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  • 1970-1974  (2,835)
  • 1965-1969  (1,880)
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  • Physics  (4,396)
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  • 101
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 1189-1193 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetics of the disappearance of propagating butadiene radicals produced in the grafting of butadiene to poly(vinyl chloride) was followed by electron spin resonance measurements. The radical species observed in the temperature range 213-298°K is the conjugated allylic radical: \documentclass{article}\pagestyle{empty}\begin{document}$$ \hbox{---} {\rm CH}_{2}\hbox{---}\rm{CH}\hbox{=\hskip-1pt=}{\rm CH}\hbox{---}{\rm CH}_2 \rightleftharpoons\hbox{---}{\rm CH}_2\hbox{---}{\rm CH}\hbox{---}{\rm CH}\hbox{=\hskip-1pt=}{\rm CH}_2 $$\end{document} The reaction conditions were adjusted to provide a highly viscous medium in which the propagation reaction took place. Under these conditions the radicals were stabilized and a precise ESR spectrum was obtained. Arrhenius plots of the second-order decay rate constants yield an activation energy of 5 kcal/mole. This suggests that the bimolecular termination reaction is controlled by the segmental motion of the grafted side chains.
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  • 102
    Electronic Resource
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 1339-1345 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: To establish optimum operating conditions for high-speed gel-permeation chromatography (GPC), the effects of column packing particle size, solvent flow rate, and column length on the separation efficiency have been investigated by using monodisperse polystyrene samples and polystyrene gel columns (TSK-GEL column, Type-H). Decreasing the particle size of the column packing reduces the time required to obtain a given resolution. Monodisperse polystyrene standards were measured under the optimum operating conditions established (gel particle size 5 μ, column length 2 ft, flow rate 2.5 ml/min). The molecular weight distribution of a polymer mixture was determined in less than 10 min with the same accuracy as by the conventional GPC. Such short analysis time enables one to use GPC for in-plant quality control.
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  • 103
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 1383-1394 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The tensile stress relaxation of carbon-black-filled SBR was studied in the linear viscoelasticity region as a function of temperature and volume fraction of fillers. Time - temperature superposition was valid, and master relaxation curves were obtained. Carbon black increases the modulus of the compound, especially in the rubbery region, and the time range over which the glass-rubber transition occurred. The shift factor is divided into three regions; an Arrhenius dependence in rubbery and glassy states, and Williams-Landel-Ferry (WLF) dependence in the transition region. The apparent activation energy in the rubbery state increases with the volume fraction of carbon black (or silica) and is unaffected by the structure of the filler. The increase in activation energy is caused by the attachment of rubber chains to the carbon surface. At 30% elongation, the activation energy for carbon-black-filled rubber has a value of 32 kcal/mole, independent of structure and concentration of the filler.
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  • 104
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 579-586 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Samples of thin, unplasticized PVC films were fatigued to rupture in nitrogen and ethanol vapor. Examination of the fracture surface edges showed unusual yielding due to the proximity of an unconstrained surface. The scanning electron microscope (SEM) photomicrographs show several indications of supermolecular order in these highly oriented edges and possibly in the relatively unoriented bulk material.
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  • 105
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dynamic mechanical properties of semicrystalline poly(tetramethyl-p-silphenylene siloxane) in three morphological preparations were measured over the wide frequency range of about 0.002 Hz to 500 Hz and the temperature range of about - 190°C to 100°C. The three samples were all isothermally crystallized at 125°C. Two samples had a spherulite size of 25 μ diameter but differed in the time allowed for secondary crystallization. The other sample had a smaller spherulite size. By assuming compliance additivity, the viscoelastic behavior could be separated into five relaxation processes with an indication that a sixth existed at low temperature. Two processes called γ1 and γ2 could be resolved at low temperatures. The γ1 process was associated with the amorphous region since the peak strength was affected by the rate of cooling through the glass transition region; the γ2 peak, unaffected by cooling rate, is attributed to the crystalline part. In the high-temperature region, the β peak is associated with the glass transition and has a shape and location that is essentially independent of the morphology. The highest temperature α2 process, whose maximum was not observed in the experimental range covered, is attributed to the crystalline region and is sensitive to changes in crystallization history. The strength of the α1 process unlike that of the other processes was found to be a function of temperature; it was associated with the noncrystalline region.
