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  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 101-109 
    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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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 111-124 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dynamic mechanical properties of cellophane, amylose, and dextran have been obtained over the temperature range 100-520°K and frequency range 10-2 to 10+2 Hz on specimens containing various amounts of water. Four mechanical transitions have been characterized. At about 180°K, there is a γ transition that has been assigned to rotation of methylol groups; no comparable transition was found to exist in dextran. At about 240°K, there is a β transition that has been assigned to rotation of methylol-water complexes, but the β transition in dextran appears to be due to some other kind of motion. In cellophane at about 450°K there is an α2 transition which appears to have contributions from motion of chain segments in disordered regions. The α1 transition for cellophane occurs at temperatures too high to measure and may be due to segmental motions in chains within crystalline regions. Dextran and amylose were found to have at these same temperatures α loss processes that probably correspond to glass-rubber transitions in amorphous material. The changes in these mechanical loss mechanisms due to moisture uptake suggest that sorbed water associates with glucose repeat units in ways ranging from those which stiffen molecular structure to those which allow greater freedom for other types of motion to occur.
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 165-171 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The preparation of chloroprene-methyl methacrylate copolymers in the presence of Lewis acids (Et1.5AlCl1.5) in hydrocarbon solvent and the effect of Lewis acids concentration on copolymer composition are described. 13C NMR spectra were obtained on these copolymers. In samples of high MMA content, tactic placements of MMA were observed as well as several different kinds of sequences for chloroprene and MMA. In samples of low MMA content, no tactic placements of MMA were found but several different kinds of chloroprene sequences were observed. From the analysis of the 13C NMR spectra of the different copolymers examined, it is apparent that all the various kinds of chloroprene sequences in these copolymers can be determined.
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 187-210 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A study has been made of the crosslinking of linear polyethylene in solution. Networks containing a low number of trapped entanglements and elastically ineffective chain ends were prepared by crosslinking high molecular weight linear polyethylene in 1,2,4-trichlorobenzene solutions with dicumyl peroxide at 120°C. No syneresis was observed during crosslinking except at high peroxide concentrations. The networks were characterized by swelling measurements, infrared spectroscopy, and differential scanning calorimetry. The crosslinking efficiency, calculated from swelling, was found to be proportional to the square of the polymer volume fraction. The proportionality constant was 0.8, indicating close to unit efficiency for undiluted polymer.Chemical modification of the polyethylene chains by attachment of peroxide and solvent fragments was of the order of one foreign unit per elastically active network chain, depending on peroxide and polymer concentration. Sol-gel analysis indicated that no chain scission occurred. These results are shown to be consistent with a “cage” mechanism for crosslinking. The possible topological consequence of this mechanism, preferential crosslinking of entanglements, is discussed. The concentration of trapped entanglements was also found to be proportional to the square of the polymer volume fraction. The proportionality constant corresponds to a molecular weight between entanglements of 4000 for the undiluted polymer, which is close to the value of 4200 found for networks prepared from the undiluted polymer. Since the results obtained are based mainly on the use of the swelling equation, different aspects of the applicability of this equation for the evaluation of the crosslinking process are discussed. As regards the reference dimensions, which should be known for a quantitative application of the elastic theory, the results strongly support the use of the dimensions of the network chains after completion of crosslinking.
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 251-262 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Isolated spherulites of poly(methyl D-glutamate) (PMDG) were nucleated in bromoform. The morphology of these spherulites was investigated by SEM and photographic small-angle light scattering (SALS). From the SALS patterns, the development and growth of the spherulites could be noted. Films of PMDG cast from bromoform solution were found to be partially spherulitic. The mechanical properties of these films, prepared by different procedures, were compared with the general behavior of PMDG films cast from chloroform, the latter of which does not contain spherulitic texture.
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  • 6
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    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 299-308 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Data are presented to show that two correlations of viscosity-concentration data are useful representations for data over wide ranges of molecular weight and up to at least moderately high concentrations for both good and fair solvents. Low molecular weight polymer solutions (below the critical entanglement molecular weight Mc) generally have higher viscosities than predicted by the correlations.One correlation is ηsp/c[η] versus k′[η], where ηsp is specific viscosity, c is polymer concentration, [η] is intrinsic viscosity, and k′ is the Huggins constant. A standard curve for good solvent systems has been defined up to k′[η]c ≍ 3. It can also be used for fair solvents up to k′[η]c ≍ 1.25· low estimates are obtained at higher values.A simpler and more useful correlation is ηR versus c[η], where ηR is relative viscosity. Fair solvent viscosities can be predicted from the good solvent curve up to c[η] ≍ 3, above which estimates are low. Poor solvent data can also be correlated as ηR versus c[η] for molecular weights below 1 to 2 × 105.
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 263-274 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A study has been carried out of the differences in mechanical properties of oriented fibers of poly(ethylene terephthalate) (2GT), poly(trimethylene terephthalate) (3GT), and poly(tetramethylene terephthalate) (4GT). The properties studied include the tensile stress-strain behavior, the recovery from strain, shrinkage at 100°C and the glass-transition temperatures. The stress-strain curves of the three materials differ markedly. 2GT shows a monotonic increase in stress with increasing strain up to failure, which occurs at ∼20% strain, and the oriented fibers possess a comparatively high initial modulus. 3GT shows a much lower initial modulus and there is an inflection in the stress-strain curve at about 5% strain. The stress-strain curve of 4GT shows a number of distinct features. Although the initial modulus of 4GT is similar to that of 3GT, the stress-strain curve shows a pronounced plateau in the region between 4% and 12% strain. At higher strains the stresses rise rapidly before failure. These features of the stress-strain curves in the three polymers can be related to previous studies where the x-ray diffraction spectrum and the Raman spectrum have been examined for fibers under stress. The ranking of both the recovery and shrinkage behavior of these materials is in the order 3GT 〉 4GT 〉 2GT. These results can also be understood in terms of the results of the previous structural studies, and it is concluded that the molecular conformations in both the crystalline and noncrystalline regions play a key role in determining the mechanical behavior.
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  • 8
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    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 285-298 
    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 concentration of the crosslinking agent (ethylene dimethacrylate) and diluent (water) during the crosslinking copolymerization on the shape and position of retardation spectra in the dry state has been investigated for poly(2-hydroxyethyl methacrylate) networks. With increasing water content during network formation, the maxima of the retardation spectra, Lm, increase and the position of the spectra is shifted toward shorter retardation times, τ. The results are in quantitative agreement with the modified Rouse-Mooney (R-M) molecular theory and suggest the influence of deformation due to the diluent during network formation on the viscoelastic behavior. With increasing content of the crosslinking agent, the retardation spectra are shifted toward longer times. At a constant reference temperature T0 = 115°C the retardation time, τm, at the maxima of the spectra increases with increasing content of effective chains in the network, νe. However, after a correction for the effect of the monomeric frictional coefficient, ξM0, τm/ξM0 decreases with increasing ve at a rate which agrees quantitatively with the R-M theory. The slope of the retardation spectra in the main transition region and the value of their maxima decrease with increasing ve; a comparison of these dependences with theory leads to the most probable distribution of submolecules in the chains. The contribution of long retardation times to the equilibrium compliance, Je, of the systems under investigation was estimated; it was shown that the application of the Thirion-Chasset extrapolation method for the determination of Je of loose networks requires a certain type of dependence of the retardation or relaxation spectra on τ.
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  • 9
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    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 367-371 
    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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  • 10
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    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 377-389 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The morphology and growth of the disordered hexagonal phase which crystallizes in films of cis-polyisoprene at pressures in excess of 3 kbar is discussed. A two-stage growth process is proposed consisting of nucleation and crystallization followed by a pressure-enhanced thickening process. The phase is metastable and is replaced by normal spherulitic growth at long times. It transforms into lamellar sheafs with higher than usual lamellar thicknesses when pressure is lowered at constant temperature.
