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  • Physics  (480)
  • 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.
    Additional Material: 3 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    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.
    Additional Material: 13 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    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.
    Additional Material: 3 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    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.
    Additional Material: 13 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    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.
    Additional Material: 19 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    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.
    Additional Material: 15 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    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.
    Additional Material: 8 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    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.
    Additional Material: 5 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    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.
    Additional Material: 14 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    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.
    Additional Material: 9 Ill.
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  • 11
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    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.
    Additional Material: 6 Ill.
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  • 12
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    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
    Additional Material: 5 Ill.
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  • 13
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    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
    Type of Medium: Electronic Resource
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  • 14
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    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.
    Additional Material: 9 Ill.
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  • 15
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    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
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    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.
    Additional Material: 13 Ill.
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  • 17
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    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.
    Additional Material: 7 Ill.
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  • 18
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    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.
    Additional Material: 7 Ill.
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  • 19
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    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
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    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.
    Additional Material: 7 Ill.
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  • 21
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    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.
    Additional Material: 8 Ill.
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  • 22
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    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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  • 23
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    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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  • 24
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    Electronic Resource
    New York : Wiley-Blackwell
    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
    Additional Material: 2 Ill.
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  • 25
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    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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  • 26
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    New York : Wiley-Blackwell
    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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  • 27
    ISSN: 0098-1273
    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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  • 28
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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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  • 29
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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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  • 30
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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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  • 31
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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
    Additional Material: 4 Ill.
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  • 32
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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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  • 33
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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
    Additional Material: 7 Ill.
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  • 34
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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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  • 35
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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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  • 36
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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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  • 37
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    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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  • 38
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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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  • 39
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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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  • 40
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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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  • 41
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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
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 42
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    Journal of Polymer Science: Polymer Physics Edition 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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  • 43
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 1357-1374 
    ISSN: 0098-1273
    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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  • 44
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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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  • 45
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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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  • 46
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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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  • 47
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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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  • 48
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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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  • 49
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 1385-1411 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The molecular mechanisms involved in the orthorhombic-to-monoclinic phase transformation in polyethylene were investigated by the computer simulation of a structure-energy map based on empirically justified intermolecular potential functions. Stable packing structures for the orthorhombic and monoclinic form were isolated as relative minima, cohesive energies were determined from the energy minima, specific chain motions involved in the transformation were identified by the minimum energy path connecting the packing minima, and the activation energy for the transformation was determined from the energy barrier along the minimum energy transformation path. The packing structure parameters predicted from the energy map were in excellent agreement with unit cell dimensions observed near 0°K. The activation energy predicted for the transformation is relatively low (∼0.5 kcal/mole of ethylene at 0°K and 0.25 kcal/mole of ethylene near the melting point, 411°K). Monoclinic packing was predicted to be slightly more stable than orthorhombic. Since this result is inconsistent with a large body of observations, we propose that the intramolecular energy of chain folds plays a dominant role in establishing chain-packing geometry. The inclusion of fold-transition energetics could give rise to transformation mechanisms which differ in details from those proposed in this work.
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  • 50
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 1413-1421 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Graft distribution functions have been derived from random grafting statistics. Among the functions, the weight fraction of ungrafted backbone chains, the molecular weight distribution of the ungrafted backbone chains and the GPC apparent molecular weight distribution of the graft copolymer have been found to agree with experimental values determined for a graft copolymer system in which grafting was expected to be random. The other functions, which are not directly measurable, are therefore probably also correct. In analytical work the entire set of graft distribution functions may be computed for a graft copolymer system from the following experimental data: (1) molecular weight distribution of the starting backbone chains; (2) the chemical composition of the mixture of the graft copolymer and ungrafted backbone; (3) the graft side-chain molecular weight distribution, which may be assumed to be identical to that of the ungrafted homopolymer separable from the reaction mixture.
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  • 51
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 1423-1434 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We report the first study of the effect of temperature on the elution volume and efficiency of the gel-permeation chromatographic (GPC) process with the use of porous glass column packings. Monodisperse polystyrenes and narrow fractions of polyisobutenes were used as solutes and 1,2,4-trichlorobenzene as the eluting solvent. This study has been made possible by the development of a successful method of eliminating the adsorptive properties of the glass surface with hexamethyldisilazane. Previously, without glass treatment, polystyrene would not elute from this system at 150°C. Previous studies dealing with this topic have been limited to the use of polystyrene gel column with ill-defined temperature-structure behavior. Several measures of polymer dimensions have been correlated with the GPC elution volumes to ascertain which best reduces the data to a common calibration for these linear chains.
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  • 52
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 1435-1440 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Longitudinal and transverse sound velocities have been measured in several samples of polystyrene crosslinked with various weight percentages of divinylbenzene. Specific heats of these same samples have been measured previously. These data obtained calorimetrically, together with similar data obtained by others for some other polymers, can be accounted for by postulating the existence of a fourth mode of vibration with a velocity close to that measured for the two transverse modes. It is suggested that this fourth mode is one arising from the torsional coupling of the side groups along the backbone chain of the polymer molecule.
