. On the other hand, as-spun filaments of polyethylene and polypropylene were characterized by a plateau in birefringence over the range of melt-draw ratios from 8 to 80. The change in orientation functions for crystals in these filaments was similar to the change of birefringence. On the other hand, the birefringence and the crystalline orientation functions for polybutene-1 increased smoothly with increasing melt-draw ratio. The most highly melt-drawn filaments of these polymers had a strongly oriented structure, corresponding to that in highly cold-drawn specimens.
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  • 6
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 1117-1138 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An attempt to interpret the prominent dielectric relaxations of poly(γ-benzyl L-glutamate) and poly(γ-methyl L-glutamate) in terms of their structures was made by applying the barrier theory of Hoffman. Potential energy maps for the rotation of the polar side group, which are required in this application, were calculated by taking account of molecular environment of the polar side group. The dichroic ratios from infrared measurements were satisfactorily calculated, based on the maps. This provides evidence that the maps are reliable. In applying the barrier theory, it was modified by the assumption that the conformations of the side groups are distributed according to the Boltzmann law. On the basis of the maps, the magnitude of the dielectric absorption and the mean relaxation time were calculated in terms of the modified barrier theory; these were in fairly good agreement with the experimental data.
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  • 7
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 1235-1245 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Creep failure in oriented nylon 6 fibers has been studied. The results suggest that the variations in the lifetime under various loading histories are inherent, but statistical, characteristics of the material itself. The treatment of experimental data by a stochastic theory shows that the creep failure can be regarded as a nucleation process. An interpretative analysis of the structural changes during creep indicates that the nucleation is brought about by bond rupture in the amorphous regions of the fiber structures.
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  • 8
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 1263-1269 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Shape changes in the electron spin resonance spectrum of spin-labeled polystyrene have been studied as a function of temperature in the range 77-340°K. Rotational correlation times have been calculated by using recent theories of slow-motional effects on ESR spectra. Three models were used, namely, Brownian, moderate jump diffusion, and large jump diffusion. The moderate jump model gave correlation times in good accord with those found by other techniques for the δ relaxation in polystyrene. The relaxation was found to be independent of molecular weight.
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  • 9
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 1489-1502 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effect on water on mechanical properties of collagen films has been studied. The S-shaped sorption isotherm is separated into an adsorption curve C1 and a solution curve C2. From the C2 curve, a value of 0.8 is calculated for the Flory-Huggins interaction parameter χ1. The dynamic shear modulus G′, loss modulus G″, and loss tangent tan δ determined as functions of water content indicate two dispersions at low and at high water content. The region of water content from about 0.05 to 0.1 g/g, G′ decreases suddenly, G″ has a peak, and tan δ increases, corresponds to the region where the C2 component of sorption becomes detectable. Another dispersion occurs at water contents above 0.2 g/g. A composite curve can be obtained by shifting stress-relaxation curves obtained at different humidities along the log time axis. When only the C2 component of sorbed water is taken into account, the shift factor ac is explained by a relation of Fujita and Kishimotos' based on free-volume theory. Shift factor for the relaxation curves of wool fibers, except for an initial part at times of less than 1 sec, are described by the same equation. The parameter β in the equation has the same value of 0.16 for both collagen and wool.
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  • 10
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 1555-1572 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Sorption, diffusion, swelling, and tensile stress relaxation measurements were made at room temperature (23°C) for the systems poly(n-butyl methacrylate) (PBMA) with liquid methanol and ethanol, and poly(methyl acrylate) (PMA) with liquid water. Stress relaxation curves for the fully swollen polymers could be superimposed approximately with those for the dry polymers by appropriate shifting along the long axes. For PMA-water the measured curve for stress relaxation with concurrent sorption could be predicted accurately by using a moving boundary theory with data measurements of stress relaxation of the unswollen and swollen polymer combined with sorption data. The modified moving boundary theory is generalized to include the effects of dimension changes through swelling and the larger effects of plasticization associated with sorption of liquids. This improved theory accurately predicts measured curves of stress relaxation with concurrent sorption for the PBMA-alcohol systems from individual stress relaxation, sorption, diffusion and swelling data. The general approach should be applicable to other amorphous polymer-liquid swelling agent systems. The anisotropic nature of swelling of polymer films and its effect on calculated diffusion coefficients are discussed briefly.
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  • 11
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 1817-1828 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The heat capacity of polyhexene-1 was measured between 20 and 300°K. The apparatus, an adiabatic calorimeter giving results with a random error of 0.2-0.4%, is briefly described. The characterization of the sample by x-ray diffraction patterns established that it was amorphous at all temperatures. Gold foil was incorporated with the sample to increase the apparent thermal diffusivity and so to decrease the time needed for the measurements. The glass transition temperature was found to be 215.5 ± 1°K. On the Cp curve, no subglass anomaly was detected, unlike the results of experiments described elsewhere. The calculation of Cv is discussed, and an explanation is given for the choice of the number of intramolecular vibrational modes per monomer which are assumed to contribute to Cv. A linear continuum model with characteristic temperature θ1 = 736°K allows us to fit the experimental curve over a temperature range of 140°K.
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  • 12
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 1849-1854 
    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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  • 13
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 1863-1864 
    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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  • 14
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 1949-1961 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Cast samples of a phenol-formaldehyde polymer with a crack of length defined by a metallic foil inclusion were fractured in tension. The stress at fracture was inversely proportional to the square root of the crack length, in agreement with the Griffith equation for brittle fracture. The behavior did not conform to the Griffith equation with respect to the experimental value of surface free energy, which was several orders of magnitude higher than a theoretically calculated value. However, as the temperature of tensile testing was raised, the experimental value did approach the calculated value. Consistently the appearance of the fracture surface was observed to change from one showing evidence of plastic deformation at room temperature to a featureless appearance, characteristic of brittle fracture, at higher temperatures.
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  • 15
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 2013-2026 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: By the differential operator representation of constitutive equations for linearly viscoelastic materials, general theoretical expressions are developed for the physical parameters of a composite system in relation to those of the constituents. The interfacial tension between the dispersed phase and continuous matrix is included in the derivation. The results show that it has effect only on the shear parameter but not on the bulk parameter of the composite system. The general expressions developed in this article represent a unified theory for composite systems. The results are shown to reduce to many special cases obtained by other investigators.
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  • 16
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 2039-2055 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The fracture surface of notched impact specimens of polycarbonate tested in the range 130°C to -196°C have been studied by use of optical microscopy and scanning electron microscopy. The morphological features associated with the initiation and propagation of fracture have been determined and interpreted in terms of the processes which occur in association with fracture, notably crazing. The fracture processes are similar to those observed in poly(methyl methacrylate) and polystyrene. The transition from ductile to brittle fracture is attributed to the case of crazing relative to shear yielding.
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  • 17
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 2099-2111 
    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 recently discovered that polymers craze at low temperatures in the presence of nitrogen or argon. A quantitative theory has been developed which explains (1) the critical temperature above which the phenomenon disappears, (2) the critical stress for nucleating a craze, (3) the effect of strain rate on the yield point and size of crazes, (4) the drop in the load during craze yielding, and (5) the increase in strength of the polymer in N2 or Ar at high strain rates so that the ultimate strength may exceed that in He or vacuum. The crazing action of the gases is described qualitatively at the molecular level.
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  • 18
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 2113-2122 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A new crystal modification was found in poly(ethylene oxide) stretched about two-fold after necking at room temperature. An x-ray diffraction analysis indicated that the planar zigzag molecule passes through a triclinic unit cell with parameters α = 4.71 Å, b = 4.44 Å, c (fiber axis) = 7.12 Å, α = 62.8°, β = 93.2°, and γ = 111.4°. The space group is P1-Ci1. Packing of the molecule is very similar to that of monoclinic polyethylene.