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  • 11
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 401-414 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dynamic piezoelectric stress constant e*25 of drawn films of poly(γ-methyl D-glutamate) (PMDG) cast from solutions in α-helix-promoting solvents 1,2-dichloroethane (DCE) and chloroform and from the nonhelicogenic solvent dichloroacetic acid (DCA) was measured from -180°C to 200°C at 110 Hz. The drawn and annealed films cast from chloroform show a small peak for the real part of piezoelectric stress constant -e′25 in the temperature range of the mechanical α2-crystalline relaxation, which is caused by the distortion motion of the backbone chain of the α-helix. On the other hand, drawn films cast from DCE show the peak of the real part of the piezoelectric stress constant, whose magnitude decreases in the range of the mechanical α1-crystalline relaxation or the β-relaxation processes, which were previously ascribed, respectively, to mutual slipping of α-helices and to the micro-Brownian motion of disordered regions. Also, -e′25 becomes virtually zero near 180°C where the α2-relaxation is located. These results suggest that the polarization change induced by applied strain is caused by distortion of the backbone chains in the α-helix. Near 0°C, the temperature range of the side-chain mechanical relaxation, -e′25 exhibits a marked peak both for films cast from chloroform and from DCE. The maximum value of -e′25 and the orientation function of the α-helix axis are linearly related and extrapolation of -e′25,max to unit orientation function gives 1.3 × 104 cgs esu which corresponds to 2.4 Debye per residue. This value corresponds reasonably to the value of 3.71 Debye for the permanent dipole moment of NHCO bond if the correction for crystallinity is made. This result also indicates the piezoelectric properties of PMDG arise from distortion of the backbone chain of the α-helix induced by applied strain.
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  • 12
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    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 521-529 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Raman spectroscopy has been used to analyze the characteristics of the crystal-crystal phase transition of trans-1,4-polybutadiene. The low- and high-temperature structures were found to coexist at the transition. The Raman spectra obtained at high temperature can be understood on the basis of the change in chain conformation associated with the phase transition.
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  • 13
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Relaxation of stress and birefringence in simple extension has been studied for two samples of 1,2-polybutadiene with 95% and 88% vinyl content and weight-average molecular weight 1.9 and 2.9 × 105, respectively. The extension ratio, λ, ranged from 1.14 to 2.08, temperatures from 0 to 15°C, and times, reduced to 0°C, up to 3 × 105 sec. The stress-optical coefficient C was negative and positive, respectively, for the two samples, the difference being attributable to opposite signs and very different magnitudes of the contributions of the 1,2 and 1,4 moieties to the birefringence. For each polymer, C was independent of time but increased (algebraically) with temperature. For one polymer a very minor dependence of C on λ was observed. At any instant of time, the dependence of both stress and birefringence on λ could be described by equations of the Mooney-Rivlin form with coefficients C1,C2 and B1,B2, respectively. At short times the contributions of the C1 and C2 terms to the stress and of the B1 and B2 terms to the birefringence are roughly equal. With increasing time, C1 and B1 decrease gradually while C2 and B2 remain constant over several decades in time. Finally, C2 and B2 decrease rather rapidly. A tentative interpretation of these phenomena in terms of motions of entanglements is given.
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  • 14
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 559-563 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 6 Ill.
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  • 15
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    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 569-571 
    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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  • 16
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 675-685 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The gas permeability and diffusion time lag may exhibit varying degrees of pressure dependence for glassy polymers. The sorption isotherm appears to consist of contributions from both Langmuir and Henry's law terms in such systems. This “dual sorption” theory advanced in the literature pictures gas held by the Langmuir mode as being completely immobilized. In the present paper, this model is extended to accommodate different degrees of partial immobilization of gas sorbed by this mode using two different formulations. One uses a transport expression based on concentration gradients while the other is based on chemical potential gradients. The predictions are that: (1) total immobilization results in a constant permeability with a time lag which strongly decreases with pressure; (2) no immobilization results in a constant time lag with a permeability which decreases strongly with pressure; and (3) incomplete immobilization results in both the permeability and time lag decreasing with pressure but neither as strongly as in the other limiting cases. The differences which may arise by the two formulations of the model are discussed.
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  • 17
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 741-747 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Brillouin scattering has been studied from amorphous bisphenol-A polycarbonate in the temperature interval 60-240°C. Both longitudinal and transverse Brillouin peaks are observed over the entire range. The behavior of both types of Brillouin splittings, Δωl and Δωt, in the region of the glass-rubber relaxation is typical of an amorphous polymer. Equilibrium values of Δωl and Δωt were obtained 20°C below the glass-transition temperature Tg determined at cooling rates of 20°C/hr. Comparison of the present results with previous ultrasonic data reveals a considerable dispersion in the longitudinal phonon velocity below Tg. The origin of the large transverse Brillouin intensities is related to the structure of polycarbonate.
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  • 18
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 783-797 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The stable packings of polyethylene chains were investigated by intermolecular potential energy calculations based on various chain-assembly models. The structures of the two crystal modifications of polyethylene (i.e., orthorhombic and the monoclinic), together with their cell constants and the setting angles, were well reproduced. The packing modes of polymethylene chains found in various alkane derivatives were also explained by the energy minima of the chain-assembly models. In these calculations, several sets of potential functions were tried and three sets of functions were found to reproduce conformations of single polymer chains, the cell constants of polyethylene at low temperature, and those at room temperature.
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  • 19
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 759-768 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Experimental data on styrene-acrylonitrile (St-AN), and styrene-methyl methacrylate (St-MMA) copolymers reported in Part I of this series are tested by “two-parameter” theoretical relations. The Fox-Flory (F-F) parameter K is estimated using the F-F, Stockmayer-Fixman (S-F), and Inagaki-Ptitsyn (I-P) equations. In general, the K values obtained by the F-F equation are low for the three St-AN copolymer samples in the systems studied while the values obtained from S-F and I-P equations agree within the limits of experimental error. Values of K obtained from Kurata-Stockmayer (K-S) equation for sample SA1 agree with values obtained by the S-F and I-P equations. The specific solvent effect on the K values is discussed. Values of the unperturbed dimension r̄02/M̄w, calculated from the K values estimated from the S-F equation and from the homopolymer data are compared. Except in one case, the calculated r̄02/M̄w values from homopolymer data are low in comparison with the values obtained from experimental data, which shows that the presence of the repulsive interactions between unlike monomer units brings about an expansion of copolymer molecule. The effect of composition on the steric factor σ values is discussed. The long-range interaction parameter B, the excess interaction parameters ΔBAB, and χAB are calculated. The effects of composition and solvent on these parameters are discussed.
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  • 20
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 879-895 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Metal-insulator-semiconductor (MIS) techniques were used to show that 86-210 nm thick plasma-polymerized tetrafluoroethylene films on silicon stored only negative charge (electron acceptors). This property persisted at a reduced level when a 7 nm thick inner layer of hydrolyzed γ-aminopropyltriethoxysilane was combined with an outer layer of plasma-polymerized tetrafluoroethylene. The dispersion force contribution to the surface energy, γds, for the fluorocarbon films was found to be 6 mJ/m2 (erg/cm2) which is comparable with the lowest values found in the literature. X-ray photoelectron spectroscopy (XPS) revealed a substantial content of —CF3 groups in the fluorocarbon films. This finding coupled with the reported effects of noncrystallinity, crosslinking, and branching on the surface energies of fluorocarbon systems were used to explain the low surface energy and electrophilicity of the plasma-deposited poly(tetrafluoroethylene)s.
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  • 21
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 913-920 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A simple treatment based on continuum mechanics shows that weak interlamellar forces in crystalline n-alkanes should result in a characteristic upward shift of the frequencies of the longitudinal acoustical (LA) modes, which is independent of the chain length and decreases inversely with the mode order. A raman spectroscopic determination of the LA mode frequencies of a series of different n-alkanes confirms the theoretical conclusion and permits a derivation of a force constant characteristic of the interlamellar forces. The discussion results in a new formula valid for the LA mode frequencies of the orthorhombic n-alkanes in the acoustical limit and yields a new determination of the limiting elastic modulus Ec of crystalline polyethylene. The value obtained, Ec = 2.9 × 1012 dyne/cm2, is markedly smaller than the value derived by Schaufele and Shimanouchi neglecting the influence of the interlamellar forces on the LA mode frequencies.
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  • 22
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 959-961 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 23
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An analytical solution of the Poisson-Boltzmann equation is presented for the cell model of a polyelectrolyte solution with two species of monovalent counterions of different size. On this basis the osmotic coefficient is calculated as a function of the mole fraction of counterions and their radii. It is shown that the degree of binding of the smaller ion species increases as its mole fraction decreases.
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  • 24
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1029-1046 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The Vibrational analysis of polyethylene terephthalate, polyethylene-d4 terephthalate, and polyethylene terephthalate-d4 has been carried out using a valence force field calculated from the infrared and Raman spectra of a series of low molecular weight aromatic esters. The Raman spectra for polyethylene-d4 terephthalate and polyethylene terephthalate-d4 are presented and band assignments for these compounds and polyethylene terephthalate are discussed.