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  • 53
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 1461-1463 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 54
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 1441-1451 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The specific heat of polystyrenes of different origin and molecular weight, of α-substituted and ortho-substituted polystyrenes, and of polystyrenes crosslinked with different amounts of divinylbenzene have been measured between 1.6 and 4°K. The specific heat of all samples shows a temperature dependence that can not be explained by assuming a Debye frequency spectrum for the vibrational modes in these polymers. Good agreement is obtained by fitting the data to a superposition of a Debye T3 term and an Einstein specific heat with a characteristic temperature of 15-18°K. This localized frequency mode may have its origin in the one-dimensional nature of the polymer chain. A simple calculation of the length of a polystyrene chain necessary to obtain these characteristic temperatures shows reasonable agreement with the number of Einstein oscillators observed in the samples.
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  • 55
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 1503-1533 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Molecular motions in poly(vinylidene fluoride) were studied by dielectric measurements. Of the three relaxation processes, the αa and the αc were studied. The αa relaxation was attributed to the molecular motions in the amorphous regions and the αc relaxation to molecular motions in the crystalline regions and their surfaces. The relaxation time and the magnitude of the αa absorption were analyzed on the basis of the Adam-Gibbs theory of the temperature dependence of the size of the cooperatively rearranging region. As a result it was concluded that the molecular structure of crystal form II holds locally, even in the amorphous regions. The relaxation time and the magnitude for the αc absorption were analysed on the basis of the two-site model. It was concluded that the αc relaxation is attributable not only to molecular motions in the folds of the lamellar crystals, but also to those in the interior of the crystal; the folded chain is relatively mobile, while the molecular chain in the interior of the crystal executes restricted rotation around the chain axis.
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  • 56
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 43-50 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Molecular weights and solution viscosities are reported for unfractionated free-radical polymers of m-fluorostyrene and p-fluorostyrene in several solvents. The estimated unperturbed dimensions lead to characteristic ratios C∞ at 25°C of 12.2 ± 0.5 and 11.6 ± 0.4 for the meta and para polymers, respectively. These are similar in magnitude to those of other polystyrenes.
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  • 57
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 51-64 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Experimental molar cyclization equilibrium constants for dimethylsiloxane cyclics having from 8 to ca 400 skeletal bonds are presented. The results for an undiluted equilibrate, an equilibrate in toluene solution, and an equilibrate in diglyme solution are compared. The increases in the equilibrium concentrations of cyclic oligomers, previously found to be large in good solvents (e.g., toluene) are found to be small in the poor solvent (diglyme). For macrocyclics, the cyclization equilibrium constants in the undiluted equilibrate and in diglyme (theta conditions) are found to be in good agreement with calculations which were carried out by assuming that chains are unperturbed and by using the rotational isomeric state model of Flory, Cresenzi, and Mark for polydimethylsiloxane. However, with chain polymer in dilute solution in a good solvent (toluene), the macrocyclization equilibrium constants are found to be lower than in the other two equilibrates. This result confirms the work of other authors who suggested that in this case the chains were expanded by excluded-volume effects.
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  • 58
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 65-74 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The diglycidyl ether of bisphenol-A, an uncured epoxy resin, has been studied by pulsed NMR. Values of the proton relaxation times T1, T1p, and T2 have been measured over the temperature range from -160 to 200°C. The resin was studied in its monomeric form and in two mixtures containing higher oligomers. The relaxation times are interpreted in terms of the molecular motion in the resins. The motion responsible for relaxation in the solid monomer form is thought to be methyl group reorientation at low temperatures and general molecular motion at high temperatures. The motions are characterized by activation energies of 5 kcal/mole and 33 kcal/mole, respectively. The solid mixtures exhibit similar effects to the monomer, but an additional relaxation mechanism is observed which is attributed to segmental motion. This motion is characterized by an activation energy of 12-15 kcal/mole. The self-diffusion coefficient was measured in the liquid monomer, and the activation energy for self-diffusion is found to be 11 kcal/mole.
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  • 59
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 75-85 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The properties of melt-crystallized poly(tetrachlorobisphenol-A adipate) were studied by using a differential scanning calorimeter. The dependence of melting point and the degree of crystallinity are reported as a function of the crystallization conditions. The heat of fusion is equal to 8.1 kcal/mole, while the equilibrium melting point, as determined by extrapolation, is 283°C. The polymer crystallized from the melt has a maximum degree of crystallinity of 0.53.
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  • 60
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 87-94 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The spherulitic radical growth rate G of poly(tetrachlorobisphenol-A adipate) was studied at different crystallization temperatures as a function of molecular weight using an optical polarizing microscope. By assuming a two-dimensional growth mechanism, with a jump factor G0 depending on the molecular weight, and assuming surface energy terms σu and σe essentially constant, it is possible to correlate the growth-rate data with the model of Hoffman.