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  • 19
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 2173-2184 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Relative tilt between two similar thin crystals may result in the formation of a moiré pattern in the electron image. Patterns hitherto interpreted as being parallel moirés or rotation moiré obtained from overlapping solution-grown polymer crystals are reconsidered, and it is shown that in some cases a tilt model is more acceptable. The general features of tilt moiré patterns predicted for crystals of this kind are discussed and compared with micrographs appearing in the literature. Methods of distinguishing tilt moiré patterns are indicated, though it is admitted that such experiments would be difficult to complete in the time limited by destruction of the crystal structure under the action of the electron beam. Extinction contours may also sometimes be confused with long-period tilt moiré patterns, and again careful experimentation is required for accurate identification. The model of the structure of solution-grown polyethylene crystals inferred from a tilt moiré interpretation of many of the electron image fringe patterns found in the literature is consistent with that derived from other sources.
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  • 20
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 2227-2235 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The thermal emission characteristics of polypyromellitimides have been examined as a function of temperature by measurement of the power required to maintain steady-state temperatures in an evacuated system. The emissivity was derived and found to increase with increasing temperature up to a saturation limit of above 0.9 at temperatures above 475°K. The effect is explained as a thermal population of excited infrared transitions. Power emitted is dominated by the most intense bands which are common to absorption and emission spectra.
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  • 21
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 317-333 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The morphological features of random block copolymers of tetramethyl-p-silphenylene (TMPS) and dimethylsiloxane (DMS) have been studied as a function of copolymer composition. Wide-angle and small-angle x-ray diffraction coupled with several electron diffraction and microscopy studies were used to investigate these materials. The results of this work clearly indicate that the amorphous segments do not enter into the crystalline lattice of the crystallizable component which is varied in content from 90% to 30%. Over the entire range of compositions the block copolymers are crystallizable. Spherulites can be grown from the melt, and single crystals and/or spherulites may be obtained from solution. Single crystals can be obtained over the entire range of compositions provided ample time is allowed for crystallization. The crystalline TMPS component exhibits tetragonal symmetry at all compositions. The amorphous phase manifests itself as a diffuse halo in patterns obtained by electron and x-ray diffraction.
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  • 22
    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 isothermal crystallization from the glassy state at low temperatures and the morphology of poly(ethylene terephthalate) (PET) filled with additives are reported. Talc, kaolin, silicon oxide, and titanium oxide have been used as fillers; they act as effective nucleating agents for PET. The overall rate of crystallization depends on the volume concentration, the size distribution, and the nucleating ability of the additives. An electron microscopic study reveals a transcrystalline morphology at the surface of the filler particles. The occurrence of transcrystallinity is attributed to extensive heterogeneous nucleation induced at the filler surface. From the shape of the crystallization isotherms, it can be concluded that the crystallization mechanism depends on the type of filler.
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  • 23
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 399-406 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The nonlinear integral equations governing phase transition kinetics with homogeneous nucleation and growth site impingement are developed and solved to the first order for the two-dimensional case. It is shown that the fractional transformed area at time t is given approximately by a(t) = Kt3/(1 + Kt3). The iteration method used to get the solution is applicable to certain other nonlinear differential and integral equations. It is shown that the theory predicts the total number of growth sites formed, and that the nucleation rate and growth constants can be deduced from this and the gross kinetic data. The extension of the method of three-dimensional growth is indicated.
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  • 24
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 417-429 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A study of the effect of excluded volume on the mean-square optical anisotropy 〈γ2〉 and the mean-square end-to-end distance 〈R2〉 has been carried out for polymer chains of up to 2000 bonds. The calculations have been made for models assuming (a) equiprobability of internal rotations and (b) interdependence of short-range intramolecular interactions. All the results indicate that 〈γ2〉 is practically insensitive to the excluded-volume effect. Concomitantly the behavior of 〈R2〉 has been analyzed.
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  • 25
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 655-664 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The 100-MHz proton NMR spectra of commercial and laboratory-prepared poly(vinyl chloride) (PVC) have been measured in various solvents at high temperature (80-150°C). Tacticity in PVC was determined by the analysis of the β-proton spectrum. The spectrum was calculated assuming that the PVC chain consists of tetrad sequences of monomer units and that their distribution in the chain is described by a simple Bernoulli-sequence statistics with a Pm (the probability of isotactic placement) of 0.45 for commercial PVC polymerized at 50°C. Tacticity calibration curves based on measurements made for the polymer in pentachloroethane and β-dichlorobenzene were established, and they provide a simple method for the measurement of tacticity in PVC directly from the observed spectra. Excluding samples prepared in butyraldehyde solution, the formation of syndiotactic structures in PVC (prepared by free-radical polymerization) was found to be favored by lowering the polymerization temperature. This preference is due to an increase in the activation enthalpy of 510 cal/mole which is required for forming an isotactic placement in the chain during the propagation step.
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  • 26
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 695-702 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Band assignments of phase-I PVF2 have been Revised by using additional data obtained by laser Raman spectra of oriented samples. A set of least-squares refined force constants was obtained which reproduce the experimental data to an average error in frequencies of 1.3 cm-1. In order to determine the effect of electrical polarization on the spectra, a Gaussian distribution of the dipole axis was assumed. The calculation shows that polarizations of less than 60% will not significantly affect the Raman spectra.
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  • 27
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 713-733 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Brillouin scattering of laser light has been used to study the temperature dependence of phonon velocity in a variety of amorphous polymeric systems, particularly internally and externally plasticized methacrylates. Discontinuities in the temperature coefficient of the hypersound velocities are observed at the glass transition temperatures (Tg). This phenomenon is related to changes in the temperature behavior of the specific volume accompanied by corresponding discontinuities in certain second-order thermodynamic quantities. This method was also used to examine the temperature dependence of the Landau-Placzek ratio.This ratio is relatively large in polymer systems and appears to be independent of temperature in the region of the glass transition, provided that there are no internal strains in the sample at the temperature of measurement. Evidence is presented which suggests that the abrupt changes in this ratio at Tg reported by earlier workers were due to kinetic effects related to the relaxation of internal strains above Tg, and the results of recent studies by other investigators, both corroborating and supplementing the present work, are reviewed.
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  • 28
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 785-793 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Analysis of the solution fractionation of ethylene-propylene copolymers was carried out by assuming a bivariate normal distribution function for the distribution of molecular weight and chemical composition. It was found that the variation of the molecular weight and composition distributions in fractions was complicated, because two distribution characteristics of the original copolymer affect fractionation to differing extents. The hypothetical cumulative weight distribution curves thus obtained agreed essentially with those obtained experimentally.
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 815-818 
    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 12 (1974), S. 871-890 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A series of polystyrenes with weight-average molecular weight M̄w up to 1.3 × 107 was prepared by anionic polymerization in tetrahydrofuran (THF). Each sample was characterized by gel-permeation chromatography, light scattering, and viscometry. It was found that each sample had an almost symmetrical and very narrow molecular weight distribution (M̄w/M̄n 〈 1.07). The mean-square unperturbed radius of gyration 〈S2〉0 was determined in trans-decalin at 20.4°C as 〈S2〉0 = 7.86 × 10-18M̄w (cm2). The particle scattering factor was well represented by the Debye equation irrespective of solvent in the range of M̄w 〈 4 × 106, and only a small deviation was observed in benzene at higher molecular weights. The penetration function Ψ ≡ A2M2/4π3/2NA〈S〉23/2 was found to approach a relatively low asymptotic value of 0.21-0.23 at molecular weights above 2 × 106 in benzene at 30°C, where A2 is the second virial coefficient and NA is Avogrado's number. It was also found that the theta temperature in trans-decalin was affected by the nature of polymer samples. A difference of about 3°C in the theta temperature was observed between two series of anionic polystyrenes, one prepared in THF and the other in benzene, but there was practically no difference in unperturbed chain dimension.