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  • 25
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The room-temperature tensile mechanical properties and fracture topographies of polycarbonate are reported as a function of strain rate, sample preparation, and thermal history above and below Tg. The bulk physical structural changes produced by various thermal treatments were monitored by density, yield stress, and differential scanning calorimetry observations. Ordered regions do not form in bulk polycarbonate at or below 145°C. The changes produced in the mechanical properties of polycarbonate on annealing below Tg, relative to a quenched or 145°C equilibrium-state glass, are caused by liquidlike packing changes in free volume. In room-temperature tensile a 125°C-6 day annealed glass exhibits transitional behavior from shear free volume, such as quenched and 145°C equilibrium-state glasses, this transition occurs at higher strain rates. Polycarbonate embrittles as a result of the cessation of shear yielding and reversion to a crazing failure mode with a corresponding decrease in molecular flow and energy to failure.Density measurements indicate that ordered regions do start to grow immediately above 145°C in bulk polycarbonate. This phenomenon allows precrystalline and/or crystalline entities to grow below the bulk Tg in thin films and on the free surfaces of thick films where mobility restrictions are less severe than in the bulk. From bright-field transmission electron micrographs of thin films and carbon-platinum surface replicas of etched thick films it is suggested that the observed spherical precrystalline structures are aggregates of 50-60 Å ordered molecular do mains.
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  • 26
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1495-1512 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Unoriented T-die flat films of nylon 6 and PET films annealed at 90°C were stretched in water at 80°C. Amorphous PET films were stretched in water at 65-75°C. Changes in the light scattering patterns from these samples upon stretching were investigated. One of the observed LS patterns from the stretched samples is the Hv eight-leaf pattern consisting of four lobes and streaks. In the nylon 6 and heat-treated PET showing this pattern, spherulitic patterns can be seen in polarization microscopy. The microscopic spherulitic superstructure may possibly be the factor responsible for producing the lobe-and-streak pattern. On the other hand, many microscopic eight-leaf patterns can be observed in amorphous unannealed PET showing the lobe-and-streak pattern. These microscopic patterns are due to retardation at stress concentrations around impurities and nuclei. The superstructure giving these microscopic patterns must be the origin of the lobe-and-streak pattern from unannealed PET. Another scattering pattern, the Vv cruciform pattern, was observed in both stretched nylon 6 and unannealed PET. This pattern is due to an orientation change across the slip lines observed under a polarizing microscope. It is noted (1) that the appearance of the slip lines in PET coincides with the occurrence of oriented crystallization on stretching, (2) that the lobe-and-streak pattern from PET in which orientation crystallization has taken place is fairly stable to heat treatment and does not disappear until just before melting, and (3) that the superstructures produced at low stretching seem to be deformed on further stretching, in accordance with affine deformation theory.
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  • 27
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1567-1573 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An Interesting kinetic effect in the environmental stress cracking (E.S.C.) of polyethylene has been observed, in which the liquid viscosity plays an important role. E.S.C. of a low density, high melt index polyethylene due to silicone oils has been studied using constant load creep experiments. For relatively low stresses, it has been found that the time to fracture is independent of the viscosity of the silicone oil, all other factors being approximately equal. However, at high stresses, the time to fracture increases with increasing viscosity for a given stress. This effect has been shown to be due to the relative ease with which the liquid penetrates a growing crack and thus always be at the crack front. Times to fracture for viscous liquids at high stresses are longer since crack propagation continues partially with and partially without liquid contact, fracture rate being much slower when not in the presence of the liquid.
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  • 28
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1717-1720 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 3 Ill.
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  • 29
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The development of the shear stress at the start of shear flow at constant rate of shear κ was measured for polystyrene solutions in diethyl phthalate with a cone-and-plate rheometer. Ranges of molecular weight M and concentration c were 3.10 × 106-7.62 × 106 and 0.112-0.329 g/cm3, respectively. The shear stress as a function of time t exhibited a marked maximum at large κ when either M or c was relatively low. When M and c were high, the maximum was broad and low. In a few extreme cases no maximum was observed in the range of κ studied. The constitutive model of Bernstein, Kearsley, and Zapas could describe approximately the shear stresses at a sudden start and on cessation of steady shear flow with a memory function evaluated from the strain-dependent relaxation modulus. The strain dependence of the memory function for solutions of low M or c was approximately expressed as exp{-α|s|} where α is a constant (ca. 0.37) and |s| is the absolute value of shear strain. When M and c were high, the strain dependence was found to be more diffuse and to require several terms if approximated by exponential functions of |s|. The Lodge model based on a strain-rate dependent relaxation spectrum was not able to describe the strain-dependent relaxation modulus as well as the interrelation between shear stresses at a sudden start and a cessation of steady shear flow.
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  • 30
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1693-1700 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Spin-lattice relaxation times (T1) for methyl, methylene, and methine carbons in an amorphous polypropylene have been measured as a function of temperature from 46 to 138°C. The carbons from isotactic sequences characteristically exhibited the longest T1's of those observed. The T1 differences increased with temperature with the largest difference occuring for methine carbons where a 32% difference was observed. Activation energies were determined for the motional processes affecting T1's for isotactic and syndiotactic sequences with essentially no dependence upon configuration noted.
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  • 31
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 2037-2045 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The similarity of the π-electron backbones of the polyenes and the polydiacetylenes suggests an analogy between these two fully conjugated, linear polymers. The extent of the analogy is discussed through the examination of a series of model compounds: the polyenes and the polyenynes. The optical band gaps and the polarizabilities of polyenynes are compared to those of the polyenes and to the predictions of a modified free-electron model. It is concluded that the chain-dependent electronic properties of the polyenes may be extrapolated with some confidence to the polydiacetylenes.
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  • 32
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Diffusion coefficients of cellodextrin alditols from DP 1 to 5 in 0.32 molar NaOH are found to be 22% less than in water. Slightly lower diffusion rates and higher friction coefficients and Einstein-Stokes hydrodynamic radii are also reported for the alditols as compared to cellodextrins in water. Considered as ellipsoids based on diffusion rates, the length-to-width ratio for the alditols, only slightly greater than for the cellodextrins in water, increase by about 100% in alkali. A similar increase in axial ratio is shown for cellodextrins in the highly alkaline solvent cadoxene as for the alditols in alkali. It is suggested that creation of the large frictional envelope occurs in alkali prior to complexing with the common cellulose solvents in which complexing with copper, cadmium, and iron in divalent from are involved. The possible nature of the enlarged frictional domain is discussed.
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  • 33
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 2073-2082 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Application of the van der Poel equation (as recently corrected and simplified by Smith) to modulus-composition data on polymer composites is discussed. The van der Poel equation is in good agreement with experimental results on systems for which the ratio of filler to matrix modulus is either much less than or, if the filler particles are large enough, much greater than unity. For these systems, it is shown that the van der Poel equation is essentially equivalent to an empirically modified form of the Kerner equation. Discrepancies between the van der Poel equation and experimental modulus values for the remaining systems are analyzed in terms of an effective volume fraction veff. A functional form for veff found to be in agreement with experimental results on several systems is: veff = vf + k′(vf/d)2/3 where vf is filler volume fraction, d is filler particle size, and k′ is an empirical parameter. For the systems studied, k′ ranges between 0.28 and 1 μm2/3.
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  • 34
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 2105-2108 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 35
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 2109-2112 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 4 Ill.
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  • 36
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 2119-2128 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polystyrene networks prepared by anionic polymerization have been characterized by small-angle neutron scattering. Two kinds of systems have been examined:(A) networks with labelled branch points allowing characterization of the spatial distribution of crosslinking points; (B) networks containing a low proportion of chains labelled with perdeuterated polystyrene in order to characterize the conformation of individual elastic chains of the polymeric network. The dependence of the results on swelling and uniaxial extension is discussed.
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  • 37
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 2137-2152 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: After annealing at low temperature, linear polyethylene displays an unusual feature in its specific heat curve. On heating, a maximum is observed just above the annealing temperature. The magnitude of this excess specific heat is dependent on the initial level of crystallinity and the temperature and time of annealing. The maximum does not reappear on subsequent cooling followed by rapid heating and represents the formation and disappearance of an unstable structure. These results can be interpreted as a crystallization-melting phenomenon and are consistent with the wide-angle x-ray diffraction patterns. The optimum effects are observed in the β-region (-50°C to 0°C) and could possibly lead to complications in interpreting other phenomena in this temperature range.