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  • 106
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 407-416 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Some dilute solution parameters have been measured for linear amylose tripropionate samples in ethyl acetate and tetrahydrofuran. Mark-Houwink relations for the molecular weight range 104 to 1.5 × 105 have been established, and the exponents are 0.58 and 0.61 in ethyl acetate and tetrahydrofuran, respectively. This indicates that the coil is only slightly expanded in these solvents. A value of 6.21 was calculated for the characteristic ratio C∞ leading to a steric parameter of σ = 2.32. The temperature dependence of the unperturbed dimensions (d In C∞/dT) was found to negative and of the order -4.05 × 10-3°K-1.
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  • 107
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 431-439 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effect of temperature T and weight-average molecular weight M̄w on the rate of spreading of polystyrene melts on plane solid surfaces has been examined. The activation energy E of spreading was estimated to be 25.2 ± 3 kcal/mole, which is of the same magnitude as the activation energy for flow of polystyrene melts. The rate of spreading was found to be inversely proportional to M̄w raised to the 1.5 power. This rate of spreading, measured as the time rate of increase in the liquid-solid contact area, dA/dt, could be expressed as \documentclass{article}\pagestyle{empty}\begin{document}$ dA/dt = Ke^{-E/RT} \bar M_w {}^{-1.5}\gamma _{1{\rm v}} (\cos \theta _{\rm s} - \cos \theta _{\rm d}) $\end{document} where γ1v is the melt surface tension and θd and θs are the dynamic and static contact angles, respectively. The numerical value of K has been calculated to be (6.025 ± 3.693) × 10-14 in the temperature range of 110-260°C and for the values of M̄w from 2000 to 37000.
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  • 108
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 501-513 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Heterogeneous network polymers composed of rigid polypeptide chains and flexible polyether chains were synthesized. That is, poly(L-glutamic acid) (PLGA) was crosslinked with poly(oxyethylene glycol) (PEG) at various carboxy/hydroxyl mole ratios K. The solubility tests and hydrolysis of heterogeneous network polymers suggest that the crosslinking reaction proceeds by esterification. The dynamic mechanical properties of these polymers(100 Hz, -100-200°C) are greatly influenced by the presence of a trace of water and the weight per cent of PLGA. In addition, some of these polymers show only one maximum in the temperature dispersion of dynamic loss modulus E″ and tan δ, although their shape is rather broad. The x-ray photographs of these polymers show an amorphous halo or weak Debye-Sherrer rings. These findings suggest that these polymers are not simple adducts; neverthless PLGA and/or PEG domains exist.
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  • 109
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 555-562 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The rules formulated by Koningsveld for the determination of the critical concentration are shown to be in accord with the Flory-Huggins theory. Sometimes, however, they may not refer to stable conditions, and their application in such cases will result in misleading conclusions.
