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  • 1965-1969  (1,881)
  • Physics  (1,849)
  • Engineering General
  • 101
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    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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  • 102
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    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1627-1638 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A new type of long-range interaction between chain segments and solvent molecules in a polymer molecule is introduced. It can be depicted as an “interfacial” free energy, due to the more or less diffuse interface between the interior of a polymer coil and the surrounding solvent. Flory's calculation of the coil expansion α is extended for this effect, by using theoretical approaches developed by van der Waals, Cahn and Hilliard, and Debye for inhomogeneous systems (interfaces). It is found that Flory's equation for α is replaced by: \documentclass{article}\pagestyle{empty}\begin{document}$ \alpha ^5 - \alpha ^3 = 2C_M \psi _1 M^{1/2} \left[ {1 - \left( {\theta /T} \right) + \left( {15/2\alpha ^2 } \right)\left( {\theta /T} \right)\left( {l^2 /\overline {r_0^2 } } \right)} \right] $\end{document} where the last term is due to the “interfacial” free-energy correction. The Debye molecular interaction length l is also found in theories on light scattering of binary mixtures near the critical solution temperature. An important result of this equation is that at T = θ, α is not equal to unity, as before, but somewhat larger, depending on the molar mass of the polymer and the solvent type. A calculation shows that the “interfacial” free energy correction may contribute substantially to the “solvent” effects on the expansion of a polymer molecule at the θ temperature, as has recently been reported in the literature.
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  • 103
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    New York : Wiley-Blackwell
    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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  • 104
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    New York : Wiley-Blackwell
    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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  • 105
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    New York : Wiley-Blackwell
    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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  • 106
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1695-1704 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The Hv cloverleaf scattering pattern sometimes found for amorphous polymers can arise from the birefringent region caused by the strain surrounding a void or an inclusion in a polymer. The form of such a pattern may be theoretically explained by extension of a theory due to Goldstein.
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  • 107
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1735-1744 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The infrared absorption of poly(ethylene glycol) was measured in the molten state. Characteristic bands of the molten state were identified. Normal vibrations and frequency distributions were treated for various conformation models with CH2CH2O repeat units. The infrared absorption peaks of the molten state closely correspond to the frequency distribution peaks of the TGT conformation with gauche O—CH2—CH2—O groups, although infrared bands due to trans O—CH2—CH2—O groups are also observed. Vibrational assignments of the infrared bands and Raman lines were made on the basis of potential energy distributions.
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  • 108
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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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  • 109
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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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  • 110
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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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  • 111
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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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  • 112
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1835-1861 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dielectric relaxation processes observed in solid polar polymers seem to be generally classified into three kinds. Amorphous polymers with flexible polar side groups usually show two kinds of relaxation process. The high-temperature process is attributed to the large scale conformational rearrangements of the main chains, while the low-temperature one results from the motion of side groups. We shall call the former αa relaxation and the latter β relaxation, where the subscript refers to the amorphous phase. Even in amorphous polymers without flexible side groups, two processes are observed. The molecular mechanism of high temperature one is the same as the αa relaxation. The low-temperature one is due to the “local relaxation mode” of the main chains. We shall call it also β relaxation because of the similarity of the observed characteristics. Semicrystalline polymers show two relaxation processes classified as αa and β, although their behavior is modified by crystallization. When the crystallinity is greatly increased, a third relaxation process with associated with crystalline phase appears. We shall call it αc relaxation, where the subscript means the crystalline phase. The effects of chemical structure, stereoregularity, pressure, and crystallization on the dielectric behavior can be explained consistently based on the above molecular mechanisms.
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  • 113
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1895-1905 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A simple, practical calculation procedure has been developed for predicting the changes in molecular weight distribution of a polymer undergoing random crosslinking and/or degradation. Simulations of the random crosslinking and degradation of narrow and broad Poisson-type distributions have been made. The results agree with those calculated from Kimura's analytical solutions to Saito's general equations after a correction has been made for a mathematical error in Kimura's solution. This method can be applied to determining the probabilities of crosslinking and scission for any arbitrary molecular weight distribution expressed in tabular form. The importance of using narrow distribution samples to estimate crosslinking from changes in molecular weight distribution is graphically demonstrated.
