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  • 2020-2022
  • 1965-1969  (1,849)
  • 1920-1924
  • Physics  (1,849)
  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 171-182 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: To clarify the deformation mechanism in polyblends of polypropylene with ethylene-propylene rubber having different compositions, simultaneous measurements of the infrared dichroism with stress and strain under a constant rate of strain of 1.64%/min have been carried out. The orientation function of the crystallographic c axis of polypropylene in the blends has been obtained as a function of strain ranging from 0 to 20% and of polypropylene content ranging from 0.3 to 1.0. These results have been compared with the temperature dependences of the dynamic Young's modulus and of the loss modulus, as well as of stress-strain curves for the same blends. The modulus data analyzed by Kerner's equation reveal the occurrence of phase inversion at polypropylene contents higher than about 0.5, and this is supported by the infrared dichroism data. The strong effect of quenching on crystalline structure and mechanical properties of pure polypropylene has also been elucidated.
    Additional Material: 12 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 183-200 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Equipment and methods have been developed which allow photomicrographic determination of the stress-strain properties of the individual craze. Serial cyclic tensile tests on polycarbonate crazes are described. Under stress the typical dry polycarbonate craze thickens solely by straining; no adjacent polymer of normal density is converted to craze material. The craze exhibits a yield stress followed by a recoverable flow to roughly 40-50% strain at 6000-8000 psi. On return to zero stress the craze exhibits creep recovery at a decelerating rate. The yield stress and loss factor of each cycle decrease with increasing initial strain and cycles initiating at 50% strain or more show completely Hookean behavior. Creep recovery results in recovery of yield stress and loss factor also. Craze tensile behavior is suggested to be essentially an extension of the craze formation process. Decrease in elastic modulus and yield stress with increasing strain are rationalized in terms of strain-produced decrease in density and resultant increase in stress concentration factor on the microscopic polymer elements of the craze. Polymer surface tension and the large internal specific surface area of the craze are suggested to be important factors in the large creep recovery rates of the craze.
    Additional Material: 10 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 241-248 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A method of determining distributions of the degree of polymerization by means of probability theory is derived. This method, based on Kolmogorov's forward differential equation, is illustrated by application to two familiar kinetic schemes and is used to derive the distribution of degree of polymerization for free-radical polymerization with diffusion-controlled termination.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 271-278 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effect of birefringence of a polymer film upon its photographic light-scattering pattern is considered for the case of a single, anisotropic, two-dimensional spherulite imbedded in a birefringent matrix. It is shown that for the case of a polarizer and analyzer crossed at +45° and -45° to the analyzer, the scattering pattern is modified in a manner agreeing with experimental observation.
    Additional Material: 5 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 285-295 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Osmotic-pressure, viscosity, and light-scattering measurements have been carried out on dilute solutions of poly-N-vinylcarbazole fractions (4 〈 10-4M 〈 230) in toluene, dioxane, and benzene. The theta temperature for poly-N-vinylcarbazole in toluene solutions has been found to be 37 ± 1°C. The intrinsic viscosity of poly-N-vinylcarbazole in toluene at 37°C is represented by [η]θ = 76.2 × 10-3M̄n0.50. Values of the characteristic ratios (〈L2〉0/M)1/2 and σ = (〈L2〉0/〈L2〉0f)1/2 have been obtained as 633 × 10-11 and 2.85, respectively. It appears that the large σ value is due to the steric repulsion between large side groups.
    Additional Material: 7 Ill.
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  • 6
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Mechanical relaxation data as a function of temperature (ca. 1 Hz) have been obtained for several samples of isotactic polypropylene crystallized from the melt, which exhibit both α and β forms as well as varying degrees of lamella orientation. The samples ranged in morphology from an unoriented sample showing only the α form to one highly oriented having approximately 90 per cent the β form. Results for the logarithmic decrement Δ and loss modulus G″ are that the low temperature (ca. -75°C) and glass temperature (ca. 0°C) relaxations show little or no sensitivity to orientation in the α form, but that the intensity of the two processes is different in the α form than in the β form for samples of nearly equal overall per cent crystallinity. In both Δ and G″, the low-temperature peak decreased and the glass temperature peak increased in intensity as the fraction of β form crystallinity present increased. Data for the high-temperature relaxation (ca. 80°C) indicate a dependence upon orientation and/or crystal form in addition to a dependence upon per cent crystallinity.
    Additional Material: 6 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 411-422 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The viscometric behavior of linear polycaprolactam has been studied in the absence of the electroviscous effect in aqueous solvents containing 85% and 64.5% formic acid and in trifluoroethanol, as a function of temperature and also under unperturbed conditions. Results are discussed in terms of the existing theories; in particular, the negative temperature coefficient of the intrinsic viscosity arises only from the variation of the expansion coefficient, the molecule in the unperturbed state being a normal random coil. The absence of aggregation and draining effects in the above solvents has been varified.
    Additional Material: 6 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 463-473 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polymers of poly(N-acyl and N-aroyl aziridines) were studied by x-ray diffraction. All the crystalline polymers studied have a triclinic unit cell with two monomer units per unit cell. The a and c (fiber direction) parameters (4.9 and 6.5 A, respectively) are essentially the same for all the cells. The b parameter for the N-acyl polymers, however, increases steadily by a factor of 2 A per methylene group added to the lateral chains. The densities calculated for the unit cells are in agreement with the experimental values obtained. The most probable structure is one in which the molecules assume a planar configuration with the main chain not fully extended. The lateral groups are tilted from the c axis by an angle of 54° in a parallel configuration and alternate on each side of the main chain. This permits these lateral groups to assume packing similar to that of polyethylene. A brief description of the techniques used in this interpretation is included.
    Additional Material: 8 Ill.
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  • 9
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Results from characterization of melt-polymerized nylon 66 by various solution property measurements are reported and employed in analysis of typical molecular weight and compositional distributions for these systems. Critical attention is paid to application of standard procedures including light scattering, viscosity, membrane osmometry and other colligative property measurements in arriving at satisfactory specification of polymer molecular weight averages. Particular consideration is given to polymers extending appreciably beyond the lower and higher limits in molecular weight normally encountered. The conclusions drawn are: (1) in the range of number-average molecular weights less than about 25 000, nylon 66 as ordinarily prepared by melt condensation consists principally of linear species approximating the “most probable” distribution; (2) small amounts of cyclic oligomers are present in all samples: (3) increase in the extent of the melt polycondensation to progressively higher stages is accompanied by secondary reactions and the formation of branched components terminating ultimately in crosslinked, insoluble gels. Intrinsic viscosity-molecular weight relationships in seven solvents, applicable to nylon polymers meeting the requirements of (1) above, are derived.
    Additional Material: 7 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 57-76 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: For an infinitely repeated regular polymer chain structure the only vibrations which are optically active are those in which the phase of the motion is the same in each unit (the factor-group modes). Frequencies for which the phase difference is nonzero are optically inactive but can become activated by the presence of defects in the chain. Such defects would normally be chemical impurities or conformational irregularities in the chain. A simple theory is developed which shows that for a dilute system of defects the major characteristics determining possible activation of the nonfactor-group modes are: (1) the strength of the coupling between the defect vibration and the vibrations of the neighboring chain, and (2) whether or not the natural frequency of the defect vibration lies inside a lattice band of the regular chain. An analysis of the low- and high-frequency regions of the spectrum of low-density polyethylene, based on the above considerations, indicates that several features of the spectrum can be associated with defect-induced absorption. A similar explanation can account for certain intensity changes in the C—Cl stretching region of syndiotactic poly(vinyl chloroide) when this polymer is submitted to mechanical treatment.
    Additional Material: 8 Ill.
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  • 11
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A general description is given for relations among the optical quantities obtained from fluorescence polarization measurements on bulk polymer stained by fluorescent groups: the moments of distribution of orientations of the fluorescent groups, and those of the structural units of the polymer (chain segments) on which the groups are adsorbed. Two assumptions as to the biaxial symmetry of the bulk polymer and the cylindrical symmetry of the optical anisotropy of the fluorescent element, both for the absorption and emission processes, reduce the intensities of the polarized fluorescence to a 3 × 3 matrix L which is asymmetric (Lij ≠ Lji), as has frequently been observed in experiments. The components of the L matrix are related to those of the J matrix which is so defined as to describe the fourth moments of the distribution of orientations of the structural units on the basis of a random distribution of the rotational angle of the unit about the segment axis. It is found that the use of the method of fluorescence polarization combined with absorption dichroism and/or emission gives the values of the optical anisotropy ratios of the fluorescent unit, and that the effects of the thermal agitation of the structural unit can be separated from the moments of the orientation distribution for the simplest case.