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  • 31
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 1015-1022 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A diffraction contrast study with the aid of an image intensifier was undertaken to obtain direct evidence for the existence of a mosaic block structure in polyethylene single crystals grown by self seeding under isothermal conditions. Dark-field microscopy indicates that the crystals do not contain a mosaic block structure. High-resolution electron diffraction confirms that the crystal is coherent (i.e., mosaic block-free) over regions of several thousands of Angstroms. It is concluded that a mosaic structure on the scale of ∼300 Å does not exist in polyethylene single crystals grown under carefully controlled conditions from dilute solutions. Possible reasons for previous results that indicate the presence of a ∼300 Å mosaic block structure are discussed.
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 1035-1052 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dynamic viscosity of aqueous solutions of poly(acrylic acid) at a polymer concentration of ca. 0.15 g/100 ml has been measured at frequencies from 2 to 500 kHz as a function of degree of polymerization P, degree of neutralization α, and salt (NaCl) concentration Cs. Relaxation spectra have been obtained from the dynamic viscosity. The spectra in the short relaxation time region can be approximated by the Zimm theory for the conformational relaxation of nonionic polymers. The maximum relaxation time τ1 of the Zimm spectra is proportional to P2 and depends rather moderately on α and Cs. Increased deviation is found, however, in the long relaxation time region, in particular for high values of P and α and low values of Cs. The major part of the deviation is interpreted in terms of rotational relaxation of a molecule as a whole. The rotational relaxation time τR is proportional to P3 and increases with increasing α and decreasing Cs. The remaining part of the excess spectra located between τ1 and τR is ascribed to the deviation of the conformational relaxation from the Zimm theory arising from ionization of the polymer.
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 1117-1126 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Single crystals of cellulose triacetate II (CTA II) free of crystallization solvent can be grown from dilute solution in mixtures of dibenzyl ether and n-tetradecane. Good results are obtained by using a polymer fraction with a degree of polymerization of 60 and a mixture of 70% n-tetradecane and 30% dibenzyl ether at 245°C. The lamellar crystals produced are lozenge-shaped with the longer diagonal parallel to the a axis of the lattice and with {110} as the growth faces. Twin growth occurs frequently with {110} as a twinning plane and less frequently with {210}.
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  • 34
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 1109-1115 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Thermoluminescence of polycarbonate irradiated by electron beams was observed in order to investigate the trapping of electrons and the luminescence mechanism. The thermoluminescence glow curve is composed of three components. The peaks appear at -150°C (α peak), -120°C (β peak), and -30°C (γ peak). The α peak is attributed to recombination of cations with electrons released from trapping sites formed by carbonate groups. The β peak is attributed to small amounts of impurities. The γ peak is perhaps due to untrapping of electrons from the phenoxy anion. The luminescence intensity of the α peak is linearly dependent on the absorbed dose, and that of the β peak is approximately proportional to the cube of the dose. The appearance of these peaks is presumably closely related to local molecular motions.
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 1163-1175 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Highly polished surfaces of nylon 6, nylon 66, polychlorotrifluoroethylene and polypropylene were etched by aromatic and chlorinated hydrocarbons at temperatures between 25 and 75°C to reveal surface morphology. Comparison with micrographs obtained with microtomed sections shows the absence of etching artifacts which are known to accompany the use of oxidizing etching agents.
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 913-924 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The polymeric hydrogen form of phthalocyanine is found to be more conductive than the metallic derivatives, in contrast to the behavior of the monomers. In addition, the polymers were found to be much more conductive than the corresponding monomers with the resistivity of the polymers ranging from 7 ohm-cm to about 3 × 106 ohm-cm. The polymers were found to have moderately high dielectric constants ranging from 16 to 1300 at room temperature, depending upon the applied pressure. Based on the dependences of the conductivity and permittivity upon the electric field strength, the average molecular length of the conductive paths within the polymer molecule has been estimated to be 100-1000 Å. In view of these estimated lengths, together with the exponential dependence of the permittivity and conductivity upon the pressure and temperature, the dispersion of the dielectric constants in the range of 10-100 KHz, and the chemical architecture of these ribbonlike polymers, the electronic behavior of these polymers is concluded to be consonant with the model of essentially one-dimensional conduction within and along the chains by freed charges. Much as in a number of previously studied highly conjugated polymers, the present polyphthalocyanines are semiconducting and exhibit nomadic polarization, with dielectric constants ranging from 70 to 1300.
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 1001-1013 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The normal coordinate analyses of tetramethylthiuram mono-, di-, and tetrasulfides have been carried out by utilizing vibrational energies obtained from infrared and Raman spectroscopic data reported here. The C=S vibration is demonstrated to be highly coupled and to contribute to frequencies in the 850-1000 cm-1 region, but can be identified based on the strong Raman intensity. The results are useful in interpreting the spectra of these complex vulcanizing agents.
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 1023-1034 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The theory of rubber elasticity relates the elastic modulus of unfilled amorphous rubber to the concentration of elastically effective strands. A theoretical relation between this concentration and the concentrations of potential entanglements, random tetrafunctional crosslinks, and chain ends was proposed recently. In the present work, the new relation was combined with the theory of rubber elasticity and verified experimentally. Polydimethylsiloxane samples were cured by 60Co irradiation and were extensively extracted to determine gel fraction, which was used to calculate concentrations of crosslinking and scission due to irradiation. Equilibrium modulus values determined from creep tests were in excellent agreement with those calculated using the new relation if the average spacing between potential entanglements is 116 (CH3)2SiO units. Thus, in typical commercial silicone rubbers, the contribution to the modulus from trapped entanglements is greater than the direct contribution from crosslinks. The new relation allows the calculation of crosslink concentrations from modulus measurements on other unfilled rubbers once the potential entanglement spacing of the polymer is determined.
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 1053-1080 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Crystallization kinetics for 12 polymers including polyolefins, polyesters, polyurethanes, polysiloxanes was measured by the evolution of heat in a modified Calvet-type calorimeter over wide temperature ranges. The results are analyzed in terms of the Avrami equation and a comparison between calorimetric and dilatometric results is carried out. It is concluded that, although in the majority of cases experimental results do not obey the Avrami equation, for some polymers the agreement is rather good. The Avrami parameter obtained, however, depends on the experimental technique. Possible reasons for this disagreement are discussed. Analysis of the calorimetric crystallization rate in the vicinity of the melting point by using the kinetic theory of crystallization shows that the growth is controlled by surface (two-dimentional) nucleation. Energy parameters for the crystallites were determined and it is shown that the surface energy of the crystallites depends on the molecular structure of the polymer. Temperature dependence of the calorimetric crystallization rate of the polymers for which crystallization rates could be determined above and below the maximum rate are analyzed using a kinetic equation with common approximations for the transport term. The influence of melting conditions on the crystallization rate was studied. The results indicate heterogeneous nucleation in the polymer melt. It is concluded that this may be due both to impurities and to high regularity of macromolecules in the polymer melt.
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 1137-1143 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Monte Carlo simulation has been used to investigate the excluded volume problem for branched polymers. The mean-square optical anisotropy and mean-square end-to-end distance were examined for two models including short-range intramolecular interactions. Molecules of regular-comb and random-comb type were studied. The various effects found are discussed.
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 1255-1258 
    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 12 (1974), S. 1319-1325 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The birefringence of an object is usually obtained from its retardation. For an object of variable refractive index and optic axis orientation, a matrix procedure should be used for relating the retardation to the birefringence. There are many cases in the literature where this correct procedure has not been used. The correct procedure is illustrated for the case of a polymer spherulite.