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  • 38
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 2211-2218 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A model for the interpretation of homogeneous nucleation data for chain molecules is presented. The two surface energies σs and σe are related to interchain and intrachain bonding. Surface energies calculated from experimental data on n-alkanes from octane to dotriacontane and polyethylene agree with estimated values. The results are discussed in relation to surface energies measured from spherulite growth rates in polymers but these values are not known with sufficient reliability to provide a good basis for comparison.
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  • 39
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 81-92 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The molecular and crystal structures of polydiketene were studied by infrared spectroscopy and x-ray diffraction. It was confirmed from the infrared spectra that diketene molecules in the crystal polymerize by ring opening upon γ-ray irradiation. The unit cell of the product as polymerized is orthorhombic, P22121-D23, with a = 5.43 Å, b = 8.94 Å, and c (fiber axis) = 7.75 Å. Two molecules pass through the unit cell The molecule has a conformation shown by the Fischer projection for a lefthanded (2/1) helix; The internal rotation angle around the O - C bond is nearly gauche (-84°), unlike other polyesters. On the basis of x-ray analysis, several molecular conformation models were selected by utilizing calculations of intramolecular interaction energies.
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  • 40
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: As part of a wider study on the crystallization of isotactic polystyrene solutions it was observed that at sufficient concentrations (〉 3-5%) gelation sets in below a certain (very high) supercooling in competition with the usual single crystal formation which in itself produces turbid suspensions. It was established that gelation is a form of crystallization (mode A) which must be of fringed micellar type to provide the connectedness as opposed to the chain folded lamellae (mode B) which gives rise to discrete particles. The gel crystals (A) display sharp melt endotherms and produce distinct x-ray diffraction patterns both of which, however, differ decisively from those provided by crystals B, a distinction which can be preserved even after removal of the solvent. The melting points of A are significantly lower than those of B and the x-ray diffraction patterns of A are incompatible with the recognized structure of polystyrene (31 helix) possessed by B; they point to a broadly planar zig-zag arrangement of the chain. This strongly suggests that we have blocks of chemically distinct sequences which could be syndiotactic or head-to-head tail-to-tail (presently with substantial support for the latter) which is responsible for the gel forming crystallization. However, so far the C13 nuclear magnetic resonance (NMR) results do not provide the evidence for these distinct species but explanations for our observations on any other basis seem to lead to unsuperable difficulties from other points of view. Consequently, the paper is left open ended with the possibilities discussed. Amongst these the existence of a very few but long, chemically distinct sequences seems most attractive. The wider implications of the facts as they stand for crystal morphology (fringed micelles versus lamellae), for the origin and structure of gels in general, for the crystallization of block copolymers and for issues relating to chemical homogeneity (tacticity, head-to-head tail-to-tail) are discussed and preliminary effects are quoted which indicate that these issues may also be relevant to the usual atactic polymers.
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  • 41
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 143-149 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Many polymers cannot be prepared as clear amorphous blocks suitable for classical light scattering studies. However, most linear polymers can be prepared as films which are somewhat transparent. With the advent of high contrast multipass interferometers, these films can now be studied by Brillouin scattering. This work demonstrates the wide range of polymeric materials that can now be studied by Brillouin spectroscopy.
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  • 42
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 151-164 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It is demonstrated by several methods (DSC, infrared spectroscopy, and small-angle and wideangle x-ray diffraction) that bromination of suspensions of single crystals of trans-1,4-polybutadiene is selective at the fold surface. As the thickness of the single crystals is increased, a larger number of double bonds per fold are brominated, i.e. a larger number of repeat units become accessible to bromine. This is consistent with an increase in the thickness of disordered surface layers with the crystallization temperature. A reduction of 40-60% in overall apparent enthalpies of transition and of melting and reduced ability of brominated single crystals to refold following annealing are also observed. Crystallization from the melt of trans-1,4-PBD with [ CH2—CHBr—CHBr—CH2 ] units along the chain is interpreted by assuming that some of these units are incorporated in the crystal lattice as defects.
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  • 43
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 211-222 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dielectric behavior of poly(L-proline) II has been studied by the dc transient method and a contactless pendulum technique. The comparison of measurements performed with and without contacting electrodes shows that the static and low-frequency dielectric behavior are due to bulk phenomena. Both mechanisms are strongly dependent upon the water content of the sample. At low hydration, the static conduction may be attributed to an electronic process. The observed low-frequency relaxation can be characterized by a relaxation time which increases with the water content. This behavior can be explained by an increase in stiffness of the poly(L-proline) chain: two adjacent carbonyl groups of the chain may be hydrogen bonded by two water molecules.
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  • 44
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A model relating crystal orientation to the deformation of nylon-6 spherulites under uniaxial stretching is discussed in terms of the orientation distribution functions of reciprocal lattice vectors of crystal planes, such as the (002) and (200) planes. The distribution functions calculated from the model are compared with those obtained from x-ray diffraction experiments. It is found that the crystal a axis and, consequently, the direction of hydrogen bonds within the crystal (α modification) orient parallel to the lamellar axis in the undeformed state, and that the crystal orientation behavior of nylon-6 is much different from that of low-density polyethylene, being characterized by much smaller values of the reorientation parameters of crystallites within orienting lamellae.Moreover, small-angle light scattering for Hv and Vv polarization is also calculated on the basis of the spherulite deformation model by taking the nylon-6 crystal as having orthogonal-biaxial symmetry in optical anisotropy. It is concluded that the Hv scattering can be realized in terms of the proposed model for spherulite deformation by taking into account a considerable contribution of hydrogen bonds to the molecular polarizability, so as to make the polarizability along the crystal a axis larger than that along the b axis. In other words, this conclusion suggests positively birefringent spherulites in the nylon-6 samples studied.
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  • 45
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 275-284 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The spin-probe technique has been employed to study the nature of the surface regions of poly(trans-1,4-butadiene) crystals grown from dilute heptane and toluene solutions. The narrowing of the ESR spectrum of the nitroxide radical probe added to the PTBD crystals and the activation energy for the rotational motion of the probes were found to very with the crystallization solvent and annealing temperature; in every case heptane-grown crystals showed a higher line narrowing temperature and activation energy than toluene grown crystals. Annealing at 80°C raised the narrowing temperature and the activation energy for crystal preparations from both solvents used, but annealing at high temperatures, near to but below the melting point, lowered both parameters again. These results support earlier assertions, based on infrared spectra, surface epoxidation, differential scanning calorimetry, broad-line nuclear magnetic resonance, and dynamic mechanical results concerning the nature and location of the amorphous regions in PTBD crystals.
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  • 46
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 309-315 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It is shown that the applicability of the Stockmayer-Fixman-Burchard plot is much more limited in the case of solvent-precipitant mixtures than in the case of pure solvents. The observed deviations can be explained by taking into account the variation of preferential solvation as a function of the molecular weight of the polymer. More precisely the average density of the segments in the region occupied by the coiled molecule seems to be the parameter governing both changes in viscosity and in preferential solvation.
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  • 47
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 373-376 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 3 Ill.
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  • 48
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 391-399 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The crystallization of cis-polyisoprene even at moderately elevated pressures results in the formation of a single-crystal species which develops through skeletal growth. The nature of these crystals, which are produced at relatively low supercooling, is described. They occur concurrently with spherulites but exhibit a much higher growth rate. In common with single crystals grown from solution the size and shape of the species is a function of the supercooling.
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  • 49
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 415-425 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The small-angle x-ray scattering (SAXS) from glassy polyethylene terephthalate has been measured using a Bonse-Hart system. The data cover the angular range (2θ) between 20 sec and 2 deg. After correcting for absorption, background, and beam divergence, the data have been placed on an absolute basis by comparison with the scattering from a standard silica suspension. The corrected absolute intensity decreases strongly with increasing angle over the range between 20 sec and 15 min, decreases more gradually in the range between 15 min and 45 min, and reaches a nearly constant asymptotic value over the range between 45 min and 2 deg. The magnitude of the scattering in the constant range, about 0.4 (electrons)2 Å-3, is very close to the value predicted by the thermodynamic fluctuation theory for fluids applied at the glass-transition temperature [0.34 (electrons)2 Å-3]. The increase in intensity at angles smaller than about 45 min cannot be described by structures on the scale and volume fraction of the nodules reported in amorphous PET (50-100 Å), but can be well represented by small concentrations of heterogeneities, ranging in size from 100 to 2000 Angstroms, superimposed on the thermal density fluctuations frozen-in at the glass transition. The bulk structure of this material seems well described as a random amorphous solid, containing simple thermal fluctuations and a small concentration (〈1 vol-%) of heterogeneities covering a range of sizes. The heterogeneities in the small end of the range may well be crystallites which formed on cooling.