    Additional Material: 2 Ill.
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  • 12
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 747-748 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 13
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 753-762 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Eight epoxy-diamine networks have been formed, diamines with 2 to 12 methylene groups being used as curing agents. Dynamic mechanical tests revealed four transition regions in the dynamic loss modulus/temperature relationship. Two possible explanations for the relaxation of the glycidyl portion of the structure are proposed. One of the relaxations could be due to the breakdown of hydrogen bonds through the hydroxyl and ether groups. The second could be ascribed to the relaxation of the unbonded glycidyl groups or a second relaxation of the glycidyl groups after the breakdown of the hydrogen bonds.
    Additional Material: 2 Ill.
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  • 14
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 783-794 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Previous theoretical calculations of elastic constants for cellulose based on force constants for bond stretching and bending of valence angles have yielded axial stiffness values admittedly too low. The present analysis accounts for a hitherto unexamined geometrical effect associated with deformation of interchain hydrogen bonds. To do this, most primary bond deformations are neglected so the resulting calculation gives an upper bound for the axial stiffness. By using two different sets of hydrogen bond force constants, values of 24.6 and 31.9 × 1011 dyne/cm2 were obtained for Young's modulus in the chain direction. These values are very much larger than earlier calculations and experimental determinations from cellulosic fibers, indicating both the importance of the effect considered here and the likelihood of an exact analysis yielding an acceptable result.
    Additional Material: 6 Ill.
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  • 15
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 845-853 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The conformational energy contribution (ΔUconf) to the heat of solution in polymer-solvent systems is presented and discussed in connection with chain conformational properties. In particular, ΔUconf has been discussed in terms of various possible mechanisms of coil deformation.
    Additional Material: 2 Ill.
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  • 16
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 889-896 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It is demonstrated that in a filled polymer the thermal stresses resulting from the difference in the thermal expansion coefficients of the filler and the polymer have significant effect on the apparent coefficient of thermal expansion of the composite. A model is constructed to aid the thermal stress analysis, and the results are found to agree well with the experimental data obtained from other sources. An expression for the apparent densities of filled polymers is also obtained but the agreement between the present prediction with an existing test result is found to be only qualitative.
    Additional Material: 6 Ill.
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  • 17
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 947-962 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Diffusion coefficients and solubilities of methane in polyisobutylene have been measured at four temperatures between 102 and 188°C. in the pressure range 23-341 atm. Diffusion coefficients extrapolated to atmospheric pressure range from 1.72 × 10-6 cm.2/sec. at 102°C. to 1.5 × 10-5 cm.2/sec. at 188°C. corresponding to an activation energy for diffusion of 8.7 ± 0.4 kcal./mole. Solubilities are small, about one molecule of methane for every forty carbon atoms in the polyisobutylene at 300 atm. partial pressure of methane. Solubilities vary little with temperature, but show an apparent minimum between 127 and 188°C. With improved methods of data analysis, diffusion coefficients and solubilities have been recalculated from previously reported studies on nitrogen in branched polyethylene and methane in branched polyethylene, linear polyethylene, and polystyrene. Recalculated diffusion coefficients are essentially the same as those reported previously, but the recalculated solubilities are decreased from 2 to 30%. The solubilities of all five systems show strong deviations from Henry's law, i.e., increases in partial pressure of methane and nitrogen with respect to solubility exceed linearity. The partial pressure (or fugacity) - solubility data may be interpreted in terms of a sorption model in which sorbed molecules are accommodated in widely dispersed, unoccupied volumes or sites in the polymer. An almost equivalent, solution model in which the first sorbed molecules to enter the polymer are accommodated to a large extent in existing volumes in the polymer, with successively sorbed molecules swelling the polymer to a greater extent (i.e., partial molal volume of sorbed molecules, V1, increasing with concentration) can also account for these data.
    Additional Material: 5 Ill.
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  • 18
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1021-1031 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The discrepancy between the values of the anisotropy of methylene groups determined from crystal refractive indices, stress-optical data, and gas and liquid light-scattering depolarization is explained on the basis of the effect of the internal field on the polarizability of the isolated molecule. The internal field may arise from intermolecular or intramolecular interactions which depend upon molecular conformation and state of aggregation. A simple continuum calculation based upon an extension of the calculation of the Lorenz-Lorentz field is shown capable of accounting for the discrepancy.
    Additional Material: 5 Ill.
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  • 19
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1059-1073 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Nylon 66 films exhibiting form I melting behavior show the γ mechanical relaxation at -140°C. Samples which have form II melting behavior do not show this relaxation. The γ relaxation disappears when material having form I behavior is converted to material having form II behavior by annealing or by cold drawing. The form I and form II types of melting behavior are also found in poly(ethylene terephthalate); the interconversions and thermal behavior of the forms are analogous to the nylon 66 case. In poly(ethylene terephthalate), the β relaxation at -40 to -60°C is present only when form I melting behavior is found. Conversion to form II melting behavior by annealing or drawing (80°C) again causes the relaxation to disappear. No β relaxation was found in amorphous polymer. The γ dispersion in nylon 66 and the β dispersion in poly(ethylene terephthalate) can therefore be associated with the crystalline structure responsible for form I melting behavior. Form I melting behavior has been associated with foldedchain crystals based on previous work. It is therefore postulated that the γ dispersion in nylon 66 and the β dispersion in poly(ethylene terephthalate) are associated with motions in the chain folds. This assignment is not inconsistent with the change in the γ dispersion of nylon 66 with the number of backbone CH2 units, since these will affect the fold structure.
    Additional Material: 10 Ill.
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  • 20
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1116-1118 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 21
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1151-1163 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The strength-limiting process in the fracture of semicrystalline fibers and highly oriented films is the rupture of tie molecules connecting the folded chain lamellae in the machine direction. This view is supported by the data on stress and temperature dependence of lifetime of fibers under load and on radical formation during the fracture experiment. The observed tensile strength, however, is about 10 times smaller and the number of fractured chains between 100 and 1000 times larger than expected on the basis of the known number of tie molecules in the fracture plane. This discrepancy is a consequence of the inhomogeneity of the micromorphology of fiber structure, which causes a much larger stress concentration on the most unfavorably located tie molecules than the average value one would expect in the case of perfectly uniform stress distribution on identical tie molecules. The fluctuation of amorphous layer thickness, of number and length of tie molecules, produces such a high stress concentration on some tie molecules throughout the sample that they rupture long before the average stress concentration is sufficient for chain fracture. By accumulation of damage caused by gradual chain rupture the weakening of the sample locally proceeds so far that at the maximum damage concentration, microcracks start to form, and the fiber breaks.
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  • 22
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 525-536 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dynamic shear behavior of four highly amorphous polymers in the unstretched and stretched states (draw ratios 3:1 to 6:1) was investigated with a torsion pendulum at temperatures from 4.2°K to 180-300°K and frequencies from 0.4 to 3.2 cps. The polymers studied were polystyrene, poly(vinyl acetate), poly(vinyl propionate), and poly(isobutyl vinyl ether). Previously unreported loss maxima were found at 48°K (1.5 cps) and 149°K (1.3 cps) for poly(vinyl proplonate), at 10°K (1.0 cps) for poly(vinyl acetate) and at 9°K (1.6 cps) for poly(isobutyl vinyl ether). Uniaxial orientation increased the shear storage modulus G, measured with the torsion axis parallel to the stretch direction and caused changes in the loss peaks which depended on the polymer material studied.
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  • 23
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    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 551-561 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Small-angle x-ray scattering studies were made on bulk-crystallized samples and annealed oriented films of TMPS. The temperature dependence of the small-angle scattering was determined over a range of annealing conditions. The effect of sample molecular weight on the small-angle peaks was also studied. The peak intensity, measured at room temperature after annealing, was strongly dependent on the annealing conditions. The position of the peak gradually moved to smaller angles (larger d spacings) as the annealing temperature was raised. Surface free energies were deduced from the melting point dependence of the crystallite size. This surface energy was found to increase with molecular weight in accord with values deduced for spherulite growth rate-temperature dependence.
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  • 24
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    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 593-600 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A model is proposed to account for the regular twisting of radial ribbons in certain polymer spherulites. The model assumes that the ribbons have crystallographically regular fold surfaces and that growth of the ribbons is nucleation-controlled. The model leads directly to a possible mechanism of spherulitic growth in some polymers.