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 1865-1874 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The relationship between the critical point and the precipitation threshold is examined in the Flory - Huggins approximation with concentration-independent interaction parameter χ. Approximate explicit expressions for the difference between the critical point and the threshold can be derived by series expansion of threshold conditions. In the first-order approximation, the concentration difference depends only on the chainlength averages xw, xz, and xz+1, in the second-order approximation it depends on xw, xz, xz+1, and xz+2, etc. For polymers of low polydispersity, the second-order approximation gives a good estimate of the concentration difference; for instance, for polymers with exponential distribution and xw/xn 〈 1.25, the error is lower than ca. 1%. The approximation is not suitable for polymers with xz+1 ≫ xz (including polymers whose cloud-point curve exhibits a triple point). Irrespective of the polydispersity of the polymer, the threshold as well as the whole cloud-point curve depend only on the weight-average and higher averages, xw, xz, xz+1, …, xz+k, where k → ∞; they are, however, independent of the number average xn.
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 1925-1937 
    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 region of crosslinked polymers prepared from poly(1,2-propylene phthalate fumarate) and styrene was studied using a torsion pendulum. The glass-transition temperature and the modulus in the rubbery region of these polymers were analyzed in terms of the crosslink density. The styrene concentration at which the maximum crosslink density occurs, as estimated from the viscoelastic data, is found to be in agreement with estimates made by other workers using chemical methods.
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 1955-1968 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A general method is described to take into account the multiple scattering effect in a small-angle light scattering from thin polymer films. It is seen that multiple scattering tends to make the scattering envelope more diffuse, reducing the intensity in the high intensity regions and increasing it in the low intensity regions. The method is applied here to a spherulitic system, but it is valid for any other system where the principal scattering is in the forward direction.
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 1969-1977 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Gel permeation chromatographic (GPC) separations have been performed with several commercially available column packing materials. The results have been analyzed in the conventional manner to obtain the ratio of weight average to number-average molecular weight, Mw/Mn, for solutes with narrow molecular weight distribution. Various other parameters proposed to measure the efficiency of GPC columns have been evaluated and compared. It is proposed that the experimentally determined value of Mw/Mn for a series of different molecular weight samples with similar, narrow distribution for a given set of columns is a convenient parameter for comparing column efficiency in GPC. This parameter may be calculated from a single chromatogram unlike resolution, R, resolution index, RI, or specific resolution, RS, which require a pair of chromatograms. Results from the Mw/Mn method are usually in agreement with those from the R, RI, and RS calculations but one exception has been found. The number of theoretical plates calculated from the elution of a small molecule or from the polymer peak bears little relation to efficiencies predicted from the proposed Mw/Mn method or from R, RI, or RS.
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 2019-2034 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Radical formation during tensile deformation of highly oriented poly[p-(2-hydroxyethoxy)benzoic acid] fibers was investigated by electron spin resonance. Stretching of fibers in vacuo and in a stream of nitrogen gas at room temperature generated a large number of radicals which increased rapidly with macroscopic strain, while stretching in air generated only a small number of radicals. The radicals formed in vacuo or in nitrogen decayed rather rapidly after introduction of air. The observed spectrum was apparently a triplet with a line separation of about 7.5 gauss and a small asymmetry. The inspection of the hyperfine structure, line separation, and total width of the spectrum and the comparison between the observed and the calculated spectrum based on a model substance proved that the observed species is a phenoxy type radical generated by rupture of main chains. A small asymmetry of observed spectrum was explained by anisotropy of the g-tensor. The alkyl end-radical generated together with one of the phenoxy type could not be detected, perhaps owing to its high reactivity.
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 2075-2089 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The Daniels-type distribution functions of the end-to-end distance of three-dimensional and two-dimensional wormlike chains are obtained to terms of order t-10, by an operational method with use of a digital computer, where t is the ratio of the total chain contour length to the Kuhn segment length in three-dimensional cases and of the contour length to the persistence length in two-dimensional cases. The convergence of the ring-closure probability and the mean reciprocal distance is examined on the basis of these distribution functions. A similar study of the moment-based distribution functions is also made.
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 1771-1783 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The time - temperature superposition principle is well-established for linear viscoelastic properties of polymer systems. It is generally supposed that the same principle carries over into nonlinear phenomena, such as the relationship between viscosity η and shear rate \documentclass{article}\pagestyle{empty}\begin{document}$ \dot \gamma $\end{document}. Guided by this principle and the forms of various molecular theories, one would expect that η - \documentclass{article}\pagestyle{empty}\begin{document}$ \dot \gamma $\end{document} data on the same polymer at different temperatures would superimpose when plotted as η/η0 versus \documentclass{article}\pagestyle{empty}\begin{document}$ \dot \gamma $\end{document}η0/ρT, η0 being the limiting viscosity at low shear rates, ρ the polymer density, and T the absolute temperature. Data on polystyrene melts, obtained in a plate-cone viscometer, appear systematically to violate this principle in the range 140-190°. Such anomalies are absent in concentrated solutions of polystyrene. The trends are similar to those reported by Plazek in the steady-state compliance of polystyrene melts near Tg, but they appear to persist to higher temperatures than the compliance anomaly.
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 1785-1804 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The conformational character of a random copolymer of ethyl acrylate and acrylic acid (mole ratio 3:1) has been examined by intrinsic viscosity and light scattering in organic and in aqueous media. The unperturbed dimensions of this copolymer in its un-ionized state in an organic theta solvent are 1.3 to 1.4 times those obtained for the fully ionized polymer in an aqueous theta solvent. The data also suggest that a change in conformation from a swollen random coil to a compact random coil occurs in aqueous media as a function of ionic strength. These results are interpreted in terms of the hydrophobic interaction of the ester groups on the chain.An application of the wormlike chain model shows that viscosity data can be used to predict the light scattering results well with in experimental error.
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 1899-1924 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The strain pattern about a spherical glass bead imbedded in a stretched rubber has been calculated and used to predict the birefringence and light scattering. This is compared with experimental measurements of the retardation pattern observed using a polarization microscope and deduced from the low-angle laser Hv light scattering pattern. The agreement with theory is favorable. The light scattering is suggestive of similar origins of light scattering from crystallizing rubbers and from inhomogeneously crosslinked rubbers.
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 2399-2407 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dc conductivity measurements were performed as a function of temperature on unplasticized poly(vinyl chloride) and on PVC plasticized with various amounts of dioctylphthalate. The conductivity curves consist of two or three straight-line segments denoted I, II, and III with increasing of temperature. The intersection of segments I and II occurs at the glass-transition temperature Tg. The slope in region I is independent of the DOP concentration, while the slope in region II decreases slowly with an increase in the amount of DOP. No dependence of the conductivity on the molecular weight was found. From the conductivity curves, activation energies were evaluated below and above Tg. These satisfactorily coincide with those determined by dielectric loss or by electrical transient phenomena. A dc conduction mechanism is proposed based on electronic hopping favored by the micro-Brownian motions responsible for dielectric losses. These motions involve smaller chain lengths below than above Tg. The experimental results are discussed and interpreted in terms of the proposed mechanism.
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    Topics: Chemistry and Pharmacology , Physics
    Notes: The energy level dispersion, along the chain wave vector, of infrared-active methylene rocking modes has been measured as a function of pressure to 40 kbar for a number of polymethylenes. They are crystalline polyethylene and n-paraffins C23H48, C24H50, C28H58, and C29H60. The crystalline factor-group splitting of each chain mode is observed at various pressures, for those polymethylenes which have orthorhombic or monoclinic structures. The effects of crystal structure, intermolecular force field and intramolecular force field on the observed energy levels as well as on the crystalline factor-group splittings are discussed A hydrogen-hydrogen nonbonded repulsion potential has been calculated as a function of interatomic distance rH••H for 2.3 Å 〈 rH••H 〈 3.0 Å from the observed volume dependence of the factor-group splittings of methylene rocking modes. It is shown that the dynamic potential wells along the normal coordinates of the rocking modes are harmonic up to room temperature.