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  • 50
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 451-478 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Creep and recovery measurements have been used to study the thermal-mechanical properties of polybisbenzimidazobenzophenanthroline-dione (BBB) over the temperature interval 30-500°C (in vacuo). The creep measurements were augmented by x-ray diffraction, isothermal contraction, and solubility measurements. It is found that extensive intermolecular association giving a supramolecular structure with (nearly) planar polymeric repeat units stacked in a “graphite-like” array dominates the properties of BBB, and that this structure is maintained at temperatures as high as 500°C. The principal mode of creep gives rise to fully recoverable Andrade creep for which the strain depends on the cube-root of time.
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  • 51
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 479-484 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Individual polyethylene molecules have been imaged in the electron microscope. Preparative difficulties are overcome by the following procedures. (1) The polymer is dissolved in n-hexadecane at 130°C; (2) the solution is deposited on a cooled substrate by spraying in an atmosphere of cold nitrogen; (3) the deposited polymer molecules were shadowed by platinum. Molecular weights obtained are in good agreement with those from light scattering.
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  • 52
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 499-508 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Since some dielectric loss peaks can be assigned to amorphous phase motions, it would appear that dielectric measurements should be a good probe to study the effects of macroscopic plastic deformation on the structure of the amorphous phase. We report here results of measurements of dielectric constant and loss in nylon 610 measured both parallel (∥) to and perpendicular (⊥) to the extrusion direction in specimens prepared by extrusion through a die at 160°. It is found that the intensity of the (∥) loss was nearly zero and the (⊥) loss intensity was greatly reduced compared to unoriented material. The other relaxation parameters (loss width and location) were largely unaffected. Since the amide dipole is nearly perpendicular to the chain axis and alternates in direction in the extended conformation, a considerable degree of chain alignment parallel to the draw direction is indicated. These results therefore show considerable permanent amorphous phase orientation even though the deformation was carried out 100° above its glass temperature.
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  • 53
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 555-558 
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    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 14 (1976), S. 565-567 
    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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  • 55
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 603-618 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The mechanics of “springy” or “hard elastic” row-crystallized polymers were investigated. It was found that their unique tensile and physical properties could be explained by adhesive fracture mechanics and simple beam deflection. The deformed lamellae had an apparent negligible modulus of flexural rigidity. An adhesive failure model was designed which duplicated all the tensile characteristics of springy polymers, including constant lateral contraction, critical stress, peel stress, rehealing, energetic elasticity, and cyclic strain behavior. The ideal relative density change as a function of strain was found to be the same for all springy polymers. Dynamic infrared analysis showed that the molecular orientation decreased during the deformation of springy polypropylene films. The latter is due to the deflection of lamellae. Rehealing was accompanied by a time-dependent reversal of orientation. The enthalpic elasticity is derived from the strain energy of the lamellar network.
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  • 56
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 631-641 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Samples of two helically wound monofilaments were used as experimental models to check the theoretical expression for light scattering from helixes. A method of estimating the pitch and tilt of the helixes was outlined and the results were compared with measurements from microscopy. The agreement was satisfactory. Layer line streaking and splitting was observed and explained in terms of irregularity of the helical parameters. Samples of several helically wound monofilaments were also prepared and their scattering patterns were compared with those from native and regenerated cellulosic fibers.
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  • 57
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 663-673 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dynamic loss modulus curves have been determined over a temperature range beginning at liquid nitrogen temperature for poly-α-olefin polymers containing various ring structures, i.e., phenyl, cyclohexyl, cyclopentyl, and naphthyl, in the side chain. Glass transition and appropriate secondary relaxation temperatures were observed for each polymer. Separation of each pendant ring structure from the main backbone chain by successive additions of methylene units results in lower glass-transition temperatures. Comparison of polymers with similar side chains and different ring structures shows that the respective glass-transition temperatures decrease in the order naphthyl 〉 cyclohexyl 〉 phenyl 〉 cyclopentyl. Secondary relaxation peaks were obtained at about -150°C for polymers containing the cyclohexyl and cyclopentyl rings. A similar peak was observed for the polymer possessing a phenyl ring separated from the main chain backbone by two methylene units. The comparable polymer containing the naphthyl ring structure exhibited a broad secondary relaxation peak centered at -20°C. The polymers possessing cyclohexyl rings separated from the main chain backbone by one or two methylene units had an additional low temperature peak at -80°C. The molecular mechanism associated with this relaxation may be related to intramolecular transformations of the cyclohexyl ring between its “chair-chair” conformations.
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  • 58
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 703-721 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Tensile deformation of poly(methyl methacrylate) carried out under hydrostatic pressures up to 4 kbar has shown that the pressure-transmitting fluid (silicone oil) strongly affects the mechanical properties of this polymer. Unsealed specimens fractured in a brittle manner at almost the same strain of 5% in the whole pressure range examined, while specimens sealed with Teflon tape and rubber showed a brittle to ductile transition at only 0.25 kbar. At this pressure, the craze initiation and shear band initiation stresses were found to become equal. The pressure dependence of the shear band initiation stress could be expressed well with a “nonlinear” pressure-dependent von Mises criterion and the onset of the shear banding was proved to relate to the enthalpy energy density stored in the specimen. The combination of the nonlinear pressure-dependent von Mises criterion and the enthaply energy density concept enabled us to predict the pressure dependence of Young's modulus.
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  • 59
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 769-771 
    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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  • 60
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 749-757 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Styrene-acrylonitrile (St-AN) copolymers of three compositions - 27.4 mole-% (SA1); 38.5 mole-% (SA2); and 47.5 mole-% (SA3) acrylonitrile - and styrene-methyl methacrylate (St-MMA) copolymer (SM) of 46.5 mole-% methyl methacrylate were prepared by bulk polymerization at 60°C with benzoyl peroxide as the initiator, and were then fractionated. The molecular weights of unfractionated and fractionated samples were determined by light scattering in a number of solvents. The [η] versus M̄w relations at 30°C were established for SA1, SA2, SM, and polystyrene (PSt) in ethyl acetate (EAc), dimethyl formamide (DMF), and γ-butyrolactone (γ-BL), and for SA3 in methyl ethyl ketone (MEK), DMF, and γ-BL. Second virial coefficients A2 and the Huggins constant were determined. From values of A2 and the exponent a of the Mark-Houwink relation it is seen that the solvent power for samples SA1, SA2, and PSt is in the order EAc 〈 γ-BL 〈 DMF, while for sample SA3 the solvent power is in the order MEK 〈 γ-BL 〈 DMF. The solvent power decreases with an increase in AN content. The solvent power of the three solvents used for SM copolymer sample is practically the same within experimental errors. From the a values it is concluded that in a given solvent the copolymer chains are more extended than the corresponding homopolymers.
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  • 61
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 773-781 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dielectric relaxation behavior of three sodium polyphosphates with different but low degrees of polymerization in aqueous solution (without salt) has been investigated between 8 kHz and 100 MHz. The highest molecular weight sample (DP 338) exhibits two dispersion regions as is generally observed with synthetic polyelectrolytes at higher degrees of polymerization and is interpreted, according to the theory of van der Touw and Mandel, by attributing a certain flexibility to the polymer chain. The experimentally determined relaxation time of the high-frequency dispersion is in fair agreement with the theoretically calculated value. For the lowest molecular weight sample (DP 112) the experimental results can best be described by a single dispersion curve pointing to a rigid, more or less stretched, conformation of the polyion in agreement with theoretical predictions. For the sample of intermediate molecular weight (DP 198) the situation is borderline as it is possible to describe the relaxation behavior by either one or two dispersion regions; it is, however, concluded from an analysis of the dielectric results that the average conformation is rather extended, but not completely rigid.
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  • 62
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 833-846 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Samples of an S-B-S three block copolymer exhibiting a lamellar morphology have been prepared, in which the macrolattice formed from the segregated amorphous is uniformly oriented throughout the sample volume. The associated optical anisotropy has been studied in the unswollen state and in the presence of preferential solvents for the polybutadiene phase. The results obtained are consistent with form birefringence being the dominant contribution to the observed birefringence. There is a small contribution from a slight molecular orientation, corresponding to polystyrene chains perpendicular to the lamellar surfaces. The form birefringence is appropriately modified when the sample is in the swollen state by molecular orientation produced in the polybutadiene, due to the anisotropic dimensional changes in the sample. The implication of the results as regards the nature of the polybutadiene phase is also discussed.