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  • 25
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    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 659-666 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A specimen of linear polyethylene was subjected to isothermal secondary crystallization at a series of temperatures below the primary isothermal crystallization temperature, the melting and primary crystallization stages being held constant throughout the investigation. Dilatometric measurements exhibit an S-character at low values of undercooling Tp - Ts, where Tp and Ts are, respectively, the primary and secondary crystallization temperatures; at larger undercoolings, however, an initial very rapid crystallization is followed by a very slow stage. When corrected for thermal contraction of the polymer, the net degree of secondary transformation is seen to peak at a temperature in the range 109-113°C. The S-character of the isotherms and the peaked temperature variation of degree of transformation lead to the conclusion that a large portion of the secondary crystallization consists of the nucleation and growth of the new crystallites. Johnson-Mehl-Avrami analysis leads to a model of heterogeneous nucleation within the remaining amorphous zones, followed by one-dimensional, diffusion-controlled growth.
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  • 26
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    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 675-685 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The strength and extensibility of an unfilled styrene-butadiene rubber vulcanizate were determined in constrained biaxial tension (essentially pure shear) by stretching thinwalled cylindrical specimens in the axial direction with an Instron tester while gas pressure was admitted to maintain constant the outside diameter of a specimen. The rupture stress, λ1b, and the extension ratio, λ1b, in the axial direction and the rupture stress, σ2b, in the circumferential direction were determined at extension rates from 0.0031 to 3.1 min-1 and temperatures from 25 to 90°C. Rupture data in simple tension were also obtained by testing ring specimens under similar test conditions. The time-temperature shift factor, aT, obtained by superposing rupture data at different temperatures, gives a constant activation energy of 35 kcal. Doubly logarithmic plots were prepared showing the dependence of σ1b/λ1b, σ2b, and λ1b from the biaxial tensile tests and of σb/λb and λb from the simple tensile tests on the temperature-reduced extension rate, \documentclass{article}\pagestyle{empty}\begin{document}$ \dot \lambda a_T $\end{document}. (The quantities σ1b/λ1b, σ2b, and σb/λb are rupture stresses based on the dimensions of undeformed specimens.) At equal values of \documentclass{article}\pagestyle{empty}\begin{document}$ \dot \lambda a_T $\end{document}, the extension ratios λ1b and λb are sensibly identical. The ratios σ1b/σb and σ2b/σb, as well as λbσ2b/σb, were obtained from rupture data read from the composite curves at selected values of \documentclass{article}\pagestyle{empty}\begin{document}$ \dot \lambda a_T $\end{document}. Also, similar ratios were derived from stress data at equal extensions in biaxial and simple tension for 1.25 ≤ λ ≤ 3.0, the range comparable to that in which rupture data were obtained. A consideration of the ratios given by both the rupture and the stress data shows that the von Mises failure criterion is not applicable, although the departure is small except at the larger values of λb.
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  • 27
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 747-747 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 28
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 750-750 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 29
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 775-782 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A statistical model for the stereospecific polymerization of vinly monomers on Ziegler-Natta catalytic systems is presented. The basic assumptions of the model are: (a) the catalytic centers are asymmetric, so that at a given catalytic center the monomer CH2=CHR is inserted into the chain with two different rates according to the two different configurations of the opening carbon atom having the R group; (b) the insertion of a monomeric unit in the growing chain is affected also by interactions with the previous monomeric unit. Isotactic, syndiotactic, atatic, or stereoblock polymers are obtained according to the relative values of the two energy parameters expressing these two effects.
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  • 30
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 821-827 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A specimen of linear polyethylene was subjected to isothermal secondary crystallization at a series of temperatures below the primary isothermal crystallization temperature, the melting and primary crystallization stages being held constant throughout the investigation. Dilatometric measurements exhibit an S-character at low values of undercooling Tp - Ts, where Tp and Ts are, respectively, the primary and secondary crystallization temperatures, whereas at larger undercooling, an initial very rapid crystallization is followed by a very slow stage. When corrected for thermal contraction of the polymer, the net degree of secondary transformation is seen to peak at a temperature about 5°C below Tp. The S-character of the isotherms and the peaked temperature variation of degree of transformation lead to the conclusion that a large portion of the secondary crystallization consists of the nucleation and growth of the new crystallites. Johnson-Mehl-Avrami analysis leads to a model of heterogeneous nucleation within the remaining amorphous zones, followed by one-dimensional, diffusion-controlled growth.
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  • 31
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 855-866 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Heats of solution (ΔHexp) in solvents of increasing thermodynamic power have been measured for four polymers: polystyrene (PS), poly(vinyl acetate) (PVAc), polyisobutylene (PIB) and polydimethylsiloxane (PDMS). After subtraction from ΔHexp of an interaction term (calculated by the Hildebrand treatment based on solubility parameters) and the excess volume term, the quantity remaining is interpreted as the conformational energy contribution (ΔUconf) to the heat of solution. ΔUconf appears to correlate well with some basic conformational properties of the chain, such as the sign of the temperature coefficient of unperturbed dimensions derived from solution properties, and shows a monotonic behavior with α, the expansion coefficient of the polymer coil in the final solution. Numerical values of ΔUconf, at least for those cases in which polymer solubility parameters are known with some certainty, are much larger than those evaluated from rubber elasticity experiments (through the experimentally accessible value of the energy component of the force of retraction im simple elongation).
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  • 32
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1101-1109 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polyvinylpyridine of molecular weight 0.77 × 106 was crosslinked by 2.5, 5, and 10% BrCH2C6H4CO(CH2)8COC6H4CH2Br and by 10% ClCH2C6H4CH2Cl; quaternization of the gel was completed with n-butyl bromide. Swelling ratios in aqueous solutions of lithium, sodium, and 4-isopropyl-N-n-butylpyridinium bromide and in methanolic lithium bromide were determined. Selectivity increased in the sequence Li+ 〈Na+ 〈PrN+-C5H5. The Flory parameter χ1, which measures interaction between solvent and polymer, decreased from 1.5 kT to nearly zero with increasing density of crosslinks in the aqueous solutions, and from 3 kT to 0.5 kT in the methanol solutions. The inverse proportionality of q2/3 (q = swelling ratio) to the crosslinking density was approximately verified for swelling of the resins in water, methanol, and dimethylformamide.
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  • 33
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1165-1186 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The proton spin-lattice relaxation times (T1) of linear polyethylenes (PE) of varying morphology were measured as a function of temperature. The T1 of oriented bulkcrystallized and solution-crystallized material was isotropic, in disagreement with calculations based on a sample dipole pair model. Motion in the non-crystalline regions of the samples is shown to be responsible for the T1 minimum occurring around -20°C. The dependence of T1 at the minimum on the long period reinforces the model of an amorphous fraction composed of disordered lamellar surface layers. The temperature of the T1 minimum and the dependence of T1 on the long period imply that the mobility of these amorphous regions is reduced in cold-drawn and solution-crystallized samples. This mobility irreversibly increases with annealing. In highly relaxed samples the motion of a small portion of the disordered regions is almost liquidlike, as indicated by the presence of a second shorter T1.
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  • 34
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 963-981 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The structural and steric isomerism of propylene polymers has been estimated on the basis of solution properties as well as infrared and high-resolution nuclear magnetic resonance spectra. Three general types of polypropylenes were prepared: polymers prepared with the cationic catalytic system AlCl3-C2H5Cl, stereoblock polymers obtained by successive extraction from a commercial product and isotactic polymers of low molecular weight obtained by thermal degradation of a highly isotactic polymer followed by hydrogenation with Adam's catalyst in dioxane at 40°C. The characterization of all samples was accomplished by equilibrium ultracentrifugation, vapor-pressure osmometry, viscometry, and gel-permeation chromatography. It is found that the molecular chain of cationically prepared polymer is somewhat branched owing to structural isomerism during polymerization. Isoamyl acetate is found to be a theta solvent for stereo-block as well as for atactic and syndiotactic polymers; the theta temperature is determined as the temperature at which the light-scattering second virial coefficient A2 vanishes. A close correlation is found between the theta temperature and stereoisomerism. The absorbances of the 1154 and 974 cm-1 bands in the infrared spectra decrease with decreasing molecular weight; in addition to the mere existence of alternating CH2 and CH(CH3) groups in the polymer chain, rather long sequences of this type are required for the appearance of these bands. Changes in the absorption band at 997 cm-1 show that chains consisting of over ten isotactically connected monomer units can assume a helical conformation. From the high-resolution NMR spectra of different polypropylenes, including isotactic polymers of low molecular weight, it is found that in estimating the microstructure, account must be taken of the effects of stereoisomerism within tetrads of monomer units on the apparent widths of the methylene proton resonances. If substantial concentrations of several of the possible types of tetrads are present (i.e., if the tactic sequence lengths are quite short), then it is difficult to determine the relative amounts of tactic dyads accurately from the 100 Mcps methylene proton resonances.