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  • 114
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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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  • 115
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1919-1935 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Batch polymerizations of vinyl acetate were conducted at 60°C and 72°C, and rate constants for branching were established from the variation of M̄n and M̄w with extent of conversion. The calculated branching densities (branch points per polymer molecule) are slightly higher at 72°C for all conversions. Selected samples were saponified and reacetylated to determine the amount of branching through the acetate group. Changes in M̄n, M̄w, and [η] indicate 63%, 75%, and 70%, respectively, of saponificable branches. These percentages are independent of branching density in the original polymer. Molecular weights extrapolated to zero conversion appear to be unchanged by saponification and reacetylation, showing that short chain branching through the acetate group is absent, or at least very infrequent.
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  • 116
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1955-1964 
    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 ratio [η]B/[η]L was calculated as a function of average branching density for trifunctionally branched, free-radical polymers. Calculations were made for the g1/2, g3/2, and h3 rules, using realistic distributions of molecular weights and branches. Experimental data on branched poly(vinyl acetate) lay between the curves obtained from the g1/2 and h3 relations.
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  • 117
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 563-574 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Solution parameters for the polymer poly-γ-trifluoro-propylmethylsiloxamer has been determined in cyclohexyl acetate, methyl hexanoate, and ethyl acetate. Interpretation of data follows the theory of Fox and Flory. In contrast to poly-dimethylsiloxane, an increased steric hindrance to rotation about the siloxane bond occurs as evidenced by the characteristic ratio of root-mean-square end to end dimensions, (r02/r0f2)1/2, found to be 1.90 and 1.96 at 25.0 and 72.8°C, respectively. This increase is considered to be primarily due to nearest-neighbor interaction of the polar substituent on the silicon atom. The relation, [η]θ ∝ M1/2, was observed to hold for this polymer system. The hydrodynamic model appropriate for the polymer is a random coil considerably more permeable to solvent flow than is generally reported for linear polymers. The universal parameter φ was determined to be 1.5 × 1021. The effect of temperature on polymer configuration is indicated to be negligible.
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  • 118
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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.
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  • 119
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    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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  • 120
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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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  • 121
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    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.
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  • 122
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 309-324 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The Huggins and Kraemer equations generally used to determine intrinsic viscosity frequently do not yield identical results, and their constants often do not add up to 1/2 as is mathematically required. To overcome these difficulties an equation has been deduced which through linear plots gives unambiguous intrinsic viscosities, constants which meet the 1/2 condition, as well as two other flow constants. Extensive tests of the equation with precise data on solutions of poly(methyl methacrylates) and polystyrenes in benzene and toluene confirm the validity of the new equation in every respect. It is further shown that the four constants involved are interrelated, and that it is possible to express the values of three of these in terms of the fourth.
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  • 123
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 377-388 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The design of a differential thermal analysis apparatus for use at elevated pressure is described. Experiments on melting and crystallization of folded-chain crystals of polyethylene and poly(ethylene-butene-1) copolymer, and melting of extended-chain polyethylene crystals have been conducted at pressures up to 4200 bars. The precision in transition temperature measurement was ±1°C. The Clausius-Clapeyron equation predicts the melting point increase with pressure at atmospheric pressure to be 32.0°C/kb. The melting point depression due to copolymerization remained constant over the complete pressure range analyzed on the poly(ethylene-butene-1) used in this study. Crystallization of polyethylene is retarded at elevated pressures, and a 50% larger degree of supercooling is necessary at 5000 bars to give a crystallization rate equal to that observed at atmospheric pressure. The difference in melting point between folded-chain and extended-chain polyethylene increases from 8.4°C at 1 bar to 25.6°C at 3000 bars.
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  • 124
    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.
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  • 125
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 405-410 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Multiphonon contributions to the directional phonon frequency functions are calculated for crystalline polyethylene. These results are compared to previously calculated one-phonon frequency functions.
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  • 126
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 423-424 
    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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  • 127
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    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.
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  • 128
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 425-427 
    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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  • 129
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 431-431 
    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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  • 130
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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.