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  • 63
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 869-877 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The photoconductivity of poly(N-acryloylcarbazole) (PACz), with the pendant carbazolyl group only a short distance from the skeletal chain of the polymer but separated from it by a carbonyl group, is investigated and compared with that of poly(N-vinylcarbazole) (PVCz). There is no significant difference between PACz and PVCz in the temperature, light intensity, and spectral dependences of the photocurrent. The photoconductivity of PACz, however, is much inferior to that of PVCz and even to that of poly(N-carbazolylethylvinylether), a representative vinyl polymer with pendant carbazolyl groups far from the skeletal chain. The poor photoconductivity of PACz is discussed in relation to the intensity of the electronic interaction between neighboring carbazolyl groups in the polymer chain and to singlet exciton migration. It is attributed mainly to an extremely low efficiency of extrinsic carrier generation via a singlet exciton, which is due to the poor electron-donating character and the extremely short lifetime of a singlet exciton in the presence of the carbonyl group.
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  • 64
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 903-911 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The thermal degradation of polyoxymethylene produced by the solid-state polymerization of trioxane crystals has been studied. Changes in small-angle and wide-angle x-ray patterns, weight loss, and density have been measured in specimens heated in air at 175°C, 185°C, and 195°C. The polyoxymethylene contained material in two different crystallographic orientations, which behaved differently. Material in the so-called “twin” orientation melted preferentially at 185°C and 195°C, and at 185°C resolidified on cooling in parallel to the main orientation, in a lamellar structure. At 195°C, randomly oriented material was produced on resolidification. At 175°C, there was no evidence of melting or the formation of a lamellar structure, but the twin material was preferentially degraded so that only material in the main orientation remained after a time of 1500 min. The more rapid loss by degradation of the twin material was attributed to its having a lower molecular weight than the material in the main orientation.
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  • 65
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 921-940 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A wide-angle x-ray method has been developed by which quantitative structural information can be obtained on nylon-6 yarns. To this end, experimental equatorial diffractometer scans measured in transmission were fitted to a mathematical model describing the profiles as the envelopes of three bell-shaped functions. Four different models were investigated using, respectively, Gauss, Lorentz (Cauchy), Logistic, and Pearson-VII functions. The last model, which can be regarded as a generalized Lorentz function, gave the best fit. On the basis of a statistical analysis of the results of well-separated x-ray peaks, two parameters could be fixed. Another reduction of the number of parameters was achieved by interrelating the peak areas of the two outer reflections. These reductions widened the applicability of a computer program based on the aforementioned model to highly overlapping x-ray peaks. So the whole variety of x-ray scans, which can be obtained from nylon-6 yarns made under widely varying process conditions, can be well described. The fitting procedures provide unique solutions and hence objectively determined parameters.
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  • 66
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 981-988 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetics of formation of a swollen surface layer by diffusion of liquid solvent into solid poly(vinyl chloride) in the glassy state has been studied. The apparent Fickian diffusion coefficients of cyclohexanone, cyclopentanone, tetrahydropyrane, 1,2-dichloroethane, N,N-dimethyl-formamide, and monohalogen derivatives of benzene in PVC is calculated with the use of Crank's model for discontinuous change of diffusion coefficient with concentration. It is found that the apparent activation energy for diffusion is in the range 6-17 kcal/mole and is dependent on the polarity of the solvent molecule.
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  • 67
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    Keywords: Physics ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Persistent polarization in poly(vinylidene fluoride) thermoelectrets prepared under high electric field has been studied by measurements of depolarization and pyroelectricity. Various polarizations are examined in detail; the polarizations related to a characteristic molecular motion near 60°C and the polarizing temperature are not responsible for the major piezoelectric effect in β-form electrets. The piezoelectricity is attributed to a polarization appearing near the melting temperature. The persistent polarization corresponding to d31 of 2 × 10-11 coul/N is about 5 × 10-6 coul/cm2. The pyroelectricity of β-form electrets is linearly correlated with the piezoelectricity.
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  • 68
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1021-1028 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Three transitions have been found with peaks at 130°C (α), 88°C (β), and -65°C (γ), by mechanical relaxation techniques for a quick-quenched sample of an alternating copolymer of ethylene and chlorotrifluoroethylene. The intensity of the α transition was found to increase with an increase in crystalline content. It was observed at 150°C by infrared and x-ray diffraction techniques and by mechanical relaxation spectra on an annealed sample. X-ray diffraction and dichroic infrared measurements were conducted on oriented specimens as a function of temperature. These data showed that the β transition was accompanied by a change in lateral bonding distances in the crystalline phase and a conformational change attributed to an “unkinking” of the molecular chain. The β transition was found to be related to the amorphous phase and the onset of the β peak corresponded to the transition at 35°C found by infrared techniques and previously by a torsional modulus method. It was tentatively assigned to the glass transition. A more definitive assignment of the β transition would depend on a detailed structural analysis of the γ transition. The γ peak was not studied in detail in the present work.
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  • 69
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1077-1085 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Neutron transmission of polydimethylsiloxane has been measured as a function of neutron wavelength in the range 4-10 Å, at room temperature. Scattering cross sections per hydrogen atom have been obtained and the slope (12.2 ± 0.2) barns/Å has been derived. Comparison with calibration curves relating the slope to the barrier hindering internal rotation as well as comparison with calculated neutron cross sections using the Krieger-Nelkin formalism for different dynamical situations indicates practically free rotation of CH3 groups about their C3 symmetry axes.
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  • 70
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1111-1119 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We report flow birefringence observations of polyethylene oxide solutions in a four roll mill where the flow field in the central region of the mill approximates well to that of pure shearing flow. When flow birefringence is observed it is seen to be highly localized within a region close to the “outgoing” asymptotic plane of flow. The phenomenon can be explained in terms of the flow birefringence corresponding to high extension of some polymer chains where the localization is caused by the chains requiring sufficient time in the flow field to become extended. This explanation has important consequences in all “persistently extensional flows” and can explain the origin of previously published results of localized flow birefringence observed for polyethylene solutions in axial compression and axial extensional flows.
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  • 71
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1133-1148 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dynamic viscoelastic properties of block copolymers of styrene with butadiene or isoprene are consistent with the growth of a diffuse interphase or interlayer as block lengths decrease. Under the conditions of the present study the interlayer does not lead to a secondary loss maximum between the two domain glass transitions. The pattern of shifts of the loss maxima characteristic of the domain Tg's suggests strongly that the interlayer composition profile must be asymmetric with an average volume composition rich in styrene. Typical block polymer viscoelastic behavior is observed even beyond the point at which the interlayer attains 100% of the polymer volume. Such block polymers no longer contain compositionally pure phases, but are visualized as retaining a residual domain structure in which composition fluctuates between ever narrowing limits as blocks become shorter, approaching homogeneity and the mechanical behavior of random copolymers.
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  • 72
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1177-1186 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The influence of thermal history on the morphology of bulk-crystallized isotactic polystyrene was investigated. Results from x-ray diffraction (both wide- and small-angle), DSC experiments, and electron microscope observations, were combined to define the influence of thermal history on the fold surface free energy σe. lamellar thickness, and crystallite perfection. The increase of the melting point with crystallization temperature is not only the consequence of an increase in lamellar thickness, but also of marked decrease of σe. Annealing above the crystallization temperature results in a fast reorganization to a more stable structure, as reflected in an increase in melting point. This reorganization, depending on the crystallization temperature, involves an increase in lamellar thickness, a decrease of σe, and eventually an increase in crystallite perfection.
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  • 73
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1169-1175 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: This paper discusses the applicability of three melting equations to the melting temperature and its pressure dependence in polymer crystals. The equations considered are the empirical Simon equation and two semiempirical equations, the Lindemann equation and the anharmonic potential barrier equation (APB equation). It was found that although the Simon equation fits melting curves of polymeric solids well, it is merely an interpolation and extrapolation formula. There appears to be no correspondence between theoretical and experimental values of the exponent in the Simon equation. With regard to the melting temperature at atmospheric pressure, the APB and Lindemann equations perform equally well. Using the value 3.5 for the universal Grüneisen constant, it is shown that TM0 (Lindemann) = 1.07 TM0 (APB). On the other hand, the different physical arguments behind the two approaches lead to a very different behavior at high pressures. For the predicated initial change of melting temperature with increasing pressure a ratio close to 5:1 is obtained between the APB and the Lindemann equation. For high-density polyethylene the Lindemann equation yields a melting temperature of 470°K when θ3 = 112°K given by Wunderlich is substituted for the Debye temperature. The observed melting temperature 405°K Corresponds to a Debye temperature of 107°K. The increase of the melting temperature with pressure for high-density polyethylene is predicted as 31°K/kbar by the Lindemann equation as compared with 23°K/kbar found by experiment.