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  • 35
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1033-1057 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The phenomenon of double melting, as manifested by two characteristic endotherms in the melting region on a differential thermal analysis (DTA) scan, has been studied in nylon 66 and polystyrene as a function of sample treatment by annealing or drawing. A variety of techniques were used in these studies including DTA, x-ray diffraction, electron microscopy, and mechanical testing. It is shown that the two endotherms are not caused by a bimodal crystal size distribution, by recrystallization, by orientation changes, or by phase changes. It is proposed that one endotherm is caused by the melting of foldedchain crystals, while the other is due to the melting of less perfect bundle crystals. This view is well supported by the results, especially by the DTA measurements made at different heating rates. Published data on the thermal behavior of annealed and drawn poly(ethylene terephthalate) and on polyethylene crystallized at various pressures may also be explained on this basis if it is allowed that in polyethylene the chains may be more extended.
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  • 36
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1745-1754 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The yield-stress behavior of two glassy polymers is studied through the glass transition region over a wide range of strain rates. For temperatures below the glass transition temperature, the yield stress behavior could be described as a non-Newtonian flow in agreement with Eyring's theory, if one excepts a narrow range relating to the slowest strain rates. For temperatures above Tg, the yield-stress behavior is still nonlinear but fits the relations based on the concept of free volume.
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  • 37
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1811-1818 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A “dual sorption” model has been proposed by Michaels, Vieth, et al. to explain extensive equilibrium sorption data for several gases in some glassy polymers. To explain data on sorption kinetics, it was further postulated that one of the sorption modes immobilizes the gas molecules. Stated mathematically, this model leads to a modified form of Fick's second law. Both normal and desorption time lags for diffusion have been computed here for this model of diffusion in glassy polymers. The computed time lags are shown to be dependent on the boundary concentrations used in permeation. Experimental measurement of these time lags would be a sensitive and critical test to ascertain the validity of this theory.
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  • 38
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1863-1882 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(methyl methacrylate) tensile bars were prepared containing nearly spherical polytetrafluoroethylene particles in concentrations from one to a thousand particles per gauge length of the bars. Particle diameters varied from 0.0035 to 0.018 in. Exhaustive tensile tests were performed at sufficiently high strain rate to assure brittle fracture and the results analyzed statistically by the theory of extreme values as proposed by Epstein. The results suggested that the polytetrafluoroethylene particles themselves did not act as flaws, but that they intensified the stress field on natural flaws which acted as the origin of fracture. Assuming a Laplace distribution as the underlying distribution of tensile strength (not to be confused with observed distribution of tensile strengths) gave predicted fracture statistics in good agreement with experiment.
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  • 39
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1937-1954 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The distribution of molecular weights in realistic free-radical polymerizations with branching was analyzed theoretically. Series solutions were obtained for the fraction of molecules with r repeating units and the number of branch points contained in molecules with r repeating units. Branching by transfer processes was found to increase the proportion of both high and low molecular weight components in the system. The apportioning of branch points among r-mer molecules was shown to be somewhat narrower than a Poisson distribution. The major difference between the calculated distributions and previous model distributions for branched systems was the absence of discontinuities in the moments at all levels of branching.
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  • 40
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1983-1986 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 1 Ill.
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  • 41
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 2005-2018 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The problem of the structural theory of macromolecular networks is formulated and discussed in general terms. The conditions required for a system to become a homogeneous macromolecular network are defined and discussed. Networks are divided according to the nature of their junctions into three classes: energetic (with chemical or quasi-chemical crosslinks), topological (with entangled chains), and contact (with frictional interactions). The main features of these three classes are discussed. A distribution density function ψ describing the configurations of macromolecules in network systems is introduced. The phase space of variables is 4(N + 1)-dimensional and includes the coordinates of (N + 1) vectors hi joining the adjacent network junctions and (N + 1) contour lengths li of the network chains. The system of simultaneous equations required for the determination of the function ψ includes the equation of continuity, kinematic equations for the deformation velocity of the individual junctions, the force balance equation needed for the determination of sliding rates li, kinetic equations for the processes of junction breakage and reformation, and the equilibrium distribution of network junctions defining the initial conditions for the distribution function ψ.
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  • 42
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 2061-2072 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Extended-chain crystals of high molecular weight polymethylene, a polyethylene with a broad molecular weight distribution, and three fractions of polyethylene were grown from the melt under elevated pressure. Comparison of the crystal size distribution in the molecular chain direction (measured on fracture surfaces by electron microscopy) with the molecular weight distribution (measured by gel-permeation chromatography) gave the following results. Up to molecular weight 10,000 all samples showed eutectic separation into fully extended chain crystals of narrow molecular weight distribution. Above molecular weight 10,000 mixed crystals were formed. Under the chosen crystallization conditions larger chain extension was achieved with higher molecular weights. However, an increase in molecular weight by a factor of 1000 led only to a tenfold increase in chain extension. These facts are discussed in the light of a proposed mechanism of crystal growth.
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  • 43
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 2115-2138 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The Kuhn-Grün theory for the birefringence and dichroism of rubbery polymers is extended to the case of copolymers consisting of two or more statistical segments of differing lengths. It is shown that the previous equations are applicable provided that the anisotropy of polarizabilities and absorptions are replaced with suitable averages in which the segment anisotropies are weighted by the squares of their segment lengths. This indicates that the stress-optical coefficient will not generally vary linearly with composition. The orientation measured from the dichroism of bands arising from different segments will be different.
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  • 44
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 2142-2143 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 45
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 2141-2142 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 46
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 47-55 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A method of determining the distribution of branching in polydisperse polymer samples is proposed. This method uses data from concurrent gel permeation chromatography and sedimentation-velocity experiments. Tedious fractionation, which must precede other methods of determining long-chain branching, is eliminated. An example of use of the method on the data of a sample of styrene-divinylbenzene copolymer is given.
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  • 47
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 87-104 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: This paper reports an electron microscopy study of the morphology of crystals of poly(vinylidene chloride) prepared under a variety of conditions and of the carbons resulting from the pyrolysis of the polymer. The structure of the polymer carbons prepared under conditions such that the polymer does not pass through a plastic phase is closely related to the morphology of the original polymer. The shapes of the crystals and of the crystal pseudomorphs are indexed in terms of the unit cell proposed by Narita and Okuda. Morphological studies of this kind are important in discussing the graphitizability of polymer carbons, their mechanical properties and pore structure, and the kinetics of the dehydrochlorination reaction.
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  • 48
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 105-111 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Heterogeneous nucleation and crystallization of FEP Teflon and nylon 6 melts against high energy surfaces (i.e., gold) produce an interfacial region, in these polymers, of high mechanical strength. Dissolution of the metal substrate rather than removal by mechanical means results in a polymer surface which is amenable to conventional structural adhesive bonding. Nucleation and crystallization of the polymer melts in contact with phases of low surface energy (e.g., vapor) result in the generation of weak boundary layers.
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  • 49
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 249-252 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: NO ABSTRACT.
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  • 50
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 497-513 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Triplet → singlet energy transfer in nylon 66 film (donor) dyed with proflavine (acceptor) is demonstrated by a decrease of the nylon phosphoresence lifetime and an increase in the proflavine delayed fluorescence/nylon phosphoresence ratio with increasing proflavine concentration. Although the observed donor phosphorescence decay is apparently exponential, the transfer is probably via a long-range dipole-dipole (Förster) interaction, rather than by triplet exciton migration. Arguments are advanced to support this view. Proflavine delayed fluorescence produced by a direct excitation process is also observed. The decay time for this process is roughly an order of magnitude less than that for the sensitized process. All emission intensities are shown to vary linearly with exciting light intensity. Finally, temperature dependence of proflavine delayed fluorescence under different excitation conditions is shown. The efficiency of direct excitation process increases markedly near -50°C as the temperature is increased; the sensitized delayed fluorescence intensity follows that of the nylon phosphorescence with increasing temperature, as expected.