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  • 131
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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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  • 132
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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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  • 133
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 77-86 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The random depolymerization model of Montroll and Simha for originally homogeneous polymers is derived analytically by utilizing a weight distribution function approach not requiring the use of any approximations. The model is then extended to consider heterogeneous initial chains having an arbitrary chain length distribution. The probabilities for breakage are assumed to be identical for all bonds joining monomeric elements in the system and to be independent of chain length and position in the chain, assumptions also used in the model of Montroll and Simha. An expression is found for estimating the probability of bond breakage.
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  • 134
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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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  • 135
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1907-1918 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A new apparatus for investigating dynamic strain birefringence in polymer films at frequencies up to 10 Hz and at various degrees of internal sample orientation is described. Samples are elongated at constant low rates while simultaneously being strained sinusoidally. Fast changes in sample retardance are recorded while slow changes are automatically compensated with a servo-controlled Soleil-Babinet compensator. The signal-to-noise ratio of the system is greatly enhanced by incorporating a highly monochromatic laser light source, a synchronous amplifier, and a light beam modulator based on a rotating polarizer. Data obtained from this apparatus can be used to elucidate polymer relaxation mechanisms at various frequencies over a wide range of static strains.
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  • 136
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1965-1982 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Raman spectra are described for the three crystalline modifications of polybutene-1. The Raman frequencies are compared with infrared results and give good agreement. A normal-coordinate analysis for A-mode vibrations is presented for five possible helical conformations. The behavior of several calculated helix-sensitive bands is characterized. These results are applied to the experimental Raman frequencies and lead to the prediction of a 103 helix for the orthorhombic form III modification.
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  • 137
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1987-1994 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The thickness of the interphase layer as a function of time at 160°C has been determined directly in a microheterogeneous polymer mixture, and the layer thickness between two bonded sheets has also been measured by phase-contrast microscopy. Two mixtures of polymers, isotatic polypropylene with polyethylene and poly(vinyl chloride) with polyethylene, were prepared by mixing size-sorted powders in suspension, followed by evaporating the suspension medium and compacting the powdered mixtures. The mutual penetration initially obeyed Fick's second law; then diffusion was retarded and stopped after 15-20 min. An equilibrium state was reached which did not correspond to the classical thermodynamic equilibrium, at which the so-called equilibrium thickness of the interphase layer for the pair isotactic polypropylene-polyethylene was about 28,000 Å and for the pair poly(vinyl chloride)-polyethylene was about 89,600 Å. The equilibrium values can be used as a quantitative criterion for the compatibility of the polymer pairs.
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  • 138
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 2019-2028 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The diffusion studies of several solvents in epoxy polymer reported by Kewi and Zupko in Part I of this series are explained with the solution obtained from the generalized diffusion equation which includes the internal stress contribution. The rate of permeation of a penetrant through a polymer film and the time lag needed to reach steady state are also given for the generalized diffusion equation.
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  • 139
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 2073-2089 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dilatometric melting experiments were performed on an extended-chain crystalline polyethylene with a broad molecular weight distribution and on four samples crystallized from fractionated polyethylenes. The melting curves were compared with computer calculations based on the assumption of eutectic separation. For the fraction of lowest molecular weight, agreement between experiment and calculation was achieved. The melting behavior of all other samples indicated that only for molecular weights up to 10,000-12,000 did eutectic separation occur. The higher molecular weight portion of each sample crystallized in the form of mixed crystals. Of the experimental maximum melting-point lowering of these mixed crystals, 0.1-0.9°C is due to the lower molecular weight diluents. Another 2-3°C lowering in melting point is due to the fact that the phase diagram of polyethylene mixed crystals has a minimum.
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  • 140
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 2091-2097 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Differential thermal analysis and electron microscopy of partially molten, extended-chain polyethylene crystals, grown under elevated pressure, was performed. It could be shown that melting peaks on the low temperature side of the main melting peak are due to narrowly distributed, low molecular weight polymer segregated in extended-chain crystals. Superheating of crystals before melting increased with molecular weight and chain extension. The melting mechanism of extended chain crystals was shown to be a successive peeling off of chains which leaves the chain extension constant up to melting of the last crystal trace.