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  • 74
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1211-1220 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dynamic modulus, G′, and viscosity, η′, in the melt were determined for styrene ionomers containing up to 7.7 mole-% sodium methacrylate in the frequency range of 10-2 to 40 rad/sec, at various temperatures. The same parameters were determined for the methyl ester of these ionomers, as well as for some acid samples. It was found that in the temperature range studied the time-temperature superposition principle was applicable to the salts as well as to the esters and acids. Furthermore, it was found that the shapes of the G′ versus ω plots for the three types of polymers were identical for a particular molecular weight and comonomer concentration, and independent of whether the sample was in the acid, ester, or salt form. The temperatures required to achieve superposition were, however, quite different. This temperature difference, ΔT (between the salt and the ester), was found to be a function of the ion concentration, c. The shape of the plot of ΔT versus c suggests that the structure of the ionic aggregates changes in the range of 4-5 mole-% of ions.
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  • 75
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1271-1286 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Pulsed NMR T1, T2, and T1ρ measurements are reported for poly(vinylidine fluoride) (PVF2). The results demonstrate clearly the presence of four relaxation processes, three amorphous and one crystalline. The α relaxation is undoubtedly a crystalline one, while β and γ are both amorphous, in agreement with earlier conclusions from dielectric and dynamic mechanical measurements. The fourth relaxation (β′) observed initially in the mechanical measurements of Kakutani, but undetected in dielectric experiments, has been confirmed in our results and the process is described by an activation energy of 15.1 kcl/mole. Motion of folds on the surface of crystal lamellae is deemed to be the responsible mechanism for the β′ relaxation. Two models have been considered in the interpretation of the α process; rotation of crystalline chains in the vicinity of defects and rotational oscillation of restricted amplitude of all crystalline chains about the main chain axes. Rotation of amorphous chains is a possible mechanism for the γ process while motions of a general nature are responsible for the β relaxation. Our experimental results again indicate that spin diffusion plays an important role in the overall NMR response of the polymer.
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  • 76
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1-10 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The scattering law S(k,w) for dilute polymer solutions is obtained from Kirkwood's diffusion equation via the projection operator technique. The width Ω(k) of S(k,w) is obtained for all k without replacing the Oseen tensor by its average (as is done in the Rouse-Zimm model) using the “spring-bead” model ignoring memory effects. For small (ka\documentclass{article}\pagestyle{empty}\begin{document}$ \sqrt N $ \end{document} ≪ 1) and large (ka ≫ 1) values of k we find Ω = 0.195 k2/β α η0 \documentclass{article}\pagestyle{empty}\begin{document}$ \sqrt N $ \end{document} and Ω = k2/βξ, respectively, indicating that the width is governed mainly by the viscosity η0 for small k values and by the friction coefficient ξ for large k values. For intermediate k values which are of importance in neutron scattering we find that in the Rouse limit Ω = k4a2/12βξ. When the hydrodynamic effects are included, Ω(k) becomes 0.055 k3/βη0. Using the Rouse-Zimm model, it is seen that the effect of pre-averaging the Oseen tensor is to underestimate the half-width Ω(k). The implications of the theoretical predictions for scattering experiments are discussed.
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  • 77
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 93-99 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It is shown that the distribution of normal stress around a craze, found by Knight using a Fourier transform method may not be uniquely determined, and that in fact the stress field cannot be computed unless the rheological properties of the craze tip material are known.
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  • 78
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 63-79 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The piezoelectric effect due to shear in oriented films of DNA is strongly dependent on the relative humidity at which the films are equilibrated. Below about 60% relative humidity, the sign of the piezoelectric modulus is negative and its magnitude passes through a maximum with increasing temperature. This type of polarization appears to be due to the stress-induced orientation of dipoles in sugar-phosphate main chain. Above 75% relative humidity, water molecules are adsorbed by the bases and stabilize the ordered structure of double strand helices. In this crystalline state, the sign of the piezoelectric modulus is positive and its magnitude decreases markedly at about-75°C. This type of polarization appears to be due to the stress-induced orientation of dipoles in bases attached to the main chain. From comparisons between piezoelectric, elastic, and dielectric measurements, it is concluded that the piezoelectric relaxation observed at-75°C and 75% relative humidity is mainly due to the dielectric relaxation of the bases in the double helix.
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  • 79
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 125-133 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Changes in dynamic mechanical properties of cellophane films due either to fungal attack or to hydrochloric acid hydrolysis have been measured. It appears that damage caused by cellulase enzymes that are released from a fungal overgrowth is localized in noncrystalline regions. These effects include a substantial reduction in elastic modulus, a reduction in temperature at which relaxation processes involving chain segmental mobility occur, and a broadening of loss tangent peaks due to segmental mobility and to rotations of methylol groups. Comparing results obtained from cellulase hydrolysis with those obtained from acid hydrolysis, it is clear that enryme attack proceeds by a characteristic and selective process. Implications regarding the embrittlement often seen to accompany biodegradation are discussed.
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  • 80
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 821-831 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The possible explanations for the temperature-induced reversible changes in long spacing in polymers are reviewed. The observation of particularly large changes in certain irradiated samples of oriented low-density polyethylene is reported. By combining these results with those obtained by DSC and other means it is concluded that the spacing changes are caused by partial melting of small lamellae within the lamellar stacks which alters the mean periodicity. The requirement of an irregular lattice explains why the effect is observed primarily in bulk samples and especially in materials which contain intrinsic irregularities.
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  • 81
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 861-867 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A technique is described which enabled exceptionally thin sections of rubbery material to be cut for electron microscopy, and applied to samples of polystyrene-polybutadiene-polystyrene (SBS) copolymers which contain the segregated S phase in the form of cylinders arranged in a regular hexagonal macrolattice throughout the macroscopic specimen, with center to center distance of 300 Å. The technique consisted of sectioning the material hardened by a combination of osmic acid treatment and cooling with liquid air. By this method longitudinal sections containing single layer S rods could be obtained as verified by appropriate tilting tests. Such sections enabled the viewing of single cylinders without overlap which in turn enables the study of the structure of individual cylinders and the effect of various treatments on this structure. Examples quoted include the yielding or breaking of individual cylinders on longitudinal deformation of the macroscopic sample relating to our mechanical studies to be reported elsewhere. The technique also enabled sectioning in the swollen state of samples which are not sectionable other wise and this leads to the recognition of new structures and results in an overall improvement of image quality even when the thinness itself is not the prime requirement.
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  • 82
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1047-1052 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: There is much controversy in the literature concerning the nature of the thermal transitions observed for segmented polyurethanes. In this study calorimetric and NMR data on a polyurethane reveal ordered structures similar to that previously observed. However, based on a recently observed semi-ordered polymeric phase and the observation of a time-dependent calorimetric effect not observed previously, the data are interpreted in terms of a high-temperature short-range order and a low-temperature long-range order. The former appears to form faster and annealing of both ordered phases increases their thermal stability.
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  • 83
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1097-1109 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Spectra of polarized light scattered from model networks of polystyrene swollen by benzene have been measured by optical mixing spectroscopy. Various series of networks of different functionalities and different lengths of the elastic chain elements have been investigated. A theoretical expression for the characteristic time constant of fluctuations has been derived from rubber elasticity theory. An analysis of the experimental results within the framework of this theory allows determination of the frictional constants of the gels.
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  • 84
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1121-1131 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Experimental observations are reported of the behavior of solutions between two rotating parallel rollers where the form of the flow field between corotating rollers corresponds to that of a col which has nonorthogonal asymptotes. The obliquity of the asymptotes of the flow gives a direct measure of the relative magnitude of the constituent pure shear and rotational components of the flow field.Flow birefringence observations of polyethylene oxide solutions between the corotating rollers show that molecular orientation is limited to a highly localized region near the “outgoing” asymptotic sheet of the flow field in accordance with the predictions of a “persistent extensional flow” analysis presented. Counterrotating rollers show no flow birefringence also as expected.The behavior of polymer solutions and Newtonian fluids are compared. With increasing strain rate using corotating rollers the obliquity of the asymptotes of the flow remains constant for the Newtonian fluid but changes significantly for the polymer solution.