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  • 51
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 587-592 
    ISSN: 0449-2978
    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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  • 52
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 601-608 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The glass transition temperatures Tg of several fluorine-containing polymers were determined by use of the differential scanning calorimeter. Values between -3 and 230°C were obtained. In polymers of α-olefins, Tg increases with the fluorine content of the backbone and the length of the n-perfluoroalkyl branch. In styrene polymers Tg also is higher if the backbone contains fluorine but nearly the same Tg's are found for polymers with phenyl and pentafluorophenyl groups. Saturated polymers of perfluoro-α,ω-dienes have lower Tg's than polyperfluoro-α-olefins. The Tg's of chloroperfluoropolymers are higher than those of perfluoropolymers. Polyperfluoropentadiene-1,3 has the lowest Tg of the polymers examined. Polyperfluoropentadiene-1,3 forms by 1,4-addition.
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  • 53
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 667-674 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Drawn poly(ethylene terephthalate), PET, yarns have been heated for 1 min in silicone oil. The resulting samples were studied by x-ray diffraction and mechanical properties were measured. The results suggest that drawn PET consists of highly extended molecules essentially parallel to one another, with few folds present. On heating, chain folding occurs. This model is very similar to that proposed by Dismore and Statton for drawn nylon 66 yarns.
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  • 54
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 143-151 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A theoretical discussion is presented on the mechanisms by which an isolated pulsating air bubble in a viscoelastic solid dissipates its energy. The analysis is limited to the situation where the amplitude of motion is assumed to be sufficiently small that the stress strain relations may be described by linear equations with convected differentiation replaced by ∂/∂t. The theoretical thermal, radiation, and viscous damping constants are calculated for resonant air bubbles in unvulcanized natural rubber; however, the results are typical of elastomers in general.
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  • 55
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 231-240 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The birefringence of several biaxially oriented polypropylene films swollen with a number of fluids has been measured and found to exhibit a minimum when plotted against the fluid refractive index, as predicted by the theory of Wiener. However, a discrepancy in the form birefringence behavior is observed when samples of different degrees of crystallinity but the same total birefringence are compared. These results are interpreted in terms of Bullough's theory and suggest that this discrepancy arises because of different morphologies. A refractometric technique was employed that makes possible the simultaneous determination of birefringence and the volume fraction of fluid.
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  • 56
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 153-161 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The morphology of polyethylenes formed upon polymerization by γ-radiation below the melting point in various reaction media was investigated by using electron microscopy and scanning electron microscopy. When the polymerization was carried out in bulk at 30°C and in methanol, the polymer was fibrillar, and a small-angle x-ray scattering curve of the polymer did not indicate the existence of a long period. This suggests that the chains in the crystals have an extended conformation. When the polymerization was carried out in the presence of xylene at 30°C, platelet crystals having a folded structure were obtained. It was thus shown that the morphology of the growing polymer crystals is very much affected by the solubility of the polymer in the reaction medium. The effect of stirring during polymerization on the crystalline morphology was also studied.
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  • 57
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 209-217 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The intrinsic viscosity of a polymer in a solvent mixture is related to the excess free energy of the solvents. Intrinsic viscosities at different temperatures are obtained for poly-2-vinylpyridine-chloroform-ethyl alcohol, poly(methyl methacrylate)-chloroform-ethyl alcohol, polystyrene-cyclohexane-benzene, polystyrene-dioxane-chloroform, and polystyrene-cyclohexane-ethanol. Qualitative, but not quantitative, agreement is found between theory and experiment.
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  • 58
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1315-1328 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The circumstances of the formation of kink bands have been investigated with a newly designed shearing device and light and electron microscopes. Kink bands having sharp edges and reflection symmetry about the edges were formed and studied in the two crystalline polymers, high-density polyethylene and isotactic polypropylene, but could not be formed in the two glassy polymers, poly(4,4′-dioxydiphenyl-2,2-propane carbonate) and poly(2,6-dimethylphenylene oxide). The characteristics of the oriented polymer that promote kink bands seem to be easy slip along the orientation axis, and resistance of the oriented fibrils to length changes. Kink bands were found to initiate at sites of shear stress concentration, where the fibrils are first deformed into an S-shaped curve, that then tightens and finally collapses into kinks.
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  • 59
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1303-1314 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Column chromatographic fractionation of polystyrene was carried out with the methyl-ethyl ketone-methanol system, and effects of various experimental conditions on the fractionation efficiency were studied. For samples with molecular weights below about 6 × 105, neither the temperature gradient (0.7°C/cm), nor the flow rate of solvent (30-270 ml/hr) seriously influences the fractionation efficiency. The effect of temperature gradient becomes apparent only in the high molecular weight region and only if the gradient of the solvent composition is too steep. High flow rates (ca. 125 ml/hr) clearly affect the fractionation efficiency for a high molecular weight sample (Mw = 5.46 × 105). Precipitation chromatography for the fractionation system was calculated from the phase equilibrium data according to the mass transport equation proposed by Schulz et al. The theoretical analysis gives support to the observed dependence of the temperature effect on molecular weight. Comparison of the observed and theoretical relations between elution volume and molecular weight of the fraction, on the other hand, indicates that the process of fractionation is simply elution of polymer off the support without reprecipitation. Certain conditions of polymer deposition on the support are required for optimal results.
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  • 60
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1435-1438 
    ISSN: 0449-2978
    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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  • 61
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1461-1472 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Thermal analysis has been carried out on drawn nylon 6 filaments annealed at various temperatures between 150 and 210°C and then methoxymethylated to various degrees. It is shown that the melting point inherent to the morphology of drawn nylon 6 can be obtained from samples in which the reorganization of defect crystallites in the course of thermal analysis is prevented by a proper degree of methoxymethylation of amorphous regions. The melting point thus obtained is in linear relation with the reciprocal crystallite size in the direction of fiber axis which has been obtained from small-angle x-ray data and crystallinity. The extrapolation and the slope of this linear relation give the equilibrium melting point of nylon 6 as 245°C and an end-surface free energy of 42 erg/cm2. The results seem to provide strong support for the presence of chain-fold surfaces in the drawn and annealed polymers.
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  • 62
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1489-1494 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The Raman scattering of nonplanar (form 2) poly(vinylidene fluoride) (PVF2) is described. Unique Raman bands not observed in the infrared spectra are found at 2973, 1437, 1327, 1198, and 1059 cm-1. Band assignments are discussed by comparing infrared and Raman spectra of form 2 PVF2.
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  • 63
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1705-1719 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The temperature dependence of relative modulus observed in filled thermoset, thermoplastic, and polyelectrolyte salt matrices is explained on the basis of induced stresses produced by the differences in the thermal expansion coefficients of the constituent materials. The analysis is based on the assumption that the modulus of the matrix in a filled polymer is less than that of the unfilled polymer. The temperature dependence of relative modulus is expressed as a function of the difference in thermal expansion coefficients, the volume fraction, the relative modulus in the unstressed state, and mechanical properties of the phases. Agreement is good between the analysis and experimental results for three systems: epoxy and glass, polyethylene and wollastonite, and a polyelectrolyte salt with mica and asbestos.
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  • 64
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1785-1809 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Infrared spectroscopic studies have been made of mixed crystals of linear polyethylene and perdeuteropolyethylene. On the basis of normal vibration analyses by Tasumi and Krimm it had been shown that the study of crystal splittings of internal chain modes in such mixed crystals could provide information on the geometry of chain folding. The present results, which include a study of n-paraffin (C36) mixed crystals, confirm these predictions. They show that (110) folding predominates in dilute solution grown crystals, and that this is transformed to (200) folding in melt-crystallized polymer. Folding with adjacent re-entry is favored, a random re-entry model being clearly eliminated.
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  • 65
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1883-1894 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Data existing in the literature for the spherulitic growth rate of molecular weight fractions of linear polyethylene, poly-(tetramethyl-p-silphenylene)siloxane, and trans-1,4-polyisoprene have been analyzed according to nucleation theory on taking into account the influence of chain length on the free energy of fusion. All three polymers display very similar behavior in that the interfacial free energy reaches an asymptotic value at high molecular weights, decreases as the molecular weight is lowered, and appears to also reach an asymptotic value at low molecular weights. Although the changes in the interfacial energy with molecular weight are quite distinct, the relative change is much less than has been previously reported when a molecular crystal analysis is used. The same general behavior observed points out the dominating influence of the chain-like character of the molecules in governing the growth rate.