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  • 141
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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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  • 142
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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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  • 143
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1525-1537 
    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 rheo-optical properties of a styrene-butadiene-styrene block copolymer of a given chemical composition are dependent upon the morphology of the polymer as affected by the solvent system from which a polymer film is cast. Films cast from methyl ethyl ketone and from toluene are compared. Properties found to differ are the stress-strain curve, the birefringence-strain curve, stress relaxation birefringence relaxation, and the dynamic mechanical spectra.
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  • 144
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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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  • 145
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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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  • 146
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 2144-2144 
    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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  • 147
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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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  • 148
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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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  • 149
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1281-1282 
    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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  • 150
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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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  • 151
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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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  • 152
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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.
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  • 153
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1357-1366 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Three types of commercial styrene-acrylonitrile copolymer were fractionated by coacervate extraction and by column-elution techniques. Both methods were studied with two different solvent-nonsolvent pairs. Glass wool was used as the support material in the column. Fractionation by the coacervate extraction method was studied with benzene-triethylene glycol as a solvent-nonsolvent system at 60°C and with dichloromethane-triethylene glycol at 25°C. Column elution was carried out with acetone-methanol as the solvent-nonsolvent system at 30°C, and with dichloromethane-methanol at 20°C. Results of excellent reproducibility were obtained by these two methods. Characterization of fractions involved determination of both the molecular weight and chemical composition. It was established that the fractionation of the samples tested was dependent upon molecular weight only. The two methods described above are compared. Each gives an efficient procedure for fractionation of styrene-acrylonitrile copolymers.
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  • 154
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1367-1378 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Thin films of polyethylene prepared from blends of fractionated polymer and a linear hydrocarbon (n-C32H66) have been used to study the role of intercrystalline links in the deformation of semicrystalline polymer under uniaxial stress. These links have been found to be strong and virtually inextensible elements of the structure. It is shown that they are firmly attached to the chain-folded lamellar crystals they bridge (both within the same spherulite and across boundaries between adjacent spherulites) and that, by concentrating applied stress, they commonly induce these lamellae to begin yielding in regions close to their points of attachment. Where there are many closely spaced links the stress is distributed fairly evenly, and drawing is relatively smooth and uniform. With more sparsely distributed links, however, stresses tend to be concentrated at widely separated points; deformation then tends to be severe and highly localized, often resulting in failure of the material upon drawing. There are indications that stress is also transmitted between chain-folded lamellae in ways other than by intercrystalline links. One such way is by means of chain ends and molecular loops that emerge from the surfaces of these crystals and are embedded in interlamellar material. Experiments in which the deformed films were subsequently heated confirm earlier conclusions that extended chains in drawn polymer may undergo refolding during annealing.
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  • 155
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1393-1403 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Attempts to prepare undamaged microtomed sections of crazes without reinforcement have failed. Several methods of reinforcing crazes in glassy polymers with impregnants prior to microtomy have been tried. Generalized characteristics of successful impregnant systems are suggested on the basis of this experience. The most successful system has involved the infusion of liquid sulfur into crazes in poly(2,6-dimethyl-1,4-phenylene oxide). After quenching, the solid sulfur reinforces the crazes successfully during microtomy but subsequently sublimes away under vacuum. The resultant, largely undamaged craze structure is seen by transmission electron microscopy to resemble an open-cell foam, the holes and polymer elements of which uniformly average ∼200 Å in diameter. A moderate degree of orientation in the original tensile stress direction is observed. Implications drawn from craze structure for the existence of order in the glassy state are discussed.
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  • 156
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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.
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  • 157
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    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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  • 158
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 725-733 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The site of chain scission and crosslinking in vulcanized natural rubber irradiated with 4 MeV electrons has been determined by analysis of stress relaxation data. Sulfur and peroxide vulcanizates of different crosslink densities were prepared and the crosslink densities determined from stress-strain measurements. Stress relaxation was measured during irradiation using modified commercial relaxometers. The specimens were maintained in an atmosphere of nitrogen to minimize oxidative side effects. Scission is deduced to take place in the vicinity of crosslinks, since the rate of continuous stress relaxation is independent of crosslink density. Scission may be associated both with crosslinks initially present and with those subsequently introduced by irradiation. Crosslinking by radiation is largely a random process. However, there is a crosslinking reaction dependent to a slight extent on crosslink density as well as a small contribution from random scission reactions. G values for the random reactions are given.