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  • 110
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 563-578 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Four samples containing 40, 60, 80, and 97 wt-% of poly(vinyl chloride), the rest being plasticizer and stabilizer, were tested by using the Weissenberg Rheogoniometer in the steady-shearing mode at temperatures between 155 and 235°C and rates of shear \documentclass{article}\pagestyle{empty}\begin{document}$ \dot \gamma = 0.01 - 400 $\end{document} sec-1. The viscosity η versus \documentclass{article}\pagestyle{empty}\begin{document}$ \dot \gamma $\end{document} follows Graessley's theoretical dependence for infinitely entangled system. The primary normal-stress difference coefficient ψ versus \documentclass{article}\pagestyle{empty}\begin{document}$ \dot \gamma $\end{document} is well described by the same theoretical function, used with the square of its argument. The temperature dependence of η0 and ψ0 shows discontinuities at T = Tb. The numerical values of Tb can be calculated from the theory of the melting point depression due to diluent. The activation energy of viscous flow Eη below Tb is 5-9 times as large as above this temperature. The activation energy of normal stress is found to be Eψ ≈ 5Eη. The characteristic relaxation times τo, ψp, calculated from superposition of η versus \documentclass{article}\pagestyle{empty}\begin{document}$ \dot \gamma $\end{document} and ψ versus \documentclass{article}\pagestyle{empty}\begin{document}$ \dot \gamma $\end{document} data, respectively, onto Graessley's master curves, and τN, computed from zero shear parameters η0 and ψ0, differ in their sensitivity to the melting of microcrystalline regions. It is postulated that in the systems investigated, aggregates with long lifetimes are being formed, increasing the effective molecular weight and introducing changes in the effective polydispersity.
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  • 111
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 633-633 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 112
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 635-643 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Semicrystalline polymers generally exhibit moduli well below their theoretical limit due to chain folding and to lack of crystal alignment. Modulus increases attainable through standard drawing procedures are limited by sample fracture before large draw ratios are reached. Using an Instron capillary rheometer which allowed a draw ratio of 〉 300, transparent polyethylene strands of unusually high c-axis orientation have been produced by a combination of pressure and shear. The virtually perfect crystalline orientation and evidence for extended chains confirm that a significant improvement in modulus can be realized by this technique. The dynamic tensile storage modulus was measured by Vibron over the temperature range -160°C to +120°C. Room-temperature moduli were 7 × 1011 dyne/cm2, higher than any reported values for drawn polyethylene. Values also remained above 1011 dyne/cm2 even at 120°C. The moduli and morphological data have been related by a model consisting of an extended-chain component in paralled with a conventional drawn morphology. Experimental and calculated moduli are compared and related to available theory.
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  • 113
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 665-683 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polystyrene radically polymerized in atmosphere of air is composed of bisegment (C-A) or trisegment (C-A-C) block copolymers consisting of styrene segment (A) and styrene peroxide segment (C). Dielectric measurements of a system of copolymers of styrene and oxygen were obtained above the glass temperature. Three primary relaxations, a, b, and c, in order of descending temperature, were found corresponding to three microphases: styrene phase (phase a), styrene peroxide phase (phase c), and an intermediate phase (phase b) which contains a low concentration of peroxide bonds. An alternating copolymer of styrene and oxygen exhibits the relaxation c alone. With heat treatment above the glass temperature, relaxation c and subsequently relaxation b vanish with thermal degradation of peroxide bonds. The sum of relaxation strengths is linearly related to the content of peroxide bonds which was evaluated by the elementary analysis and DTA. Below the glass temperature, the temperature dependence of dielectric loss of carefully purified polystyrene without peroxide bonds shows very weak peaks which correspond to γ (200°K at 10 kHz) and δ (50°K at 10 kHz) peaks, respectively, in the activation plot. When low molecular degradation products of peroxide bonds are occluded or impurities such as benzaldehyde are added into the specimen, the height of the γ peak is appreciably enhanced, indicating that the reorientation of small polar molecules in polystyrene accompanies the vibration of the phenyl group about the C—C6H5 bond which gives rise to the γ relaxation.
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  • 114
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 1211-1213 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 115
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 1221-1230 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We feel that the lengthy comments given here come down to a few simple points. For uniform, homogeneous swollen membranes the internal driving force for transport in hydraulic permeation experiments is a concentration gradient not a pressure gradient. Equation (1) is in error because it neglects the frame of reference term 1/(1 - ν1). Equation (19) shows properly the connection between K0 and the various diffusion coefficients. In the particular case discussed here and previously we see no evidence to say that a viscous flow mechanism is operative since we can explain all of the K0 data in terms of reasonable diffusion coefficients if proper consideration is given to the frame of reference correction. This is not to say that in many other cases a viscous flow mechanism will not be present or even predominate.