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  • 61
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 2209-2225 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The permeation of benzene and acetone vapors through sulfur-cured natural rubber was studied by the time-lag method. The experimental results were analyzed by a method suggested by Meares. The zero concentration diffusion coefficient D0 was obtained by the early-time method. The Frisch time-lag equation was utilized to estimate both the solubility coefficient s and the additional parameter b required to define the concentration dependence of the diffusion coefficient: D(c) = D0 exp {bc}. This form of concentration dependence was manifested by the corresponding permeability coefficient values. At low entering penetrant pressure, where the transport coefficients are constant, indirect evidence was obtained that D0 is the mechanistically correct diffusion coefficient. The solubility coefficient values calculated for benzene vapor in natural rubber are in reasonable agreement with published equilibrium sorption data for a similar rubber compound. At higher entering penetrant pressures, average diffusion coefficients obtained at steady state tended to be larger than the corresponding average diffusion coefficients derived from the time lags. This same effect has been detected by other experimental approaches. Permeation experiments designed for this rapid method of analysis appear capable of yielding information consistent with that obtained by more time-consuming traditional methods.
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  • 62
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 2291-2295 
    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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  • 63
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 275-287 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: As model polymers for isolated short-chain branches in low-density polyethylene, a series of ethylene-1-olefin copolymers was examined by use of 13C NMR at 25.2 MHz. An array of 13C resonances was observed that could be associated independently with methyl through amyl branches. The 13C chemical shifts became insensitive to branch length with hexyl and longer branches. Assignments of the various carbon resonances associated with branching were accomplished by using off-resonance decoupling techniques and the behavior of alkane chemical shifts previously observed by other investigators. The ratio of certain backbone and branch resonances could be used to establish the short-chain branch distribution in a low-density polyethylene.
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  • 64
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 289-296 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The question of viscous flow versus molecular diffusion mechanisms for pressure-induced liquid transport through membranes is critically examined for the specific case of homogeneous swollen membranes. It is shown that previous attempts to compute diffusion coefficients from hydraulic permeabilities for such systems have used an equation which is grossly in error. It estimates diffusion coefficients which are orders of magnitude too high and often exceed self-diffusion coefficients. This has frequently led to the conclusion that viscous flow predominates. The origins of the errors in this equation are indicated, and a substitute equation is developed which gives diffusion coefficients well below that for self-diffusion when applied to literature data. As a result it is concluded that molecular diffusion is the dominant mechanism in homogeneous systems.
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  • 65
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 297-311 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Stress-strain behavior in extension and the swelling of polymer networks with different lenghts of crosslinks is reported. These networks were prepared by copolymerization of butyl acrylate with different amounts of various difunctional comonomers which yield crosslinks of 4, 7, 10, and 16 bonds in length. The efficiency of the comonomers in crosslinking is low, improving with increasing length of the chain between their unsaturated endgroups. Analysis of a large number of stress-strain data obtained at elongations between 2 and 8% elongation showed that in this deformation range the stress-strain relation based on the statistical theory of elasticity represents the data better than does Hooke's law or the Mooney-Rivlin relation. It was found that the relation between the modulus at small deformations and the swelling ratio of the various samples inindependent of the length of the crosslinks. Also the shapes of the Mooney-Rivlin curves are the same for all networks. Furthermore, the creep behavior of various networks with different crosslink lengths is the same for networks compared at the same elastically effective chain concentration. It is concluded that the lenght of the crosslinks, at least up to 16 bonds, does not affect the elastic response of polymer networks.
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  • 66
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 313-329 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Specimens of regenerated cellulose films (cellophane) have been inoculated with cellulolytic fungi and the resulting degradation monitored through change in physical properties. Investigation of structure-property relationship in cellophane have revealed that surface microfibrils are highly oriented parallel to the manufacturing machine direction, while those in the film interior exist in a somewhat disordered array. Cellulase enzymes have been observed to diffuse appreciable distances from their point of application and to attack disordered regions more readily than the crystallites. Damage to surface microfibrils appears to involve their being cleaved into short segments. The fungus studied in this work forms a network of hyphae that covers much of the specimen surface soon after growth starts; hyphae penetrate into the film and proceed to remove its core more rapidly than surface layers. Tensile strength declines progressively as this degradation occurs, but vapor barrier properties remain essentially unchanged over the period of these studies. The suggests that intrusion of hyphae, in combination with enzymatic digestion of cellulose, rapidly lowers load-bearing characteristics, but moisture permeation rates stay nearly constant owing to the presence of fungal material at sites where cellulose has been removed.
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  • 67
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 345-358 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A microstructural model for the phase-separated states of ABA triblock copolymers is proposed. It postulates the simultaneous existence of three phases: pure A, pure B, and a mixed region. Incorporation of the mixed region distinguishes this treatment from all other theories and is responsible for considerable flexibility in the model without increased numbers of parameters. Calculations of free energy changes required to establish specific microstructures permit the prediction of a favored one from among five possibilities: discrete spheres of A (or B), discrete cylinders of A (or B), and lamellae.