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    Keywords: Physics ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Physics
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 1573-1584 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The molecular weight distribution of polyethylene produced by radiation was calculated according to a kinetic scheme. The calculated molecular weight distribution was compared with the results deduced from gel-permeation chromatography. The observed distribution curve from GPC was broader and showed a lower degree of polymerization than the calculated one. Discrepancies between observed and calculated curves can be explained if the polymer contains nonsteady-state products and if the reaction mechanism includes chain transfer to dead polymer. By this reaction long-chain branching would occur. Several long-chain branches per polymer molecule were indeed found, as inferred from solution properties.
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 1619-1629 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Direct examination of different polymerization catalysts with an electron scanning microscope is made possible by modification of the inlet port. This represents the first time that polymerization catalysts are thus directly observed at high magnification. The procedure differs from the more tedious and restricted examinations usually performed with electron transmission microscopes. Distinct differences between various catalysts are observed depending on their mode of preparation. These differences account for diverse physical properties of polymers produced with these catalysts.
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  • 57
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 201-216 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A series of linear, aliphatic polyamides in which the number of carbon atoms in the repeat unit ranged from three to twenty-four was crystallized from solution. All gave lath-shaped crystallization products (usually aggregated in the form of sheaves) that were unmistakable lamellar. Sedimented mats of the crystals were examined by lowangle and wide-angle x-ray diffraction. Each polyamide had a characteristic layer thickness (fold length) which was determined by the length of the repeat unit and the number of hydrogen bonds in the lamella. The thickness was independent of other variables examined including crystallization conditions. The polyamides studied cover a wide range: they border on polypeptides at the one extreme and approach polyethylene at the other. For all these materials there emerged a unifying pattern which relates chemical structure directly to chain folding.
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  • 58
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 2303-2306 
    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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  • 59
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 2329-2337 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The resolution attainable in gel-permeation chromatography (GPC) was investigated by using columns packed with polystyrene gel particles of about 5 μ diameter and mixtures of two monodisperse poly-α-methylstyrene samples studied previously. The resolution of GPC was found comparable to that of the sedimentation velocity method and slightly better than that of precipitation chromatography. Standard polystyrene samples obtained from Pressure Chemical Co. also were measured with the same columns. It was found that weight-average to number-average molecular weight ratios (M̄w/M̄n) of these samples with molecular weight in the range 97,000-411,000 are smaller than 1.006. For samples with molecular weight of 10,000-51,000 and 498,000-860,000, M̄w/M̄n is larger than 1.006, and the width of molecular weight distributions of these samples differed. In particular, molecular weight distributions of samples with molecular weights 19,800 and 51,000 were shown to be bimodal. It is therefore concluded that GPC is useful for samples of very narrow molecular weight distribution if high-resolution columns are used.
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  • 60
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 2357-2369 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Bulk-crystallized high-density polyethylene is subjected to cyclic tensile stress and then irradiated by γ-rays to “spin-label” polymer molecules. The change of crystalline texture in the fatigue process before initiation of necking is detected by the ESR method. The line-resolution parameter of the ESR spectrum, which reflects the degree of regularity of molecular arrangement, first decreases, then increases somewhat, and finally becomes almost constant during fatigue cycling. The concentration of radicals trapped in a fatigued sample is larger than that in the unfatigued one. The excess radicals disappear during heating by a process of low activation energy in the temperature region of the mechanical γ dispersion. The degree of crystallinity evaluated from x-ray diffraction and density scarcely changed during fatigue cycling. The size of the mosaic block crystals estimated from the radical trapping capacity showed a rapid decrease at the initial stage of fatigue. The x-ray paracrystalline analysis indicates a similar but not so drastic decrease. These results lead to the conclusion that the slight disordering of crystalline texture accompanying the decomposition of mosaic block crystals in the lamellae occurs at the initial stage of the fatigue process, following which crystals reform somewhat and then remain unchanged until the initiation of necking.
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  • 61
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Solution-crystallized single crystals of various paraffins were investigated at room temperature by nuclear magnetic resonance and by small-angle and wide-angle x-ray scattering. The samples were crystallized from various solvents and annealed 2, 5, 6, and 12°C below the melting point. The NMR spectra are separated into three components (α, β1 and γ) of different chain-segment mobility. On combining these results with x-ray measurements and with results on polyethylene, enough information is obtained to propose a model of the paracrystalline superlattice built up by at least 30 paraffin lamellae and to find where the chains of various conformation are located in the structure. The phase transition of C44H90 in the solid state gives further hints for this allocation. For instance, the β1 component of intermediate mobility increases anomalously from 3% before to 10% after the phase transition. The paracrystalline g value of the macrolattice of the orthorhombic phase is 1.5% and the gap between the lamellae is 2.2 Å. At the beginning of the phase transition, the chains incline stepwise to the lamella surface retaining the orthorhombic macrolattice distance P0 = 58 A and enlarging the gap to 8.8 Å without changing the g value of 1.5%. The growing monoclinic phase, on the other hand, has a constant g value of 3.5% from the beginning with Pm = 52 Å and has gaps of only 3 Å between adjacent lamellae. This explains the large β1 (ca. 10%) of these two new phases, because the mobile chain ends consist of approxiamately 1 CH3 and 1 CH2 group on the average. The γ component of highest micro-Brownian mobility corresponds to the γ component in polyethylene with a line width of ca. 0.07 gauss. Unlike the case of polyethylene it is produced by only a small amount (0.02-0.13) of free CH3 groups per chain. Another fraction of the CH3 groups belongs to the rigid component α of the crystalline phase. They are located where adjacent lamellae touch each other in crystalline-like order. Because of these contacts, stacks of lamellae about 1000 Å thick scatter coherently, and the long period Po of the orthorhombic phase remains undestroyed by annealing until the monoclinic domains collapse to the smaller period Pm of the monoclinic phase.
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  • 62
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 2467-2482 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The Rouse equations for the dissipative motion of long-chain molecules are reformulated in terms of coupled Langevin equations. While in the conventional Rouse model the random forces acting on each bead are supposed to be uncorrelated, the calculation given here admits of any correlation between the forces. By virtue of the second fluctuation dissipation theorem this corresponds to an added friction factor, called the “internal viscosity” in agreement with earlier work of Kuhn and Kuhn, Cerf, and of Peterlin. In the mode decomposition, this added friction factor happens to be an even function of the mode frequency. From this general model it is possible to compute formally the mean-square displacement function. It takes a simple form if one assumes that forces are correlated only on adjacent beads and that their correlation functions are δ functions. The results of the calculation are best displayed in the Fourier transform of the meansquare displacement, which is directly related to the neutron incoherent scattering cross section. It is seen that the presence of internal viscosity modifies the behavior of the chain for a time scale of the order of the relaxation time of the elementary segment.
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  • 63
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 919-927 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The unit cell of an alternating copolymer of ethylene and tetrafluoroethylene was determined by x-ray diffraction. In spite of uncertainties due to irregularities in the chain structure and a low level of crystallinity, a reasonable unit cell and structure was derived which gives a calculated crystalline density of 1.9 g/cm3. The unit cell is believed to be either orthorhombic or monoclinic with the following parameters: a = 9.6 Å, b = 9.25 Å, c = 5.0 Å, (γ = 96°). The molecular conformation is that of the extended zigzag, and the molecular packing appears to be orthorhombic, each molecule having four nearest neighbors with the CH2 groups of one chain adjacent to the CF2 groups of the next.