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  • 116
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 1245-1249 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 117
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 1259-1265 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Phase heterogeneity of vulcanizates based on cis-polybutadiene (cis-Europrene) and SBR (Europrene 1500) blends obtained by radiation, thermal, two-stage radiation-thermal, and two-stage thermal-radiation processes was investigated by the radiothermoluminescence method. Unvulcanized blends of these polymers are found to be heterogeneous, exhibiting two glass transition temperatures Tg, which coincide with the values for the initial components. Following vulcanization, the difference between the two Tg values for a polyblend decreases. The decrease is more distinct for polyblends crosslinked at high temperatures. When the vulcanization temperature exceeds 140°C and the crosslink density (or 1/Mc) exceeds 5 × 10-5-1 × 10-4 mole/cm3, the glass temperature ranges of the crosslinked blend are practically superimposed. Such crosslinked mixtures should be considered pseudohomogeneous in phase.
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  • 118
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 1327-1338 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The bivariate distribution function and the ring closure probability for a continuous wormlike chain derived by Gobush et al. and by Yamakawa and Stockmayer are translated into the two-dimensional case. The results may be written in terms of Fourier series instead of spherical harmonics. Evaluation is carried out to terms of order t-3, where t is the ratio of the total contour length to the persistence length.
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  • 119
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 1347-1354 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The molecular weight distribution in various celluloses degraded by methanolysis has been studied by gel-permeation chromatography. It is shown that the accessible portion of the sample apparently degrades preferentially into molecular fragments with a size distribution centered on species with a degree of approximately 8. This result is interpreted as indicating the presence of weak links in the cellulose chains.
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  • 120
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 1395-1406 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The root-mean-square end-to-end distances of isotactic poly(tert-butylethylene oxide) fractions were determined in xylene at 80°C from intrinsic viscosity measurements and in o-dichlorobenzene at 80 and 100°C by light scattering. The characteristic dimension (〈L2〉0/M)1/2 was 1.04 × 10-8 cm in xylene and 0.9 and 0.7 × 10-8 cm in o-dichlorobenzene at 80 and 100°C, respectively. The value in xylene corresponds to a C∞ of 15.9. This observation and the large negative temperature coefficient of (〈L2〉0/M)1/2 suggest that poly(tert-butylethylene oxide) exists in a helical block conformation under these experimental conditions. This conclusion is in agreement with earlier reported NMR measurements.
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  • 121
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 1417-1439 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Information, not previously measurable, about the internal crystallization processes occurring within spherulitic films can now be obtained by combining refractive index, birefringence, and small-angle light-scattering measurements. The surroundings of a spherulite in a solid film are composed of both the adjacent spherulites and their interstices (boundaries), and it is shown that different crystallization processes can occur in each of these regions. Upon annealing a quenched isotactic polypropylene film, the rate of crystallization within the interstices of the space-filling spherulites is observed to be greater than the rate of crystallization within the spherulites themselves.
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  • 122
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 1457-1463 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The elastic tensile modulus of the crystalline regions parallel to the chain axis E1 for poly(isobutylene oxide) (PIBO) was determined by an x-ray diffraction method. The stress-strain (σ - ε) curve calculated from the meridional reflection of (002) shows an inflection point at about 75 MN/m2 or an extension of 0.25%. The observed moduli below and above this point are 29 and 47 GN/m2, respectively, at room temperature. The initial lower modulus agrees well with the value, 29.7 GN/m2, calculated on the basis of the double zigzag structure of PIBO chain determined by Kaji and Sakurada. The higher modulus may be due to an intrachain steric hindrance between the hydrogen atoms of the methylenic group in the main chain and those of the two side methyl groups.