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  • 85
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1157-1160 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 3 Ill.
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  • 86
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1201-1209 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The glass-transition temperatures of a series of copolymers of ethyl acrylate and acrylic acid neutralized with various cations were investigated. It was found that a plot of Tg as a function of ion content, for every type of ion investigated here, gives an unusual sigmoidal curve, which can be correlated with the onset of the failure of time-temperature superposition in viscoelastic studies, as will be shown in a future publication. Also, all of the Tg versus concentration curves for the various counterions can be superposed if the plots are made against cq/a, where c is the metal acrylate content, q the cation charge, and a the distance between centers of charge. Furthermore, in one region of water content, a linear relation is obtained between the glass transition and the water content (in weight-%) independent of the ion concentration over wide ranges of ion content. Finally, above an ion concentration of 12 mole-%, the rate of change in Tg per water molecule per ion pair at constant ion content, (∂Tg/∂n)c is linear but with different slopes above and below two water molecules per ion pair.
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  • 87
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1221-1234 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dynamic viscoelastic measurements, E′ and E″, were carried out on solution-crystallized and melt-crystallized samples of fractionated isotactic polypropylene over the temperature range of -100°C to 150°C. The molecular weight ranged from 1.26 × 104 to 1.77 × 105. The effects of swelling and annealing on the α and β peaks were more pronounced for the lower molecular weight fraction than for the higher one. It was found that both the untreated solution-crystallized and quenched melt-crystallized samples contain a fair amounts of a constrained amorphous phase in which the molecular motions were so depressed that the corresponding peak could be observed as the low-temperature component of the α peak. These constraints on the molecular motions are considered to originate from the spatial restrictions imposed by the presence of the surrounding crystallities.
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  • 88
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1235-1240 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An x-ray back-reflection rotating camera has been used to measure the lattice constant, thermal expansion, and compressibility in the polymer chain direction of a polydiacetylene, poly[bis(p-toluene sulfonate) of 2,4-hexadiyne 1,6-diol]. The thermal expansion coefficient of the polymer chain is small and positive (0.9 ± 0.2 × 10-6 °K-) at 300°K, but negative below about 70°K. Application of 3.43 kbar hydrostatic pressure at 299°K changed the unit cell dimension in the polymer chain direction by less than 10 ppm.
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  • 89
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1297-1304 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dielectric relaxation measurements at very low frequency were carried out on polycarbonate. Two prominent peaks were resolved from the broad β-relaxation peak with activation energies of 0.28 and 0.52 eV, respectively. Thermally stimulated discharge current was also studied and compared to the results obtained from the dielectric relaxation measurements.
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  • 90
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1325-1336 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dynamic mechanical and thermally stimulated depolarization current data have been obtained on polyethylene, γ-irradiated in the molten state, as a function of irradiation dose. The β peak which appears in mechanical experiments has been attributed to motions of the chain backbone. The branches, like the crosslinks coming from γ-irradiation, are fixed tie points for the chains.
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  • 91
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1379-1389 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polyethylenes were prepared by γ-ray-induced polymerization in ethyl and n-butyl alcohols, tert-butyl alcohol containing 5 vol-% of water, 2,2,5-trimethylhexane, 2,2,4-trimethylpentane, and cyclohexane in the temperature range 25-90°C. The morphology of the polymers as-polymerized and studied by electron microscopy depends on three factors through the degree of undercooling: the affinity of the solvent, polymerization temperature, and the polymer molecular weight. Large lamellar crystals are formed even in the alcohols when at least two of them are chosen properly.
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  • 92
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Solvent-cast films of blends of poly(∊-caprolactone) (PCL) with poly(vinyl chloride) (PVC) were examined by low-angle x-ray scattering and by small-angle light scattering. X-ray scattering from crystalline compositions were analyzed using the Tsvankin-Buchanan technique and led to values of the repeat period of the lamellar structure and the thickness of the crystalline and amorphous layers. With increasing content of PVC, the amorphous layer thickness increased sufficiently to accommodate the PVC, leading to values of the linear crystallinity consistent with macroscopic measurements by density and DSC techniques up to about 50% PVC by weight. Above this concentration, the lamellar structure no longer appeared to be volume filling. At high concentration of PCL, the polymer consisted of volume-filling spherulites containing the lamellar substructure. Spherulite sizes were measured by light scattering and absolute light scattering intensities were consistent with calculations based upon the degree of crystallinity and anisotropy of the spherulites. Compositions containing more than 60% PVC were amorphous. Low-angle x-ray scattering was interpreted in terms of the Debye-Bueche theory which leads to values for a correlation distance lc and the mean-square electron density fluctuation 〈η2〉 (which was also obtained from the invariant). By the method of Porod, the correlation distances were resolved into persistence lengths within the two phases, which were determined as a function of composition. The fluctuation 〈η2〉 was analyzed in terms of a two-phase model to show that its value was somewhat larger than would be obtained if the phases were composed of the pure components. It was not possible to uniquely determine their compositions. The data were consistent with the existence of a transition zone of the order of 30 Å thick between phases.
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  • 93
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1485-1493 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The universal calibration for gel permeation chromatography (GPC) has been applied to amylose and dextrans. The molecular weight distribution of amylose has been measured starting from known data on dextrans. The agreement found between the molecular weight averages resulting from GPC and those obtained by other methods justifies the procedure followed. The GPC measurements were performed with dimethylsulfoxide as the elution solvent and deactivated silica gel (Porasil) as the column-filling material.
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  • 94
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1591-1599 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dielectric β-relaxation in oriented poly(ethylene terephthalate) was investigated over wide ranges of frequency and temperature, with the electric field applied at inclinations of 0°, 45°, and 90° to the draw direction. Pronounced directional anisotropy is observed over the entire range of temperature and frequency. With the external field parallel to the draw direction the dielectric loss is considerably smaller than the value obtained with the field normal to the draw direction. The value obtained with the electric field at 45° to the draw direction is intermediate between the other two. On the other hand, the activation energy is largest for 0° inclination and smallest for 90° inclination. It is suggested that motions of the dipoles involve localized rocking of the molecular chain backbone, particularly when the external electric field is parallel to the chain direction.
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  • 95
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1659-1669 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dynamic mechanical properties of cold-compacted films of polyethylene prepared by γ-ray-induced polymerization in bulk at 30°C are discussed in connection with the fine structure. The cold-compacted films show a broad α-relaxation at a lower temperature than do single-crystal mats or melt-crystallized polymer. From the effects of annealing and swelling by carbon tetrachloride on the relaxation, it is concluded that the α-relaxation, like the α-relaxation in the single-crystal mats, originates from molecular motions within lamellar crystals. This is consistent with the finding that these films are composed of stacked small irregular lamellar crystals. The γ-relaxation is also similar to that in crystal mats.
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  • 96
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1725-1727 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 3 Ill.
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  • 97
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1743-1753 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The azimuthal angular dependence of the depolarized component of the light scattered from spherulitic materials is derived by an algebraic method that avoids the difficult angular integrations of the usual approach. The result appears as a sum of products of two factors, a molecular factor, that depends only on the structure and the scattering angle θ, and a geometrical factor that depends only on the azimuthal angle φ and the scattering angle θ. The molecular factors are evaluated for models of spherulitic structure that assume a constant tilt of the optical polarizability tensor. The radial distribution, in principle, is arbitrary, and an evaluation for the layered spherulite is made. If the tilt angle is ω when the azimuthal patterns depend only on a linear combination of P2(cos ω) and P4(cos ω), where Pn(x) is the Legendre polynomial of order n. In our theory the VH scattering pattern is a four-leaf clover whose axes are restricted by the theory to be at either 0 or 45° to the polarization directions.
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  • 98
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1839-1854 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Highly porous interpolymer ion-exchange membranes have been prepared from poly(styrene sulfonic acid), PSSA and poly(vinylidene fluoride) PVdF using a casting solvent of dimethylformamide and hexamethylphosphoramide. The membranes have been characterized by their water content, concentration potential, ionic conductivity, and their hydraulic permeability. An estimation of the porosity of the membranes has been made from the relative conductance of the potassium and the tetrabutylammonium ions in the film. This porosity has been compared with that derived from a consideration of the water flux through a Poiseuille-type pore.
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  • 99
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1903-1907 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 4 Ill.
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  • 100
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    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1913-1916 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 2 Ill.
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