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  • 66
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1111-1115 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 67
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1187-1195 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Extensive studies of the kinetics of spherulitic crystallization have been made on fractionated samples of TMPS. An analysis of these results reveals that a two-dimensional growth rate mechanism is a more likely mode of growth than a three-dimensional one. This conclusion is substantiated by experimental evidence from optical microscopy and light scattering from within spherulites. The crystallite end surface energy is found to increase as the molecular weight is raised.
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  • 68
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1275-1278 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 69
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A modus operandi is developed for determining the molecular structure of hydroxypropylcellulose (HPC), and characterizing, in quantitative terms, the morphological changes occurring when a water-cast film of the polymer is deformed. This involves the application of the following eleven different physical measurements: wide-angle x-ray diffraction, differential scanning calorimetry, density, melt rheometry, infrared spectroscopy, refractive index, birefringence, sonic modulus, small-angle light scattering, optical and electron microscopy. In addition, a computer was utilized as a mathematical diffractometer. Morphologically, water-cast HPC was observed to have structure at all levels, from the molecular to the supermolecular. The HPC molecule has a backbone of anhydroglucose units twisted into an irregular 31 helix. Intramolecular hydrogen bonding of the poly(propylene oxide) side chains leads to a stiff, rodlike molecule. The molecules are packed into microfibrillar crystallites 470 Å long and 34 Å in diameter. The microfibrils in turn, associate into supermolecular rodlike structures. The structural rearrangements that occur at each morphological level during deformation of HPC film are quantitatively examined and described.
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  • 70
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1329-1355 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Mechanical relaxation has been studied at 0.67 cps in linear polyethylene (LPE) and polytetrafluoroethylene (PTFE) between -190 and -20°C. Specimens were prepared by use of various thermal treatments to produce in LPE a range of crystalline fractions from 0.690 to 0.825 and in PTFE from 0.615 to 0.870. An empirical theory is proposed relating the modulus of the crystalline-amorphous composite solid to the moduli and the volume fractions of the two phases. The empirical theory is shown to be in accord with the bounds of Hill and of Hashin and Shtrikman. The theory is used to determine the magnitudes of the crystalline and amorphous components of the low temperature relaxations in LPE and PTFE from measurements of logarithmic decrement and shear modulus. In PTFE the γ relaxation occurs in the amorphous fraction alone. In LPE the γ relaxation is a composite one, formed from the superposition of a small crystal relaxation and a large amorphous relaxation. For the crystal relaxation in LPE the ratio of relaxed to unrelaxed modulus equals 0.78; for the amorphous relaxation, the ratio equals 0.23. In a specimen of LPE with crystal fraction 0.69 the crystal contribution to the relaxation is 25% of the total. The magnitude of the unrelaxed modulus of the crystal fraction of LPE (modulus of polycrystalline LPE at -190°C) is in reasonable agreement with theoretical calculations of Odajima and Maeda.
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  • 71
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1385-1392 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Shear viscosity and dielectric dispersion measurements have been made on a series of concentrated solutions of poly-p-chlorostyrene in toluene, chlorobenzene, and diethylbenzene, as well as on the pure polymer. It is found that the product ηνm/T is nearly temperature-independent in the present range of measurement (30 ≤ νm ≤ 30 ≤ 104 Hz), where νm is the frequency at which the dielectric loss maximum occurs. For the pure polymer, ηνm (200/T) is 1011.5 poise/sec. This leads to a segmental jump distance of 5 Å. Although the results in this range correspond quite well to the concept of a segmental friction constant determined by the matrix viscosity, deviations appear as the apparent energy of activation for viscous flow decreases below 13 kcal/mole. There is reason to believe that these deviations reflect the increasing importance of bond rotation barriers at low matrix viscosity. It is speculated that the damped torsional oscillator interpretation of f0 proposed by Tobolsky will become valid in systems still more fluid.
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  • 72
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A new light-scattering experiment which allows a direct determination of the conformation of macromolecules deformed in flow is described. Light-scattering relationships based on the interference function are developed, and results of an experimental study are detailed. The deformed conformation of high molecular weight polyisobutylene was determined in a Couette-type shear field. Decalin was the solvent. Variables investigated were the shear rate (0 to 600 sec-1), the polymer molecular weight (1.0 × 107 to 1.6 × 107), and the polymer concentration (2.0 × 10-4 to 8.0 × 10-4 g/cc). Conformation variables determined were the orientation of the molecule in the shear field and its maximum and minimum extension ratios in the plane defined by the direction of flow and the direction of the shear rate. The deformation of the macromolecule was found to be markedly discrepant when compared to the dynamic macromolecular models which assume complete coil flexibility, and more closely in agreement with the recent theories of Cerf, developed for nonfree-draining coils which exhibit a finite internal viscosity.
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  • 73
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1439-1443 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 74
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1473-1481 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The mechanical and dielectric low temperature absorptions of poly(vinyl chloride) (PVC) and several modified PVC's have been studied over the temperature range from -60 to +60°C. with some tests extending to -150°C. and others to +170°C. The results indicate that the low-temperature absorption near -50°C (β2 absorption) decreases in intensity with chlorination, while the absorption at a higher temperature near 0°C (β1 absorption) decreases in intensity with hydrogenation. The apparent activation energies of the β1 and β2 absorptions were calculated to be 16 kcal/mole and 10.7 kcal/mole, respectively. Besides, the β2 absorption markedly decreases in intensity with addition of plasticizer, while the intensity of β1 absorption is not much affected by increasing plasticizer content. From these results, the β1 and β2 processes are concluded to be the results of molecular motion in crystalline and amorphous region in PVC, respectively. For samples of reduced Cl content, another low-temperature absorption was located near -120°C (γ absorption) and attributed to the presence of short sequences of ethylene units. It has also been observed that the temperature location of the high temperature absorption near 100°C (α absorption) shifts linearly to higher temperature with increasing chlorine content and to lower temperature with increasing hydrogen content.
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  • 75
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1513-1523 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Six homologs of the cellulose triester series were found to exhibit, in general, three second-order transitions as determined dilatometrically. A parallel study of torsional modulus versus temperature revealed one glass-rubber transition, which allowed molecular assignment of one of the above. The dependence of the remaining two transition temperatures on length of the ester group permits some speculation with regard to their origin. The glass-rubber and secondary transitions exhibit an inversion for cellulose trivalerate and higher homologs, the two secondary transitions occurring at temperatures higher than the glass-rubber transition. A possible explanation for this anomaly in terms of side-chain crystallization is discussed.
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  • 76
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1639-1649 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The melting transitions of both crystalline forms of trans-1,4-polyisoprene, as detected by differential thermal analysis, have been identified by attendant studies with optical microscopy and x-ray diffraction. The lower-melting (LM) form melts initially at a temperature which depends upon the crystallization temperature but which, under our experimental conditions, is between 45 and 53°C. If recrystallization is allowed to occur, the apparent final melting point, which depends upon the recrystallization temperature, is about 58°C. The initial melting point of the higher-melting (HM) form, also crystallization temperature-dependent, is upwards of 57°C. Under the most easily accessible experimental conditions, it may be obscured by the final melting of the LM-form. The apparent final melting point of the HM form is approximately 66°C. Conversion of the LM form into the HM form occurs only by fusion and crystallization. No evidence of a solid-solid transition was found. The rate of conversion is governed principally by the rate of nucleation at the conversion temperature. If fusion of the LM form is incomplete, recrystallization of the LM form takes place instead of conversion to the HM form.
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  • 77
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1681-1694 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Creep compliance data, J(t), at 35°C for poly(β-hydroxyethyl monomethacrylate), crosslinked by ethylene glycol dimethacrylate in a range of concentration C from 0.0855 to 2.053 × 10-4 mole/cm3 and swollen to various degrees in diluents, were examined for time-concentration superposition. From the dependence of time scale shift factors on v2, the volume fraction of polymer, free volume parameters were calculated for two samples with C = 0.0855 × 10-4 and 0.136 × 10-4 mole/cm3, swollen in the range of v2 from 0.134 to 0.591. Special attention was given to the magnitude of the shift factor on the log J(t) axis and its dependence on concentration, which was found to depend substantially on the crosslinking and the swelling degrees of the samples. This shift was approximately log v2 for lightly crosslinked samples, swollen to a small degree, measured in the neighborhood of the main transition. For higher degrees of crosslinking and/or swelling, the shift was much less and for the most highly crosslinked networks swollen to equilibrium it was even negative. The correction appears to be very sensitive to the strain of the effective chains and to the location on the time scale with respect to the transition and rubberlike zones of viscoelasic behavior. It was found that the parameters of the WLF equation calculated in our previous study from the time-temperature superposition of the creep curves in the rubber-glass transition are valid also for the rubberlike region.