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  • 159
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    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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  • 160
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    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.
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  • 161
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    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.
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  • 162
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 257-270 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The orientation of crystallites grown isothermally in several drawn trans-polychloroprene networks is studied as a function of crystallization temperature tx, degree of crystallinity ω, and elongation ratio α. The orientation distribution is particularly simple for this polymer since the crystallographic c axis (chain axis) orients preferentially along the stretching direction, while a and b are randomly arranged about c. Hence the parameter cos2 χc adequately characterizes the distribution, where χc is the angle between the c axis and the fiber axis, and the average is taken over all crystallites. A treatment due to Krigbaum and Roe is utilized to obtain values of v (the number of statistical segments comprising the crystallization nucleus of critical size) through comparison of the average orientation of crystallites and amorphous statistical segments. The behavior observed falls into two categories. First, if the initial amorphous network is well oriented, 〈cos2 χc〉 is independent of crystallinity during both crystallization and melting, and v varies with tz (or the degree of supercooling) as predicted by nucleation theory. If different networks are to have the same crystallite orientation distribution, they must not only be crystallized at the same supercooling, but must also have the same distribution of amorphous segment orientations. Both the relative elongation and the network crosslink density affect the latter distribution. Next, we consider the second category. If the initial amorphous orientation is poor, 〈cos2 χc〉 decreases linearly during crystallization and increases along approximately the same path during melting. Further, 〈cos2 χc〉 for a given tz yields v values which are too large. These two behaviors can be explained if, in the former case, nucleation involves the best oriented statistical segments of all network chains, while in the latter there is a selection according to the chain displacement vector orientation. Thus, if the amorphous orientation is poor, both the orientation and thermodynamic stability of the crystallites decreases with further crystallization. If this decreased stability is reflected in shorter fold lengths, the reversible variation of long period spacing with temperature reported earlier for an oriented polychloroprene network can also be explained as a preferential melting process.
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  • 163
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    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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  • 164
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Thermogravimetric Analysis (TGA) is finding increasing utility in investigations of the pyrolysis and combustion behavior of materials. Although a theoretical treatment of the TGA behavior of an idealized reaction is relatively straight-forward, major complications can be introduced when the reactions are complex, e.g., in the pyrolysis of cellulose, and when experimental imperfections arise. Consequently, a fairly large number of analytical methods have been proposed for obtaining kinetic parameters from TGA curves. Among the proposed methods are several graphical procedures, mostly involving relatively inaccurate tehniques, such as obtaining slopes on a rapidly changing curve. Included among the proposed procedures is one which permits a linear plot of TGA data. The sensitivity with which such a plot can be used to identify and correct for a variety of experimental complications seems to have escaped even the proponents of the techniques. This paper provides an illustration of the use of this graphical procedure in a hypothetical first-order pyrolysis typical of those occurring in the TGA behavior of cellulose.
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  • 165
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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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  • 166
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1819-1833 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Annealed polyethylene single crystals have been degraded with fuming nitric acid, and the molecular weight distribution of the fragments determined by using a gel-permeation chromatograph. Peaks due to chain folding were observed in these distributions as for unannealed single crystals. The peaks moved to lower molecular weight with increasing degradation time. Comparison of the lowest molecular weight peak length after a given degradation time with the low-angle x-ray periodicity before degradation gave information about a disordered surface layer. The thickness of this layer at early states of degradation was dependent solely on annealing temperature, though changes in the layer must have occurred with annealing time, since there was an increase in reaction rate with annealing time. At higher degradation states, the thickness of the layer was dependent solely on the original low-angle periodicity. This has been related to the depth at which some folds are buried beneath the lamellar surfaces. The relevance of these observations to the structure of annealed single crystals is discussed.
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  • 167
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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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  • 168
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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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  • 169
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    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.