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  • 64
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 2273-2282 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The relevance of diamagnetic susceptibility as a tool for the structure analysis of solid high polymers is stressed in the light of some new examples. The present results complement previous data and offer new aspects on the diamagnetic investigations of longchain hydrocarbons, especially polyethylene (PE). The molecular susceptibility is proportional to the average number of repeat units in the chain. The proportionality factor defines an intermolecular constant μk which characterizes different physical states. This was found to be 2.5 × 10-6 for the liquid and 3.5 × 10-6 cgs for the crystalline state of paraffins and polyethylene (solution-crystallized). For melt-crystallized material, μk, approaches the typical value of the liquid paraffin in agreement with previous results. Such a low μk is probably related to the increased disorder of the paracrystalline lattice domains, in contrast to the more ordered microparacrystallites in the so-called “single crystals,” where μk = 3.5 × 10-6. In single crystals of branched PE, μk approaches 2.5 × 10-6 with increasing branching ratio. Like paraffins in the gaseous state, molten PE, with chains longer than 1000 Å, has μk = 0. If the solution-crystallized material is molten for 10 min and thereafter cooled, μk retains the original value 3.5 × 10-6 cgs characteristic of the crystalline state. Hence, solution-crystallized polyethylene apparently possesses a kind of “memory.” Such a “memory” can, nevertheless, be partly destroyed when molten PE is stirred for 10 min and then quenched. Aggregates of solution-precipitated crystals with 3% branching concentration give μk = 2.9 ± 0.2 × 10-6 in good agreement with x-ray diffraction data. Finally, experimental details on the magnetic measurements are critically discussed, and various aspects of improvements for further investigations are also described.
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 2297-2301 
    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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  • 66
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 2315-2328 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The depolarization thermocurrent (DTC) method gives the dependence of the dielectric relaxation time on temperature. It has been used for investigations of relaxations obeying an Arrhenius-like law in crystalline polymers. The analysis of this method shows it is possible to study mechanisms described by the Williams-Landel-Ferry (WLF) equation. The critical temperature appearing in the free-volume theory of Cohen and Turnbull and also in the statistical thermodynamic theory of Adam and Gibbs can then be measured with good accuracy. The thermal coefficient of expansion of the free-volume and the WLF coefficient for any reference temperature can also be obtained. Since analysis of the experimental DTC spectrum is particularly simple, this method seems to be a very useful tool for examination of relaxation transitions in amorphous polymers. As an example, results obtained for poly(methyl methacrylate) are presented; they are consistent with published data.
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 2393-2401 
    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 11 (1973), S. 2423-2439 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The extension and fracture under tension of poly(vinyl chloride) strips of different lengths have been studied. It was found that, in spite of decreasing strain rate, long pieces are subject to a type of brittle fracture (necking rupture) occurring immediately after neck formation. This result, which could be expected from previous work, is shown to depend on the elastic energy stored in the longer test pieces. This energy is converted to heat under conditions of neck formation, leading to a temperature rise of 24 ± 4°C, determined by a thermal imaging system. With short test pieces the rise in temperature is much smaller, and a transition to stable neck propagation occurs. Optical and electron micrographs provide additional evidence of heating at the fracture surface. A semiquantitative treatment of the adiabatic process gives upper and lower limits for the predicted temperature change neglecting thermal losses. It is also possible to estimate a minimum length for the initiation of adiabatic deformation. Both calculations give results in reasonable agreement with experiments. Observations with polycarbonate show a similar length effect at low temperatures.
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 2483-2488 
    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 12 (1974), S. 7-21 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The thermoelastic behavior of poly(vinyl alcohol)-poly(acrylic acid) networks was evaluated in pure water and CaCl2 solution. The ratio fe/f of the energy component of the force to the total force, evaluated without taking into account polymer-diluent specific interactions, ranged from -0.75 for networks swollen in pure water to -5.7 in 0.1M CaCl2. However, an analysis based on Flory's theory of polyelectrolyte gels yields fe/f constant at -1.32 when specific interactions are accounted for. In addition, the variation of In (r2)0 with CaCl2 concentration is 2000 times that with water. In neither pure water nor CaCl2 solution can specific interactions be neglected.
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 239-254 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The influence of the solvent-nonsolvent gradient and the temperature gradient on the efficiency of the precipitation chromatography is investigated with radically and anionically prepared polystyrene samples. Only a combination of both gradients gives optimal effectiveness of the column. The separating power of the column was determined by using mixtures of well defined samples. From the elution curves of the mixtures the nonuniformity Ufr of fractions can be estimated. For fractions of anionically prepared polystyrenes Ufr is on the average 0.001; this value is of the same order of magnitude as the statistical error. These results show that with this chromatographic method it is possible to determine the narrow molecular weight distributions of anionically prepared polystyrenes (or other polymers) with an accuracy sufficient for kinetic studies.
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 1189-1193 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetics of the disappearance of propagating butadiene radicals produced in the grafting of butadiene to poly(vinyl chloride) was followed by electron spin resonance measurements. The radical species observed in the temperature range 213-298°K is the conjugated allylic radical: \documentclass{article}\pagestyle{empty}\begin{document}$$ \hbox{---} {\rm CH}_{2}\hbox{---}\rm{CH}\hbox{=\hskip-1pt=}{\rm CH}\hbox{---}{\rm CH}_2 \rightleftharpoons\hbox{---}{\rm CH}_2\hbox{---}{\rm CH}\hbox{---}{\rm CH}\hbox{=\hskip-1pt=}{\rm CH}_2 $$\end{document} The reaction conditions were adjusted to provide a highly viscous medium in which the propagation reaction took place. Under these conditions the radicals were stabilized and a precise ESR spectrum was obtained. Arrhenius plots of the second-order decay rate constants yield an activation energy of 5 kcal/mole. This suggests that the bimolecular termination reaction is controlled by the segmental motion of the grafted side chains.
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  • 73
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), 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: To establish optimum operating conditions for high-speed gel-permeation chromatography (GPC), the effects of column packing particle size, solvent flow rate, and column length on the separation efficiency have been investigated by using monodisperse polystyrene samples and polystyrene gel columns (TSK-GEL column, Type-H). Decreasing the particle size of the column packing reduces the time required to obtain a given resolution. Monodisperse polystyrene standards were measured under the optimum operating conditions established (gel particle size 5 μ, column length 2 ft, flow rate 2.5 ml/min). The molecular weight distribution of a polymer mixture was determined in less than 10 min with the same accuracy as by the conventional GPC. Such short analysis time enables one to use GPC for in-plant quality control.
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  • 74
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 1383-1394 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The tensile stress relaxation of carbon-black-filled SBR was studied in the linear viscoelasticity region as a function of temperature and volume fraction of fillers. Time - temperature superposition was valid, and master relaxation curves were obtained. Carbon black increases the modulus of the compound, especially in the rubbery region, and the time range over which the glass-rubber transition occurred. The shift factor is divided into three regions; an Arrhenius dependence in rubbery and glassy states, and Williams-Landel-Ferry (WLF) dependence in the transition region. The apparent activation energy in the rubbery state increases with the volume fraction of carbon black (or silica) and is unaffected by the structure of the filler. The increase in activation energy is caused by the attachment of rubber chains to the carbon surface. At 30% elongation, the activation energy for carbon-black-filled rubber has a value of 32 kcal/mole, independent of structure and concentration of the filler.
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  • 75
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 929-938 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: By means of an extrusion technique, a uniformly oriented macrolattice based on an alternating sequence of polystyrene and polybutadiene lamellae has been obtained. This is confirmed by the techniques of low-angle x-ray diffraction, electron microscopy, and electron diffraction. Layer thicknesses and spacings have been derived, and good quantitative agreement exists between the values obtained by the different methods. In addition, the electron micrographs exhibit many singular features which are of potential importance both in their own right and for the macroscopic properties.
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  • 76
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    Keywords: Physics ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Physics
    Notes: The Polarized lower-frequency infrared spectra (800-33 cm-1) of nylon 66 (α form), nylon 77 (γ form), and nylon 6 (both α and γ form) have been examined. The spectral changes which occur on complex formation of the polyamides with iodine-potassium iodide solution and on subsequent iodine desorption have been studied in relation to the changes in the polymer structures. On the basis of these results, most of the stronger bands have been reasonably assigned to the vibrations characteristic of the amide group and the methylene chain of the polyamides, and some new structure-frequency correlations have been established for the polymers.