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  • 68
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 331-343 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dilute solution properties of fractionated poly(butyl methacrylate-co-styrene) PBMAS prepared by bulk polymerization, have been investigated by means of light scattering, viscometry, and osmometry. As the composition heterogeneity was narrow, the characterization of the copolymer was effected in a single solvent by light scattering. Infrared and nuclear magnetic resonance spectra were used to determine the composition and sequence distribution of monomer units of the copolymer. The molecular weight dependence of the limiting viscosity number and of the root-mean-square end-to-end distance have been established. The Mark-Houwink relation showed that methylethyl ketone is a good solvent compared with cyclohexane. The validity of various extrapolation procedures that have been proposed to calculate the unperturbed dimensions have been examined. Root-mean-square end-to-end distances have been calculated from the Debye-Bueche and Kirkwood-Riseman methods and compared with the experimental values. The molecular weight dependence of the second virial coefficient agreed well with that calculated from the Orofino-Flory equation. The value of the steric hindrance parameter σ for the copolymer has been found to be 2.27 compared to 2.05 for poly(butyl methacrylate) and 2.22 for polystyrene, which indicates that PBMAS is a stiffer chain in solution than those of the constituent homopolymers.
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  • 69
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 737-758 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dielectric dispersions of reconstituted collagens and gelatin were measured from 0.1 to 10 kHz and -160 to +160°C. At 0.1 kHz there is a γ transition at -80°C which is attributed to the H2O-coupled local modes. The process has an activation energy of 7.5 kcal. A devitrification process is observed at 10-20°C. Both of these processes have their counterparts in the dynamic mechanical measurements. The tan δ values are up to 3 times as great for the dynamic mechanical dispersions. There is an additional hightemperature dielectric loss transition which does not correspond to any seen with the mechanical experiments. A probable mechanism for this absorption is the Maxwell-Wagner-Sillars effect.
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  • 70
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 759-768 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The crystallographic unit cells of melt-crystallized 3,3-bischloromethyloxetane and 3,3-bisbromomethyloxetane were determined by the Weissenberg method. The two isomorphous lattices are triclinic with two molecules in the unit cell. 3,3-Bisfluoromethyloxetane forms plastic crystals in the temperature range between -36°C and +22°C, as shown by differential calorimetry and NMR broad-line spectroscopy. The Debye-Scherrer diagram and the general physical properties indicate the formation of a face-centered cubic lattice. No correlation between the lattice parameters of the monomer and polymer can be found On the basis of these results, the question is raised as to whether a topochemical polymerization of bishalomethloxetanes, i.e., a solid-state polymerization without destruction of the crystal lattice, can take place at all. The halomethyl side groups of the oxetanes can be shown to possess different conformations in monomer and polymer crystals, so that a conformational change of the groups and rearrangement of the molecules must take place during polymerization. Therefore, a topochemical mechanism for the solid-state polymerization of bishalomethyloxetanes seems to be impossible.
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  • 71
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 801-805 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 72
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 769-784 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The radiation-induced solid-state polymerization of 3,3-bischloromethyloxetane (BCMO) was investigated by direct observation of the development of the morphology of the growing polymer phase in single crystals of the monomer. Electron microscopy shows that the polymerization gives rise to amorphous polymer in the first step. The polymer forms irregular platelets which aggregate into larger units without reflecting the crystalline order of the monomer. Subsequent to polymerization, the amorphous polymer crystallizes to the β-modification of poly-BCMO. If the partially polymerized crystals are extracted by solvents of the monomer, crystallization of the polymer is enhanced, and morphological artifacts arise which were previously mistaken for the true morphology of the “as polymerized” polymer. The copolymerization behavior of solid solutions of 3-ethyl-3-chloromethyloxetane (ECMO) and BCMO does not differ from the liquid bulk copolymerization with respect to copolymer composition, which is different from the composition of the monomer mixture. It is concluded that the polymer chains grow in noncrystalline zones as in a polymerization in the liquid state by which amorphous polymer is formed. No lattice control was observable in this solid-state polymerization.