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  • 170
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 297-307 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The molecular weight distributions of three polydimethylsiloxanes (PDMS) have been determined by gel-permeation chromatography (GPC), by gas-liquid chromatography (GLC), and by precipitation fractionation. The GPC data are greatly improved by correction for band spreading. For a high molecular weight polymer the corrected distribution agrees closely with the theoretical molecular weight distribution calculated from polymerization kinetics.
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  • 171
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 357-375 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The assumed analogy between polymer solutions and polymer-network gels as regards the thermodynamics of swelling - a fundamental assumption implicit in all previous analyses of swelling measurements on gels, aimed at checking the statistical theories of rubber elasticity - is shown in fact to be rather limited. In particular, excluded volume effects, which play a dominant role in both solutions and gels, are quite different in the two types of systems. A new thermodynamic description of swelling equilibria, taking account of differences in excluded volume effects, is given, and analogies and differences between gels and solutions are pointed out.
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  • 172
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 993-1003 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effects of ultraviolet radiation on dilute aqueous solutions of poly(acrylic acid) and of other polyelectrolytes were studied by viscosity measurements in connection with the effects of ionizing radiation. It was found that ultraviolet light of wavelength below about 2300 Å brought about degradation of polymer chains mainly by indirect action via water, while light of wavelength above 2300 Å caused degradation by direct action in some polymers. It was deduced from the experiments that the protective effect of NaCl could be largely attributed to a decrease in the indirect action. It was also found that a low concentration of methanol was effective in preventing degradation by direct action, although methanol promoted degradation when present in high concentration. Since the promotive effect was not observed when light of wavelength below 3700 Å was eliminated by a filter, this effect was attributed to active products of the irradiation of methanol.
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  • 173
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    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.
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  • 174
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1005-1019 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Measurements of T1ρ as a function of temperature have been made on three polyethylene oxides (PEO) with molecular weights of 550, 6000, and 2.8 × 106 in order to try to elucidate various problems arising in the interpretation of previous T1 measurements on PEO. In contrast to the T1 measurements, the T1ρ measurements show discontinuities at the melting or softening points of the respective polymers concerned, and also show nonexponential magnetization decay in the case of PEO 6000 and 2.8 × 106, which is presumbly due to the existence of “mobile” and “crystalline” regions, in qualitative agreement with NMR studies and x-ray measurements. Motional correlation frequencies and activation energies have been derived where possible by using the BPP theory adapted to the rotating frame and also the strong collision Slichter-Ailion theory. There is reasonable correlation with other data on motional frequencies where it is available, although the overall situation for the so-called α transition in PEO 6000 and 2.8 × 106 is still not clear. It is suggested that spin-diffusion is an important mechanism for all three polymers; for PEO 550 because it contains CH3 endgroups which act as sinks, and for the other two polymers where the mobile fraction performs the same function.
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  • 175
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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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  • 176
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 2099-2113 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polyethylene crystals of different degrees of perfection were annealed at 5.1 kb pressure for 20 hr at various temperatures and analyzed by electron microscopy, thermal analysis, and density determination. No annealing took place until the temperature was close to the melting point of the starting material. Up to 235°C increasing solidstate annealing was observed. Mixed crystals of up to 0.989 g/cm3 density and 1500 Å thickness in the chain direction could be produced. At slightly higher temperature recrystallization to extended-chain crystals rather than annealing occurred. The annealing process at atmospheric pressure seems to be similar in nature, but takes much longer for comparable perfection. From a comparison of annealing and crystallization it is concluded that polymer crystallization goes through a stage of internally imperfect order during which most of the observed chain extension occurs. Estimates of this outer imperfect layer of a growing crystal place its depth at 30,000 Å.
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  • 177
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 2139-2140 
    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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  • 178
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 2140-2141 
    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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  • 179
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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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  • 180
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1495-1511 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Measurements are reported of the vapor pressures and the heats and volumes of mixing of solutions of poly(ethylene glycol dimethyl ether) in chloroform and in carbon tetrachloride. The measurements have been used to calculate the thermodynamic mixing functions for mixing with zero volume change. These values have been compared with the predictions of the lattice theory of mixtures at three different levels of approximation, viz., the generalized “first approximation” theory of Barker, the “zeroth approximation” theory, and the Flory theory. In the hydrogen-bonding chloroform solutions the Barker theory is more successful than the other forms of the lattice theory. The results have also been used, in conjunction with those for solutions of poly(propylene glycol dimethyl ether) in the same two solvents, to test the ability of the Barker theory to correlate the properties of related systems. Good correlation is found between the two carbon tetrachloride solutions but not between the chloroform solutions. It is probable that the side-chain methyl groups in the propylene oxide repeating unit cause the hydrogen-bonding interaction to be weaker in this polymer than it is in the polymer with the ethylene oxide repeating unit.