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  • 78
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1775-1783 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A systematic study of factors affecting the GPC separation showed that peak spreading with increasing flow rate was much less than predicted from the Van Deemter equation. Viscous fingering decreased and peak symmetry improved at increased flow rates. As a result, fast GPC analysis was shown to be readily attainable through optimization of operating parameters.
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  • 79
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 279-284 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effect of birefringence on light scattering is considered, using classical theory. It is shown that in conjunction with polarized light scattering, the use of birefringence can aid in the reduction of experimental errors; also how new checks on theory can be made. The treatment is applied to scattering from simple gaseous molecules and thin polymeric films.
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  • 80
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 433-462 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The intrachain and interchain vibrations below 900 cm-1 of polydimethylsiloxane (PDMS) have been studied by slow neutron inelastic scattering. A composite motion observed at +25°C for the methyl groups corresponds to nearly free rotation about the threefold axis of symmetry together with a large-amplitude rotation of the entire methyl group. At -123°C, rotation about the threefold axis evolves to a torsional oscillation. The large-amplitude rotation evolves to the skeletal vibrations of a helical conformation. Vestiges of the cooperative skeletal vibrations of the conformation at -123°C persist into the 25°C spectrum. The results indicate the presence of interrupted helical conformations at 25°C, which result from thermal disordering of the low temperature helices. The effects of crosslinking, low molecular-weight oils, and silica filler on the freedom of the methyl group motions and on skeletal vibrations have been determined. The effects of different crosslinking agents and different relative amounts of filler and oil on both the macroscopic physical properties and the observed molecular motions of PDMS can also be interpreted in terms of an interrupted helix.
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  • 81
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 475-481 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Experiments in which an oscillatory shear flow is superimposed on a steady state shear flow were performed on polyethylene melts by the use of a cone and plate type rheogoniometer. The phase difference between oscillatory shear stress and shear strain increases in all cases and for all frequencies with the increase of the superimposed shear rate. Between ω0, the frequency at which the phase difference is π/2 and the steady shear rate \documentclass{article}\pagestyle{empty}\begin{document}$ \dot \gamma $\end{document}, as found by Booij for polymer solution, the relation ω0 = 1/2 \documentclass{article}\pagestyle{empty}\begin{document}$ \dot \gamma$\end{document}. holds also for polyethylene melts. The significance of this relation is discussed briefly from the viewpoint that the entanglement density decreases with the increase of the imposed shear rate.
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  • 82
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 37-45 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The well known procedure of determining the degree of crystallinity by means of measuring the density presupposes the knowledge of both the densities ρc and ρa of the crystalline and of the noncrystalline regions. By combination of small-angle and wide-angle x-ray scattering and of density measurements it can be shown that this method is not justified in the case of drawn polyethylene if the values of ρc and ρa known from isotropic material are used. Both ρc and ρa depend considerably on annealing and drawing conditions. In addition the effective density ρc* of the more densely packed phase in a two-phase structure is much lower than the value ρc calculated from the positions of the x-ray reflections due to a large number of lattice defects. This conclusion is based on the results of three independent sets of experiments: determination of the mean-square fluctuation of density 〈η2〉 by means of x-ray small-angle scattering; x-ray wide-angle measurements of the positions of the crystal reflections and of the halo arising from the noncrystalline regions; and comparison of densities and long periods of samples treated at various annealing temperatures.
    Additional Material: 4 Ill.
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  • 83
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 123-142 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Isothermal and nonisothermal spherulitic crystallization in even-odd and poly(ω-aminocarboxylic acids) has been studied for a range of fusion conditions and solidification temperatures. The variety of spherulites so formed are classified mainly by optical microscopy. It is found that polyamides with similar types of repeat units generally exhibit similar morphological features under corresponding crystallization conditions. The basic patterns are illustrated in the text. Changes in spherulitic birefringence with temperature are also discussed. In some cases, at temperatures not far below the polymer melting point, platelet-like crystalline aggregates are formed in thin film preparations. These platelets exhibit properties characteristic of single crystals.
    Additional Material: 19 Ill.
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  • 84
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 483-495 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The peak separation in gel-permeation chromatography (GPC) is attributed to the contributions of the steric exclusion and the lateral diffusion processes. The advantage of using the distribution coefficient KGPC of the solute molecule in interpreting the GPC separation mechanism is assessed. The physical significance of KGPC and its relation to measurable GPC parameters are examined in detail. A simple mixing experiment for determining the exclusion effect is described. The results of this experiment, as well as those of the flow rate study, show that the exclusion effect plays the primary role in GPC peak separation. For a column packed with Bio-Rad porous glass of 200 Å designation, the diffusion effect does not contribute significantly to peak separation. However, for the case of a Waters Associates column packed with polystyrene gel of 104 Å designation, both the exclusion and the diffusion effects are shown to be important. A diffusion theory which includes the concept of a restricted diffusion coefficient is proposed to interpret the diffusion effect observed in the polystyrene gel column. The results of the theoretical calculation are found to agree with the observed flow rate dependence of the calibration curve.
    Additional Material: 4 Ill.
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  • 85
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 537-549 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Thermogravimetric analyses (TGA) of catalyst-free polydimethylsiloxanes (PDMS) have been carried out in controlled atmospheres and a kinetic analysis of the results has enabled the various decomposition processes to be separated and identified. The calculated activation energy for thermal depolymerization is 42 ± 3 kcal/mole, while thermo-oxidation has an apparent activation energy of 30 ± 2 kcal/mole. Quantitative analyses of the major degradation products and molecular weight distribution studies of the residues from degradation studies under isothermal conditions have shown that in vacuo, PDMS fractions depolymerize to cyclic dimethylsiloxanes and low molecular weight linear residues by a randomly initiated mechanism which, it is postulated, involves the formation of an intramolecular, cyclic, four-centered transition state followed by siloxane bond rearrangement. This mechanism is a basic property of linear PDMS fractions and is independent of molecular weight. Molecular weight distribution (MWD) changes observed from further isothermal investigations on hydroxy endblocked PDMS fractions, have shown the presence of a chain-lengthening process in vacuo below the depolymerization temperature. This process, with an apparent activation energy of 8.6 ± 1 kcal/mole, is attributed to the intermolecular condensation of terminal hydroxyl groups.
    Additional Material: 6 Ill.
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  • 86
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 575-586 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The intrinsic viscosities of fractions of poly(ethylene oxide) in the molecular weight range 1.5 × 103 to 106 have been measured at 25°C in benzene, carbon tetrachloride, and acetone; at 35°C in 0.45M aqueous potassium sulfate; and at 50°C in methyl isobutyl ketone and diethylene glycol diethyl ether. The latter three are practically theta solvents. The value of (r02/M)1/2 for poly(ethylene oxide) is calculated to be 0.84 Å from the molecular weights of the high molecular weight fractions, and their intrinsic viscosities in the theta solvents and acetone. Erroneous values result if the usual methods of determination are applied to the data obtained for the low molecular weight (〈104) fractions or to the intrinsic viscosities in the very good solvents, benzene and carbon tetrachloride.
    Additional Material: 3 Ill.
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  • 87
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 609-633 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Molecular weight determinations by light scattering and osmometry and intrinsic viscosity measurements were made in various solvents on fractions of styrene-methyl acrylate copolymers with different compositions and on acrylate homopolymers prepared by free-radical reaction. Relations between intrinsic viscosity [η] and molecular weight M thus established are compared with those reported by other authors. 2-Methylcyclohexanol was found to be a theta solvent for the copolymers and both parent homopolymers, and isoamyl acetate was a theta solvent for poly(methyl acrylate). From theta point viscosity data obtained with these solvents, unperturbed chain dimensions were estimated. The results are compared with the unperturbed dimensions estimated from the [η]-M relations obtained in good solvents. On the basis of the experimental data it was found that the unperturbed dimension depends linearly on the copolymer composition, in contrast to the case of styrene-methyl methacrylate copolymers. Composition dependences of the theta temperature and of the parameter describing the long-range interactions between nonadjacent segments in polymer chains were investigated. The result implies that long-range interactions between monomeric units never disappear even when those between the same monomeric units vanish. The Huggins constant for copolymer is discussed in terms of the excluded volume variable.
    Additional Material: 9 Ill.