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  • 73
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 785-799 
    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 roughness on wettability of skived polytetrafluoroethylene (PTFE or Teflon) and Na-treated PTFE film were studied by advancing contact angle measurements. The effect of an anisotropic force field of elongated Na-treated PTFE on the shear bond strength were also studied as a function of elongation. The results are analyzed in terms of London dispersion γsd and Keesom polar γsp contributions to surface energy γs.It was found that the roughness effect on wettability of PTFE is significant for untreated PTFE and negligible for Na-treated PTFE. Our shear bond strength σb analysis of elongated Na-treated PTFE showed that σb is influenced by an anisotropic force field and the σb increases with the fractional polarity p = γsp/γs but decreases with the dispersion fraction d = γsd/γs of solid-vapor surface tension γs = γsd + γsp
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  • 74
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 807-811 
    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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  • 75
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 813-813 
    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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  • 76
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 815-823 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The thermal behavior of random copolyamides which are used as model polymers with hydrogen bonds has been investigated by differential scanning calorimetry (DSC), x-ray diffraction, and infrared spectroscopy. The quenched copolyamides have only halo patterns in their x-ray diffraction photographs. A random copolymer of nylons 6, 66, and 610 (in a composition ratio of 3: 4: 3) was found to have 20% of unbonded amide groups immediately after quenching. When the sample was kept at the glass transition temperature (20°C), no change in x-ray diffraction was observed after the treatment. The free amide band in the infrared spectrum at 3450 cm-1, however, was decreased in intensity by keeping the sample at the glass transition temperature. The transition peak height observed in a DSC curve also increased in the same experiment. Large glass transition peaks were found in DSC curves after annealing of the random copolyamides in the vicinity of the glass transition temperature. It is probable that the free amide groups in the amorphous chains were rearranged and formed new hydrogen bonds during the heat treatment at the glass transition temperature. Packing and restriction of the amorphous chains due to the increase in hydrogen bonding seemed to increase the height of the transition peak in a DSC curve. It is inferred from the above results that in the case of the random copolyamide, structures corresponding to a given enthalpy of the glassy state can be related to the number of hydrogen bonds.
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  • 77
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 841-854 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The rate of peroxy radical accumulation as a function of strain at various temperatures in AC1220 high molecular weight polyethylene has been determined by EPR spectroscopy. The results of isothermal radical decay experiments are used, where appropriate, to correct the apparent accumulation rate to the actual rate. An exponential dependence of radical concentration [R], on true strain is observed at all temperatures investigated in the range from 160 to 294°K. For constant effective strain, measured from the approximate strain at which radical accumulation initiates, it is found that d[R]/de exhibits two sharp transitions as a function of temperature. One of these, at low temperature, is believed to be associated with the glass transition of the amorphous phase of the material; the other, at higher temperature, is believed to occur as a result of a change in the rate-controlling mechanism of deformation.
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  • 78
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 855-860 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The sensitivity of the light-scattering method for the determination of the composition heterogeneity of copolymers is discussed in terms of the accuracy of measurements of the intensity of scattered light. When the composition is independent of molecular weight, a nomographic solution has advantages. The nomograph is used to investigate the feasibility (a) of the determination of heterogeneity by a single measurement at zero refractive index increment of the copolymer and (b) of the determination of the heterogeneity from two measurements. The results show that in the case of low heterogeneities the light-scattering method can be used only at higher molecular weights. By using the heterogeneities calculated elsewhere, the possibility of determining them for the individual types of copolymers is discussed. It appears that reported discrepancies between measured and calculated heterogeneities are mostly found in cases where the sensitivity of the light-scattering method for the determination of the composition heterogeneity is low.
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  • 79
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 2199-2208 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Lexan polycarbonate specimens in the form of tubes were deformed in torsion. The deformation occurs by the nucleation and growth of discrete shear bands. Shear bands are initially formed at the upper yield point. Development of the bands is accompanied by a drop in the stress to a lower yield point. At the lower yield point the strain inside the bands is approximately 70% and remains constant thereafter. Further deformation occurs by growth of the bands until they cover the entire sample. When the direction of twisting is reversed after the shear bands are formed, the deformed material untwists uniformly, without deformation in the previously undeformed material, and the stress required for untwisting the deformed material is lower than the stress required to propagate the band into undeformed material.
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  • 80
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 2253-2260 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Cloud-point curves and relative volumes of the coexisting phases just below the cloud-point temperatures were observed for a commercial sample of “monodisperse” polystyrene and one of its fractions. As expected from theoretical considerations, the cloud-point curve for the more monodisperse sample was flatter near the peak over a greater concentration range than that of the parent sample. Furthermore, the critical point for the fraction appeared to be closer to the peak of the cloud-point curve than was that of the unfractionated polymer. In addition, it was learned that one type of impurity could be detected with extraordinary sensitivity by means of the cloud-point curve.
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 939-949 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(N-ethyl laurolactam) and poly(N-benzyl laurolactam) were prepared from the corresponding monomers by hydrolyic polymerization. Unlike the partially crystalline poly(N-methyl laurolactam), these two homopolymers were completely amorphous by x-ray diffraction. Diffraction patterns of copolymers of N-ethyl laurolactam or N-benzyl laurolactam with laurolactam were shown to be composition-dependent. For N-ethyl laurolactam copolymers, crystallinity developed with 20% laurolactam as a comonomer and increased steadily with a subsequent change in the x-ray pattern, up to 50% laurolactam. Higher laurolactam percentages resulted in copolymers having a nylon 12 x-ray pattern. N-Benzyl laurolactam copolymers with 30% laurolactam showed only 6% crystallinity. The x-ray patterns of N-benzylated nylon 12 made with more than 50% laurolactam showed patterns similar to that of nylon 12. Differential scanning calorimetry data of all these polymers substantiate the x-ray findings. The effect of type and concentration of the N-substituent on the glass transition, melting, and crystallization temperatures of the polymers is discussed.