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 1189-1200 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The parameters in the Mark-Houwink relationship, [η] = K′M̄va, for linear polyethylene in 1-chloronaphthalene and 1,2,4-trichlorobenzene at 130°C have been estimated. They were found by measuring the limiting viscosity numbers of a series of fractions with molecular weights ranging from less than 10,000 to almost 700,000. The results are for 1-chloronaphthalene, [η] =0.0555 M̄v0.684 (with a standard error of 0.0064 in K′ and 0.010 in a) and for 1,2,4-trichlorobenzene, [η] = 0.0392M̄v0.725 (with a standard error of 0.00703 in K′ and 0.015 in a), where [η] is expressed in ml/g. The unperturbed end-to-end distance calculated from the viscosity-molecular weight data agrees with the theoretically expected value.
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 1201-1218 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The elastic displacement of an axially stressed chain within crystalline surroundings, which was first treated by Chevychelov, is reexamined. We compare the results obtained for homogeneously distributed masses with that for discrete atoms, considering the nonuniformity of the potential of a crystal containing hydrogen bonds. In polyethylene and polyamide the maximum mechanical excitation of a chain penetrates into the crystal a distance of 15 to 20 chain atoms. The effect of the relative position of the crystal boundary on the stress-strain field was studied and the energy of defects calculated.
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 1219-1233 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A New method for evaluating SAXS curves of polymer samples with lamellar structure is applied to two typical scattering curves measured with a solution-crystallized linear polyethylene and a melt-crystallized branched polyethylene respectively. The method permits a rigorous check of the validity of the two-phase model and yields, without additional measurement, the volume fractions of the two phases and the difference in their densities. The densities can than be obtained by measuring the overall density of the sample. The results are: ρc = 0.996 g/cm3,ρa = 0.854 g/cm3, wa = 0.20 for the solution-crystallized sample; ρc = 0.967 g/cm3,ρa = 0.850 g/cm3, wa = 0.36 for the melt-crystallized sample.
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 1247-1249 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 1347-1355 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dynamic light-scattering experiments were performed on an ethylene-methacrylic acid copolymer and its sodium salt. The in-phase ΔI′ and out-of-phase ΔI″ components of the light scattering were measured in a temperature range between 25 and 65°C for both samples. No transition is seen in this temperature interval for the acid, but a clear transition occurs around 40°C for the salt. This transition is associated with the softening point of the ionic domains present in the sample.
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 1357-1374 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A general equation describing the small-angle Hv light-scattering intensity for a system of N undeformed spherulites located at random within the sample and taking into account the truncation and interference effects is given. Scattering contour plots or radial scans are reported for various arrangements of the N spherulites. The results show that the interference effect may explain the speckled appearance of the experimental patterns. Moreover, the interference and truncation effects (for the special cases where truncation is considered here) do not seem to shift the position of the maximum scattering angle of the cloverleaf pattern as calculated from the single spherulite theory. Finally, the calculations show that the truncation effect increases the relative intensity of the pattern at large and low scattering angles and at azimuthal angles 0 and 90°C, as compared with the intensity at the position of maximum scattering angle.
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 1683-1701 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A general two-dimensional theory is derived to explain the light scattering from truncated spherulites. The severity of the truncation is expressed by a statistical parameter σ2/ā2 which is the ratio of the variance σ2 of the size of the spherulite to the square of its average size ā. The Hv light-scattering patterns are calculated for different values of the truncation parameter. It is observed that the truncation decreases the position of maximum scattering intensity of the pattern. It also increases the scattering intensity at small and large angles, but reduces it at intermediate angles. For a spherulitic polyethylene sample, the truncation parameter is found to equal 0.100 ± 0.030 as measured microscopically. The theory can also be used to calculate light-scattering patterns from row-nucleated spherulites. If it is assumed that the interference effect averages out to zero when a large number of spherulites is involved, a single “sliced” spherulite model can be used. Then, the scattering intensity per unit area decreases as the “slice” becomes very thin.
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  • 84
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 1713-1721 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Various methods of determining polymeric molecular compatibility were applied to blends of poly(vinyl chloride) (PVC) and poly(ethylene-co-vinyl acetate-co-sulfur dioxide) (E/VA/SO2). In one series, where the E/VA/SO2 had a mole composition of 72.7/18.5/8.8, true compatible blends were demonstrated by phase-contrast microscopy, torsion pendulum studies, and differential scanning calorimetry experiments for blends containing up to 40% E/VA/SO2. These blends exhibited a single Tg whose compositional variation was found to follow the Fox expression. Experimental densities were slightly greater than predicted on assuming volume additivity. This observation implies better packing and a negative heat of mixing and thus is in harmony with a negative free energy of mixing and the observed molecular compatibility.
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  • 85
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 1747-1758 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The basis for obtaining the steady-state compliance from stress relaxation upon cessation of steady flow (SRUCSF) data is derived. Measurements on three polymer solutions of differing molecular weight, polydispersity, and degree of entanglement coupling show good agreement between results from SRUCSF and creep-recovery experiments in both linear and nonlinear viscoelastic regions. The stress overshoot phenomenon is interpreted in terms of a change in entanglement spacing upon imposition of a shearing field. The phenomenon is analyzed in terms of a relaxation time for re-entanglement, which is found to be much longer than the relaxation time of the shear stress upon cessation of steady flow.
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  • 86
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 1779-1791 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The morphological character of uniaxially oriented poly(ethylene terephthalate) (PET) films was investigated as a function of draw ratio. Dynamic mechanical, infrared, and crystallite-size measurements were made on the samples. In addition, selective degradation experiments and molecular weight determinations were employed. The dynamic mechanical measurements indicated a sharp decrease in irregular folds for draw ratios of 3.0 and higher, which also coincided with the essentially complete disappearence of regular folds (from the 988 cm-1 band in the infrared spectra) in unannealed samples. Infrared studies of drawn samples annealed under different conditions gave evidence in support of a structure in which the chains are stretched out. Apparent crystallite-size measurements showed a sudden increase in length of the crystals in the direction of the draw beyond a draw ratio of 3.0. Molecular weight measurements showed a large increase in average chain length in the residue after selective degradation of amorphous material and folds; undrawn and slightly drawn samples gave a much lower Mn. Based on these observations, it is postulated that for higher draw ratios and present drawing conditions, the crystals are of the straight chain type, somewhat similar to the fringed-micelle crystal concept.
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  • 87
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 2413-2421 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effects of temperature and pressure on the dielectric relaxation time τ, relaxation strength Δε, distribution of relaxation time β, and shape of absorption curve of the local mode relaxation in polychlorotrifluoroethylene are discussed from the viewpoint of intermolecular interaction. Changes of τ and Δε with temperature and pressure are explainable in terms of changes in intermolecular distance. The temperature and pressure dependences of the dielectric retardation spectrum for the local mode relaxation are different from each other.
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  • 88
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 579-586 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Samples of thin, unplasticized PVC films were fatigued to rupture in nitrogen and ethanol vapor. Examination of the fracture surface edges showed unusual yielding due to the proximity of an unconstrained surface. The scanning electron microscope (SEM) photomicrographs show several indications of supermolecular order in these highly oriented edges and possibly in the relatively unoriented bulk material.
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  • 89
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dynamic mechanical properties of semicrystalline poly(tetramethyl-p-silphenylene siloxane) in three morphological preparations were measured over the wide frequency range of about 0.002 Hz to 500 Hz and the temperature range of about - 190°C to 100°C. The three samples were all isothermally crystallized at 125°C. Two samples had a spherulite size of 25 μ diameter but differed in the time allowed for secondary crystallization. The other sample had a smaller spherulite size. By assuming compliance additivity, the viscoelastic behavior could be separated into five relaxation processes with an indication that a sixth existed at low temperature. Two processes called γ1 and γ2 could be resolved at low temperatures. The γ1 process was associated with the amorphous region since the peak strength was affected by the rate of cooling through the glass transition region; the γ2 peak, unaffected by cooling rate, is attributed to the crystalline part. In the high-temperature region, the β peak is associated with the glass transition and has a shape and location that is essentially independent of the morphology. The highest temperature α2 process, whose maximum was not observed in the experimental range covered, is attributed to the crystalline region and is sensitive to changes in crystallization history. The strength of the α1 process unlike that of the other processes was found to be a function of temperature; it was associated with the noncrystalline region.