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  • 88
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 635-658 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Stress-strain and rupture data were determined on an unfilled styrene-butadiene vulcanizate at temperatures from -45 to 35°C and at extension rates from 0.0096 to 9.6 min-1. The data were represented by four functions: (1) the well-known temperature function (shift factor) aT; (2) the constant strain rate modulus, F(t,T), reduced to temperature T0 and time t/aT, i.e., T0F(t/aT)/T; (3) the time-dependent maximum extensibility, λm(t/aT); and (4) a function Ω(χ) where χ = (λ - 1)λm0/λm, in which λ is the extension ratio and λm0 is the maximum extensibility under equilibrium conditions. The constant strain rate modulus characterizes the stress-time response to a constant extension rate at small strains, within the range of linear response; λm is a material parameter needed to represent the response at large λ; and Ω(χ) represents the stress-strain curve of the material in a reference state of unit modulus and λm = λm. The shift factor aT was found to be sensibly independent of extension. At all values of t/aT for which the maximum extensibility is time-independent, the relaxation rate was also found to be independent of λ. These observations indicate that the monomeric friction coefficient is strain-independent over the ranges of T and λ covered in the present study. It was found that λm0 = 8.6 and that the largest extension ratio at break, (λb)max, is 7.3. Thus, rupture always occurs before the network is fully extended.
    Additional Material: 17 Ill.
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  • 89
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The ultimate properties of an unfilled styrene-butadiene rubber vulcanizate in equal biaxial tension were determined by inflating a circular membrane into a bubble. Tests were made at several extension rates (evaluated at the pole) from about 0.15 to 4 min-1 and at temperatures from -43 to 90°C. The stress in the vicinity of the pole when rupture occurred was evaluated from the pressure, the radius of curvature, and the extension ratio λ, the latter two quantities being obtained from photographic data. Below 70°C, the ultimate extension ratio λb is approximately 5.2 and is essentially independent of extension rate and temperature, in striking contrast to the behavior in simple and constrained biaxial tension (pure shear). Likewise, the rupture stress is manyfold greater than in either simple or constrained biaxial tension. From the extremum points of failure envelopes, the maximum extension ratio (λb)max in equal biaxial tension is 5.7 and in simple tension is 7.2. An examination of ruptured membranes showed that, except at 70 and 90°C, rupture began away from the pole in a region where the stress state is unequal biaxial tension. Hence, values of the ultimate properties in truly equal biaxial tension are no doubt somewhat greater than those obtained from the membrane tests. However, it is shown that (λb)max in truly equal biaxial tension must be lower than that in simple tension by at least 10%. A consideration of rupture data in simple, constrained biaxial, and equal biaxial tension leads to the conclusion that no simple failure criterion is applicable for interrelating data obtained under the several states of combined stress. The rupture patterns and factors that affect the site of rupture initiation and the mode of crack growth are also discussed.
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  • 90
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 735-742 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It is shown that, at the yield stress, glassy polymers exhibit viscous flow which is in agreement with the generalized theory of Eyring. The study of the yield stress over a wide range of temperatures and strain rates provides evidence on the secondary transitions found by other methods. From our measurements we conclude that every secondary transition corresponds to the liberation of one of the degrees of freedom of a segment of the main chain.
    Additional Material: 3 Ill.
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  • 91
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 751-751 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 92
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 795-807 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dynamic mechanical properties determined with a torsion pendulum were used to ascertain the glass transition temperature Tg of poly-ε-caprolactone. By measurements on compatible blends of poly-ε-caprolactone and poly(vinyl chloride), the Tg of amorphous poly-ε-caprolactone was shown to be 202°K at about 1 cps. This is 16°K lower than the Tg of annealed, crystalline polymer. The blend transition data were well fitted by both the Fox and the Gordon-Taylor expressions. The Fox expression was also used to describe the decrease from 233°K of the secondary low-temperature relaxation due to poly(vinyl chloride) by assuming the low temperature relaxation of poly-ε-caprolactone, 138°K, was responsible for the decrease in the blends. The 138°K relaxation due to poly-ε-caprolactone was decreased when more than 50% poly(vinyl chloride) was present.
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  • 93
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 829-844 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(vinyl chloride) sheet was oriented by hot drawing. The yield behavior of the oriented sheet was then investigated under uniaxial tension at room temperature as a function of the angle between the tensile axis and the molecular alignment direction. The onset of yield was localized in deformation bands. The variation of yield stress with direction and the direction in which the deformation bands formed were found to be satisfactorily accounted for in terms of a yield criterion based on that of von Mises, provided that a term representing internal compressive stress in the molecular alignment direction was included. The internal stress was found to increase from zero with increasing draw ratio of the prior hot drawing. It is pointed out that other workers have found polymers to obey the yield criterion of Coulomb rather than that of von Mises.
    Additional Material: 9 Ill.
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  • 94
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 879-887 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The Fickian diffusion coefficient of methylene chloride in a glassy epoxy polymer is calculated with the use of Crank's model of discontinuous change of D with concentration C. The diffusion constant is obtained as 1.93 × 10-6 cm2/sec. The swollen layer behind the advancing solvent front is essentially in the rubbery state of the same polymer. The case II swelling by benzene is discussed in terms of a convective transport arising from the partial stress (internal) tensor of the penetrant. The superposition of Fickian and case II diffusion found with mixtures of methylene chloride and benzene is also discussed briefly.
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  • 95
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 929-945 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: “Regular” sequence copolymers having the structure {[—CH2—C(CH3)(C6H5)—]m(CH2—CH2)n}p with relatively small values of m and n were prepared by means of “living” polymerization techniques. The intrinsic viscosities of fractions of these copolymers were obtained in various solvents including a theta solvent. The molecular weights of these fractions were determined by the Archibald ultracentrifugal method. The results show that the intrinsic viscosity-molecular weight relations of the regular sequence copolymers are affected not only by the average composition of the copolymer, but also by the sequence length in the copolymer molecule. It is suggested that the effective conformation of a chain element in the copolymer is not always the same as that in the homopolymer.
    Additional Material: 6 Ill.
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  • 96
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1619-1621 
    ISSN: 0449-2978
    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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  • 97
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1651-1667 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The plastic deformation of poly-4-methylpentene-1 (P4MP1) crystals on a unidirectionally drawn substrate has been investigated by electron microscopy. In addition to cracks spanned by fibrils and buckling perpendicular to the stretch direction, both features found in deformation studies of other polymers, a unique slip mechanism leading to sectorization of P4MP1 crystals is observed; deformation was also found to occur by means of localized lamellar thinning. The exact type of plastic deformation occurring in P4MP1 crystals is found to depend on the orientation of the lamellae with respect to the tensile axis. Some evidence for a periodicity on the fibrils studied is given.
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  • 98
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1669-1679 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A method for evaluating the relaxation time as a function of both temperature and volume from volume contraction experiments, as proposed by Kovacs, was experimentally examined by using monodisperse poly-α-methylstyrene samples of various molecular weights and blends. It was concluded that his theory can be successfully applied to the present experimental data, though his two different approximations give somewhat different values of the shift factor for the time-temperature superposition of volume contraction data. A difference was observed between the temperature dependence of the shift factor of monodisperse polymers and that of blends.
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  • 99
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Electron microscopic textures of A-B type block copolymers of styrene and isoprene cast from several solvents were investigated by means of the osmium tetroxide fixation technique. The two-phase structure, i.e., the semimicro heterogeneous structure due to the microphase separation of block segments, was observed to change systematically with the fraction of block segments and the kind of solvent. Three types of fundamental domain structure were found. With the assumption that domain structure originates from micellar structure at a critical concentration in relatively dilute solution during solvent casting, the formation of the three types of domain structure and the sizes of their elements were treated in terms of the equilibria governing the formation of micelles at the critical concentration. This analysis takes into account such thermodynamic and molecular parameters as the incompatibility between the A and B segments, the solvation of the segments, the casting temperature, the total chain length of the block copolymer, and the weight fraction composition of the block copolymer. It was concluded that the block segments are preferentially oriented along the direction perpendicular to the interface between the two phases. This particular orientation-aggregation of the block segments must make the bulk properties of the block copolymer much different from those of merely mechanical mixtures of the corresponding homopolymers, even if the same semimicro heterogeneous structures are formed in the mechanical mixtures.
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  • 100
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1379-1383 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The surface tensions of solutions of polyisobutylene fluids in n-heptane and tetralin have been measured at room temperature. The polyisobutylene samples studied range in molecular weight from 400 to 2800. The results conform closely to the predictions of equations previously developed from a simplified lattice theory calculation.
    Additional Material: 2 Ill.
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