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  • 82
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 1013-1021 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Modification of the Griffith theory for the presence of liquids has been shown to explain some facets of the environmental stress cracking of polyethylene. In the absence of intercrystalline links and tie molecules, we find that one important factor is the interfacial tension generated between the spherulite boundary and the liquid environment. Judicious incorporation of silanes into polyethylene appear to reduce the tendency to stress cracking by modifying the interfacial tensions between the environment and the polymer.
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  • 83
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 1047-1054 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The scattering from a two-dimensional spherulite is calculated on the basis of an assembly of anisotropic rods imbedded in an isotropic matrix and arranged in a spherulitic distribution. Provided the dimensions of the rods are small compared with the wavelength of the light, the scattering from such an assembly is shown to be identical with that from an internally uniform spherulite. The effective polarizabilities of this uniform spherulite in the radial and tangential directions are equal to the average polarizabilities in these directions of the constituent rods together with their surroundings.
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  • 84
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The possibility of constructing zero-shear viscosity master curves valid for the entire range of concentration for a large number of polymer solutions in different solvents independent of molecular weight and the nature of the solvent is considered. The results obtained show that the parameters characterizing the individual macromolecular chain., viz., the dimensions of the polymer coil and the rheological effectiveness of segmental interactions, are significant in determining the viscosity of polymer solutions from very dilute to highly concentrated ones. The relation between the parameter of rheological interaction and characteristics of polymer solutions such as the flexibility of the polymer chain and the Flory-Huggins parameter is discussed. This permits one to separate the influence of the energy and entropy factors on the concentration dependence of zero-shear viscosity.
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  • 85
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 1151-1171 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(p-phenylene pyromellitamic acid)s were synthesized over the weight-average molecular weight range 8,000 to 22,000. The polymers were recovered as amorphous powders composed of 3-4 × 1-2 μ platelets 0.1-0.2 μ thick containing 20-30% associated solvent. Consumption of reactants and attainment of the ultimate molecular weight of the polymer were found to occur within the first few minutes of reaction. The polymers were characterized by scanning electron microscopy; ultraviolet, visible, near-infrared, and infrared spectroscopy; x-ray analysis; viscometry; and light-scattering photometry. The intrinsic viscosity-molecular weight relation for the polymer in DMF was \documentclass{article}\pagestyle{empty}\begin{document}$ [\eta ] = 25.2 \times 10^{ - 4} \bar M_w^{0.56} $\end{document}.
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  • 86
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 1139-1150 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The hydrodynamic volume concept can be used effectively with gel-permeation chromatographic (GPC) and viscosity data to estimate the molecular weight of a variety of polymers. Agreement is within ±5-10% of the absolute values and thus is satisfactory for many purposes. An iterative computer technique and a method developed by Funt and Hornof for analyzing GPC-viscosity data were found to be equivalent with respect to estimating the molecular weights for the five cases studied. The latter is easily employed but restricted to the case where the sample of interest and the GPC calibration standards have approximately equal Mark-Houwink parameters. Since GPC measurements are commonly performed in thermodynamically good solvents, the general applicability of the method is not impaired. Using the unperturbed dimensions of the polymer chain to estimate the molecular weight of a variety of polymers was not as satisfactory as the above techniques. This approach generally gave biased molecular weight values (consistently low or consistently high). Agreement with the absolute values ranged from 10 to 30%. We therefore believe that either of the techniques based on the hydrodynamic volume concept can be used more effectively to estimate the molecular weight of a series of polymers than the treatment based on the unperturbed dimension.
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  • 87
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 1285-1292 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A theoretical determination of the elastic modulus, the breaking strength, and breaking strain is made for a single infinitely long molecule of polyethylene (CH2)∞. These results are compared with those of a similar calculation on a molecule of polyethylene with a side chain attached. It is found that the presence of a side chain weakens the molecule by approximately 17%.
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  • 88
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 1251-1262 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The composition heterogeneity has been calculated for some block and graft copolymers. General relationships have been derived for a model of the poly(A-g-B) or poly-(A-b-B) type fulfilling the assumption of random grafting. Numerical results have been calculated for special cases of particular interest. These include a copolymer having independent molecular weight contributions from units of species A and B (a special case of which is a block copolymer) and a graft copolymer where the grafting is not accompanied by crosslinking or degradation side reactions and no homopolymer B is formed. Two other model systems represent the effects of the presence or absence of both homopolymers. For the above models, the dependence of the composition heterogeneity on the structure-determining parameters (average number of grafts in the molecule, polydispersity index of the molecular weight of the backbone and graft) is discussed. The heterogenities thus calculated are in many cases comparatively low. The composition heterogeneity of the system is in most cases increased by the presence of homopolymers.