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  • 181
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1539-1558 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The scattering patterns are calculated from anisotropic rods having an arbitrary angle of the polarizability axis with respect to the rod axis. The effect of a distribution of orientation of the rods is explored. This leads to a change in scattering patterns produced by orienting the rods upon stretching the sample. The scattering patterns are affected by the relationship between the refractive indexes of the rods and that of the surroundings. The influence of the optic axis orientation angle changing upon orienting the rods is explored. Theoretical patterns are compared with experimental ones obtained upon stretching polytetrafluoroethylene (PTFE) films.
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  • 182
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1585-1594 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A comparison is made between the experimentally obtained molecular weight distributions of nitric acid-oxidized polyethylene with a wide range of initial morphologies and the predictions of a random attack model. Deviations from the theoretical expectations are explained.
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  • 183
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1577-1583 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Melting temperatures were observed visually for poly-(2,6-dimethyl-1,4-phenylene oxide) in methylene chloride at nine concentrations (polymer weight fractions ranging from 0.0042 to 0.2362). The data were analyzed upon the assumptions that ΔHu and ΔSu, the molar heat and entropy of fusion per polymer unit, are constant over the temperature range studied, and that a Flory-Huggins chemical potential expression with a concentration-independent pair interaction parameter, χ1 = (0.5 + ψ1) + ψ1Φ/T, satisfactorily describes the polymer unit activity in the binary solutions. Computation gave ΔHu = 1404 cal/mole of units (therefore Δh = 11.7 cal/g), ψ1 = -0.5691, and Φ = 342.4°K. The effect of using various combinations of data points upon the values of these three parameters, as determined by least-squares linear regression treatment of the melting temperature expression, is indicated.
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  • 184
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1559-1575 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dielectric constant and dielectric loss of copolymers of methyl methacrylate (MMA) with n-butyl methacrylate (nBMA) and isobutyl methacrylate (iBMA) have been measured in the frequency range 30 cps to 1 Mcps at temperatures from 70°K to 370°K. Results lead, together with those of previously published investigations on copolymers of MMA, to the following conclusions. (1) The loss-peak temperature attributed to side-chain relaxation (β peak) of PMMA varies with the comonomer ratio when the comonomer does not have an α-methyl group, but remains almost unchanged for comonomers having an α-methyl group. (2) In both cases, the β peak height of PMMA decreases with increasing ratio of comonomer B and completely vanishes for poly-B, and the loss peak temperature plotted against the fraction of B does not extrapolate to the β peak of poly-B. It is suggested on the basis of the above facts that the moving unit in the side-chain relaxation consists of a single side chain with a segment of the backbone chain and that the change in mobility of the side chain upon copolymerization results from the distortion of the helical structure of the backbone chain due to random distribution of α-methyl groups. Dielectric studies of the low-temperature side-chain relaxation (β2 peak) in PnBMA, poly(n-octyl methacrylate), and poly(n-dodecyl methacrylate) (130°K at 1 kcps) have been made and an interpretation is offered for the molecular nature of this relaxation.