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  • 90
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 407-416 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Some dilute solution parameters have been measured for linear amylose tripropionate samples in ethyl acetate and tetrahydrofuran. Mark-Houwink relations for the molecular weight range 104 to 1.5 × 105 have been established, and the exponents are 0.58 and 0.61 in ethyl acetate and tetrahydrofuran, respectively. This indicates that the coil is only slightly expanded in these solvents. A value of 6.21 was calculated for the characteristic ratio C∞ leading to a steric parameter of σ = 2.32. The temperature dependence of the unperturbed dimensions (d In C∞/dT) was found to negative and of the order -4.05 × 10-3°K-1.
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  • 91
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 431-439 
    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 temperature T and weight-average molecular weight M̄w on the rate of spreading of polystyrene melts on plane solid surfaces has been examined. The activation energy E of spreading was estimated to be 25.2 ± 3 kcal/mole, which is of the same magnitude as the activation energy for flow of polystyrene melts. The rate of spreading was found to be inversely proportional to M̄w raised to the 1.5 power. This rate of spreading, measured as the time rate of increase in the liquid-solid contact area, dA/dt, could be expressed as \documentclass{article}\pagestyle{empty}\begin{document}$ dA/dt = Ke^{-E/RT} \bar M_w {}^{-1.5}\gamma _{1{\rm v}} (\cos \theta _{\rm s} - \cos \theta _{\rm d}) $\end{document} where γ1v is the melt surface tension and θd and θs are the dynamic and static contact angles, respectively. The numerical value of K has been calculated to be (6.025 ± 3.693) × 10-14 in the temperature range of 110-260°C and for the values of M̄w from 2000 to 37000.
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  • 92
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 501-513 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Heterogeneous network polymers composed of rigid polypeptide chains and flexible polyether chains were synthesized. That is, poly(L-glutamic acid) (PLGA) was crosslinked with poly(oxyethylene glycol) (PEG) at various carboxy/hydroxyl mole ratios K. The solubility tests and hydrolysis of heterogeneous network polymers suggest that the crosslinking reaction proceeds by esterification. The dynamic mechanical properties of these polymers(100 Hz, -100-200°C) are greatly influenced by the presence of a trace of water and the weight per cent of PLGA. In addition, some of these polymers show only one maximum in the temperature dispersion of dynamic loss modulus E″ and tan δ, although their shape is rather broad. The x-ray photographs of these polymers show an amorphous halo or weak Debye-Sherrer rings. These findings suggest that these polymers are not simple adducts; neverthless PLGA and/or PEG domains exist.
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  • 93
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 555-562 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The rules formulated by Koningsveld for the determination of the critical concentration are shown to be in accord with the Flory-Huggins theory. Sometimes, however, they may not refer to stable conditions, and their application in such cases will result in misleading conclusions.
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 563-578 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Four samples containing 40, 60, 80, and 97 wt-% of poly(vinyl chloride), the rest being plasticizer and stabilizer, were tested by using the Weissenberg Rheogoniometer in the steady-shearing mode at temperatures between 155 and 235°C and rates of shear \documentclass{article}\pagestyle{empty}\begin{document}$ \dot \gamma = 0.01 - 400 $\end{document} sec-1. The viscosity η versus \documentclass{article}\pagestyle{empty}\begin{document}$ \dot \gamma $\end{document} follows Graessley's theoretical dependence for infinitely entangled system. The primary normal-stress difference coefficient ψ versus \documentclass{article}\pagestyle{empty}\begin{document}$ \dot \gamma $\end{document} is well described by the same theoretical function, used with the square of its argument. The temperature dependence of η0 and ψ0 shows discontinuities at T = Tb. The numerical values of Tb can be calculated from the theory of the melting point depression due to diluent. The activation energy of viscous flow Eη below Tb is 5-9 times as large as above this temperature. The activation energy of normal stress is found to be Eψ ≈ 5Eη. The characteristic relaxation times τo, ψp, calculated from superposition of η versus \documentclass{article}\pagestyle{empty}\begin{document}$ \dot \gamma $\end{document} and ψ versus \documentclass{article}\pagestyle{empty}\begin{document}$ \dot \gamma $\end{document} data, respectively, onto Graessley's master curves, and τN, computed from zero shear parameters η0 and ψ0, differ in their sensitivity to the melting of microcrystalline regions. It is postulated that in the systems investigated, aggregates with long lifetimes are being formed, increasing the effective molecular weight and introducing changes in the effective polydispersity.
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  • 95
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 633-633 
    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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  • 96
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 635-643 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Semicrystalline polymers generally exhibit moduli well below their theoretical limit due to chain folding and to lack of crystal alignment. Modulus increases attainable through standard drawing procedures are limited by sample fracture before large draw ratios are reached. Using an Instron capillary rheometer which allowed a draw ratio of 〉 300, transparent polyethylene strands of unusually high c-axis orientation have been produced by a combination of pressure and shear. The virtually perfect crystalline orientation and evidence for extended chains confirm that a significant improvement in modulus can be realized by this technique. The dynamic tensile storage modulus was measured by Vibron over the temperature range -160°C to +120°C. Room-temperature moduli were 7 × 1011 dyne/cm2, higher than any reported values for drawn polyethylene. Values also remained above 1011 dyne/cm2 even at 120°C. The moduli and morphological data have been related by a model consisting of an extended-chain component in paralled with a conventional drawn morphology. Experimental and calculated moduli are compared and related to available theory.
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  • 97
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 665-683 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polystyrene radically polymerized in atmosphere of air is composed of bisegment (C-A) or trisegment (C-A-C) block copolymers consisting of styrene segment (A) and styrene peroxide segment (C). Dielectric measurements of a system of copolymers of styrene and oxygen were obtained above the glass temperature. Three primary relaxations, a, b, and c, in order of descending temperature, were found corresponding to three microphases: styrene phase (phase a), styrene peroxide phase (phase c), and an intermediate phase (phase b) which contains a low concentration of peroxide bonds. An alternating copolymer of styrene and oxygen exhibits the relaxation c alone. With heat treatment above the glass temperature, relaxation c and subsequently relaxation b vanish with thermal degradation of peroxide bonds. The sum of relaxation strengths is linearly related to the content of peroxide bonds which was evaluated by the elementary analysis and DTA. Below the glass temperature, the temperature dependence of dielectric loss of carefully purified polystyrene without peroxide bonds shows very weak peaks which correspond to γ (200°K at 10 kHz) and δ (50°K at 10 kHz) peaks, respectively, in the activation plot. When low molecular degradation products of peroxide bonds are occluded or impurities such as benzaldehyde are added into the specimen, the height of the γ peak is appreciably enhanced, indicating that the reorientation of small polar molecules in polystyrene accompanies the vibration of the phenyl group about the C—C6H5 bond which gives rise to the γ relaxation.
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  • 98
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 1211-1213 
    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 12 (1974), S. 1221-1230 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We feel that the lengthy comments given here come down to a few simple points. For uniform, homogeneous swollen membranes the internal driving force for transport in hydraulic permeation experiments is a concentration gradient not a pressure gradient. Equation (1) is in error because it neglects the frame of reference term 1/(1 - ν1). Equation (19) shows properly the connection between K0 and the various diffusion coefficients. In the particular case discussed here and previously we see no evidence to say that a viscous flow mechanism is operative since we can explain all of the K0 data in terms of reasonable diffusion coefficients if proper consideration is given to the frame of reference correction. This is not to say that in many other cases a viscous flow mechanism will not be present or even predominate.
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 1245-1249 
    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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