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  • 89
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 1271-1284 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The low-strain-rate tensile stress-strain properties of cis- and trans-polybutadienes and -polyisoprenes, polybutadiene (cis/trans/vinyl), butyl rubber, and two SBR copolymers have been investigated from 77°K to up to 25°K below the glass transition temperature Tg. The energy Ep dissipated in a stress-strain test in the region of previously reported secondary glass transitions is found to be a function of both the free volume f̄Tg at the Tg and the damping A4Tg from 4°K to Tg -25°K. The complex relationship between the impact strength, the free volume and the damping is briefly discussed. The effect of quenching through the Tg with liquid nitrogen was found to increase the value of Ep for all materials. In a number of cases this increase was associated with the presence of internal crazes. The surface-craze initiation stress is increased by the presence of surface residual compressive stresses caused by quenching. The internal tensile stresses balancing the surface compressive stresses together with the applied tensile stress cause internal dilatation and hence preferential initiation of internal crazing.
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  • 90
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 1331-1336 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The relation between the fractive index n and the density ρ of a liquid mixture is formulated as \documentclass{article}\pagestyle{empty}\begin{document}$$ {{\left( {n^{{2 \mathord{\left/ {\vphantom {2 3}} \right. \kern-\nulldelimiterspace} 3}} - 1} \right)} \mathord{\left/ {\vphantom {{\left( {n^{{2 \mathord{\left/ {\vphantom {2 3}} \right. \kern-\nulldelimiterspace} 3}} - 1} \right)} {\rho = }}} \right. \kern-\nulldelimiterspace} {\rho = }}\sum\limits_i {w_i R_{Si} } $$\end{document} where wi and Rsi are the weight fraction and the specific refraction, respectively, of component i. The calculation of the specific refraction of straight-chain polyethylene and polystyrene from data for pure compounds of low molecular weight is discussed. The result is applied to dilute solutions of polystyrene in toluene. The calculated values of (dp/dw)0 and (d2ρ/dw2)0 at three different temperatures are compared with measured values. The agreement is satisfactory.
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  • 91
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 1337-1345 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Research on liquid tellurium is reviewed and interpreted in an effort to obtain a consistent picture of the effect of pressure and temperature on the structure and properties of tellurium in the liquid state. Electrical resistance experiments on liquid tellurium support the existence of reaction boundaries in the p-T diagram. The boundaries are believed to identify stages in the reaction whereby the 2-coordinate covalent chain structure transforms to a 3-coordinate covalent network structure which eventually dissociates with pressure and temperature into a metallic system. The increasing liquid density associated with the molecular reaction is given as the cause of the maximum on the P-T melting curve. The melting curve maximum in tellurium is shown to be related to maxima in selenium and sulfur. Quenching tellurium from different liquid fields, delineated by reaction boundaries, resulted in materials with different x-ray spectra.
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  • 92
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 1453-1459 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The curing process, during which the monomeric diglycidyl ether of bisphenol-A is cured with 4,4′-methylenedianiline, has been studied by pulsed NMR. Values of the proton relaxation times T1, T1ρ, and T2 have been measured as a function of time as the resin system cures at constant temperature. The relaxation times are interpreted in terms of the decrease in general molecular motion which results from the cure. Plots of correlation frequency versus time for the constant-temperature cure were constructed for three temperatures. It is shown that these three plots can be represented by a reduced curve. With certain simplifying assumptions, the shape of this reduced curve. With certain simplifying assumptions, the shape of this reduced curve can be accounted for in terms of the chemical rate constant and an exponent relating molecular weight to viscosity. The activation energy for the cure is estimated to be 11.7 kcal/mole.
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  • 93
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 1601-1617 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A new morphological structure has been shown to be a general feature of polyolefin powders. This feature is a fiber approximately 0.5 μ in diameter and is common to a large number of samples of polyethylene, ethylene-propylene copolymer, polypropylene, polybutene-1, and poly-4-methylpentene-1 samples. Polymer particles prepared with different catalysts under different conditions are composed of these fibers. The fibers grow from globules formed during the initial phase of polymerization, and their formation at high catalyst efficiency suggests that not all primary catalyst particles have equivalent activities.The fiber structure is one of at least six levels of order prevailing in the polypropylene particle. While the catalyst particle is responsible for some of the distinctive morphological arrangements, polymer morphology is the primary cause for the other structures. The primary catalyst particle is thought to be the determinant for the fiber.
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  • 94
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 1641-1652 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Complex dielectric constants at frequencies of 110 Hz, 1 kHz, and 10 kHz and complex elastic moduli at 34 kHz and 3 MHz were measured in the temperature region the of δ relaxation of poly(ethyl methacrylate) (PEMA) down to 4°K. The temperatures of the loss maximum correlate well with literature values of the temperatures of mechanical loss maxima and with T1 minima. The activation energy is 2.1 kcal/mole. The energy map for the internal rotation of the ester ethyl group of PEMA was calculated; the activation energy and the energy difference between the two energy minima (0.31 kcal/mole) were found to agree well with those determined from experiment. The strength of dielectric relaxation is interpreted on the basis of 0.11 D as the dipole moment of the ethyl group. The strength of mechanical relaxation obtained in the present study as well as the previously published values are discussed. The volume change arising from the internal rotation of an ethyl group is found to be comparable at low temperatures with the van der Waals volume of the ethyl group and to decrease with increasing temperature.