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  • 185
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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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  • 186
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1595-1618 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A combination of electron-microscopy, light-scattering, and stress-birefringence studies on chemically crosslinked polyurethanes point toward the existence of rodlike regions (“bundles”), approximately 3000-8000 Å in length and involving about 5% of the volume, in which molecular orientations are correlated. The elastic behavior of these networks - as indeed that of most rubberlike networks - deviates substantially from the Gaussian behavior. The empirical representation of the data in Mooney-Rivlin plots yields C1 and C2 constants which depend on the type of imposed strain. It is thus impossible to identify C1 with the Gaussian behavior and C2 with the deviation there-from. Instead, it is found that the elastic behavior can be adequately described if it is assumed that, as a result of the bundle structure, about 5% of the segments of each chain are not free to assume the normal random-walk configurations. The determination of the number of chains in the network from the elastic behavior remains ambiguous, however, and the behavior upon swelling is not (yet) adequately reproduced by the theory. It is conceivable that in many cases deviations from Gaussian elasticity behavior may be caused by an intermolecular structuring effect, rather than by various minor deficiencies in the Gaussian model for the single chain statistics or by anisotropic excluded volume effects, as has been proposed in the past. In the present case, the amount of bundle structure, as well as the C2/C1 values, increase with the number of urethane couplings per chain, and this suggests that the interaction of the highly polar urethane couplings is responsible for the structuring. In other networks one often finds a dependence of C2/C1 on the previous history of the sample, which suggests that an accidentally trapped order may be responsible for the elastic behavior.
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  • 187
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1623-1626 
    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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  • 188
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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
    Additional Material: 1 Ill.
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  • 189
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1279-1279 
    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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  • 190
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1259-1274 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Model fibers of polyethylene and nylon 6 were strained in the direction of the fiber axis and the internal deformation of the samples was studied by large-angle and small-angle x-ray diffraction. The compression of samples along the fiber axis was successfully carried out, and the results obtained by x-ray methods yielded more interesting information on the structure of the fibers than was obtained in extension. A model for the structure of the fiber was constructed on the basis of the results on compressed fibers. In this model, crystals are distributed in cylindrical symmetry around the fiber axis keeping a crystal axis tangential to circles in the section normal to the fiber axis. The characteristic crystal axis is the b axis in polyethylene and the a axis in nylon 6. The chain axis of the crystals varies in orientation with respect to the fiber axis. In compression of fibers with such a structure, the crystals rotate around the characteristic axis indicated above. In the case of nylon 6 fiber, only this simple rotation seems to occur, while additional changes occur in polyethylene fibers. However, the simple rotation predominates even in polyethylene fibers. This fiber structure is correlated with the structure of thin films of the materials. This similarity proves the existence of a common mechanism for the origin of the structure of fibers and films.
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  • 191
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    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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  • 192
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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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  • 193
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1721-1733 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dielectric measurements of carefully purified specimens of polystyrene and poly(2,3,4 or 3,4-chlorostyrene) have been obtained at audio frequencies ranging from 0.1 to 20 kHz and at temperatures between 4 and 300°K. Each of the samples exhibits a dielectric loss maximum in the range 15-50°K. The temperature of the maximum loss decreases with the addition of a substituent which lowers the symmetry of the pendant phenyl group. The results are explained by a model which invokes a coupling mechanism between two distinct modes of side group motions. This same model also explains some results of previously reported measurements of mechanical losses in similar polymers.
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  • 194
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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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  • 195
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    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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  • 196
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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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  • 197
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    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1995-2004 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Solution characterization measurements indicate that cylization of the polyamic acid from 2,4-diaminoisopropylbenzene and pyromellitic dianhydride (PMDA) to the polyimide can be effected with small change in number-average degree of polymerization. An increase in weight-average molecular weight on conversion to polyimide is attributed to branching side reactions. Inherent viscosities of polyimides from 4,4′-diaminodiphenyl ether and PMDA decreased slowly with time in concentrated (97%) sulfuric acid, probably as a result of hydrolytic cleavage. The zero-time viscosity intercepts were related to both the precursor and the estimated polyimide molecular weight. The latter gave ηinh (c = 0.5% solids) = 2.76 × 10-3M̄0.53w for 60,000 〈 Mw 〈 300,000. The exponent is near the lower limit of 0.5 found in theta solvents. The characteristic ratio of the root-mean-square end-to-end distance of a chain to the square root of its molecular weight is 1.1 Å and the steric factor is 1.1; these results suggest that the unperturbed polyimide chain is almost as extended as an equivalent freely rotating chain, a general feature of long-bonded polymers with p-phenylene rings in the chain backbone.
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  • 198
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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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  • 199
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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.
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  • 200
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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
    Type of Medium: Electronic Resource
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