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  • 95
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 1723-1733 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: By using a simple version of Treloar's torsion method the internal energy contribution Me to the restoring couple M has been determined for stretched testpieces subjected to small torsions. Values obtained for Me/M decreased significantly with increasing extension. Corresponding decreases were observed on swelling, but no specific effect of swelling liquids could be detected. The degree of crosslinking had no effect on Me/M. Thus, Me/M at small strains appears to reflect a characteristic molecular property, largely independent of local environment, network density, or type of deformation, as Flory has maintained. The present values are generally consistent with previously published data, except in the case of polyethylene, for which a much larger negative value is obtained, i.e., -1.6 compared to -0.5. The reason for this discrepancy is not known.
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  • 96
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 1759-1767 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The purpose of the work was to test existing theories of chain folded polymer crystallization over a supercooling range which is much is excess to what could be hitherto realized. This was made possible by the recognition that crystallization of isotactic polystyrene in solution could be conducted over an exceptionally wide range of temperatures in an isothermally controlled manner. The results revealed that the familiar inverse dependence of the fold length on supercooling (the behavior observed and studied in polyethylene) was only displayed at the lowest supercooling; at high supercoolings the fold length reached a constant lowest value unaffected by further lowering of the crystallization temperature. This is in conflict with present theories, which predict a catastrophic upswing in fold length at high supercoolings. It is demonstrated that the observations cannot be made compatible with this prediction by any conceivable adjustment of the numerical parameters. The implications of these findings are discussed.
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  • 97
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 1793-1801 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Chain folding in unoriented poly(ethylene terephthalate) (PET) films has been investigated as a function of annealing time and temperature. To meet this objective dynamic mechanical, infrared, and molecular weight measurements were used, together with selective chemical degradation to remove chain folds and amorphous regions. The β dispersion in the dynamic mechanical spectrum of PET is here tentatively associated with motions of methylene and/or carboxyl groups in irregular chain folds; the β dispersion is not found in quenched amorphous polymer, in polymer where amorphous regions and chain folds have been removed, or in highly annealed PET where the irregular folds have regularized. Upon mild crystallization and annealing (30 min at 110°C) of initially amorphous film a large β dispersion appears and then diminishes upon further annealing at 220°C. As the β dispersion diminishes, the infrared regular fold band increases more than the crystallinity band, indicating regularization of folds. The molecular weight of the degraded residue corresponds approximately to typical fold-period dimensions (∼130 Å), and increases on annealing as expected from lamellar thickening. The degradation process has, by fold removal, reduced the chains in the crystals to a very short, uniform length.
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  • 98
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 1829-1839 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The sorption and diffusion of gases in poly(ethylene terephthalate) (PET) films have been measured by using a newly devised apparatus which gives the sorption rate curves from the initial to the equilibrium state. By analysis of sorption data for carbon dioxide in PET film, it was shown that the diffusion rate, as well as the equilibrium solubilities, could be explained by the dual-mode sorption mechanism proposed by Vieth et al. Constants of their equation were used in the analysis of our experimental results, in which the apparent diffusion coefficients were dependent on pressure. The result showed that the dual-mode sorption mechanism indeed applies to diffusion. The value of the real diffusivity obtained in amorphous PET was 5.7 × 10-9 (± 8%) cm2/sec in the range of pressure from 0 to 1 atm. It is believed that this apparatus has wide applicability, not only to diffusion of gases in polymers, but also to the measurement of surface properties, and can be used to study the morphology of a variety of polymers.
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  • 99
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 1855-1857 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 1 Ill.
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  • 100
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    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 2261-2272 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A styrene-butadiene-styrene block copolymer (SBS) and a plasticized SBS were studied as a function of temperature by an ultrasonic wave propagation technique at 9 MHz. Two absorption maxima were found for each of these polymers, one being attributable to the primary glass transition of the polybutadiene blocks and the other to that of the polystyrene blocks. The SBS was cast from two different solvents, namely benzene and tetrahydrofuran-methyl ethyl ketone. Parallel dielectric loss measurements were also made of the SBS in the frequency range of 50-105 Hz. Relaxation temperatures determined from the ultrasonic and dielectric loss maxima over a range of measurement frequencies can be correlated by an Arrhenius-type equation. The polystyrene loss peak in the ultrasonic data was found to be much weaker than the polybutadiene loss peak. However, these two peaks were of comparable magnitude in dielectric data. This observation was interpreted as being due to the onset of structured-unstructured (heterophase to homogeneous) transitions at sufficiently high temperatures. Ultrasonic data were also compared with low-frequency dynamic mechanical data (11 Hz) and stress relaxation data (102-105 sec) through the use of simple time-temperature superposition principle. Considerable discrepancies were found by using this principle, indicating that the heterophase SBS block copolymer was thermorheologically complex.
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