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  • 123
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 1499-1508 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Viscosity, light scattering, and precipitation temperature measurements on dilute solutions of high-density and low-density polyethylene fractions have been carried out and a theory by Flory for phase equilibrium of linear polymers has been extended to branched polymer. From the results, it is shown that the entropy parameter ψ, depends on branching; a method for the determination of long-chain branching in polymer fractions is proposed combining precipitation temperature and molecular weight measurements. The method has been applied to the evaluation of long-chain branching in low-density polyethylene.
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  • 124
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The crystallite sizes of α and β forms of nylon 6 along the chain axis were determined by Wallner's method. First the shifts of the maximum positions of meridional reflections from their ideal reciprocal-lattice positions were calculated for the various crystallite sizes. Second, using these relationships, crystallite sizes were estimated from the observed maximum positions of reflections. The estimated values agree well with those from the integral widths of reflections by the method of Hosemann and Wilke.
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  • 125
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 1547-1553 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dielectric properties of a series of semiconducting polyazophenylenes were studied as a function of temperature and molecular weight in the temperature range 293-600°K and for molecular weights between 5,100 and 62,800 at a constant frequency of 1 kHz. The compounds studied included poly-2,4-diaminotoluene, poly-2,4-diaminoanisole, and poly-2,5-diaminotoluene. The dielectric properties are presented in the usual way in terms of a complex dielectric constant ε* = ε′ - jε″. Activation energies of relaxation processes were evaluated from the areas and widths of the dielectric loss factor, ε″, against reciprocal temperature at constant frequency. The dielectric activation energies were found to be roughly equal to the activation energies from the DC conductivity. This indicates that the conduction mechanism is based on rotational movements of molecules or parts of molecules.
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  • 126
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 1177-1188 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An explicit mechanism is described for the anomalous increase in dielectric constant and dielectric loss at low frequencies and high temperatures for poly(vinylidene fluoride) containing ionic impurities. Relations are proposed for the ionic contributions, εi″ and εi″, to the dielectric constant and dielectric loss: \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{*{20}c} {\varepsilon _i ^\prime = (2v_0 q^2 /\pi ^{1/2} lkT){\rm }(D_0 /f)^{3/2} e^{ - (3Ed/2 + W/2\varepsilon 0)/kT} } \\ \\ {\varepsilon _i ^\prime = (2v_0 q^2 /kT){\rm }(D_0 f){\rm }e^{ - (Ed + W/2\varepsilon 0)/kT} } \\ \end{array} $$\end{document} where v0 and D0 are the concentration and the diffusion coefficient of the mobile ions at infinite temperature, q is the charge of an ion (in cgs electrostatic units), l is the distance between electrodes, k is the Boltzmann constant, T is the absolute temperature, Ed is the apparent activation energy for diffusion of the ions, and W is the dissociation energy of the ionic impurities. From the slopes of curves of log εT′ versus 1/T and log ε″T versus 1/T for poly(vinylidene fluoride), energies Ed = 34 kcal/mole and W = 342 kcal/mole were obtained.
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  • 127
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 1195-1205 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Contact angles θ of liquids of different polarity were measured on a series of mixtures of solid high polymers and a series of copolymers. The mixtures were composed of an alternating poly(ethylene-co-maleic anhydride) (EMA), and its addition product with n-octadecylamine, poly(ethylene-co-N-n-octadecylmaleamic acid) (EOM). The co-polymers were composed of the same monomeric units as the mixtures. The surface tension γs of EOM, calculated from θ by the Good-Fowkes-Owens-Wendt treatment, decreased slightly with increasing molecular weights and then reached a limiting value. Plots of γs against EOM concentration indicated large negative excess surface tension of the units with lower surface tension, EOM, in both series studied. For the mixture series, γa first sharply decreased with the EOM concentration; then it reached a limiting value, the γs of pure EOM, at a very low EOM concentration. This indicates phase separation of the two polymers, and the thickness of a monomolecular surface layer was calculated from these data. For the copolymers, γs varied logarithmically with the EOM concentration. Throughout the whole concentration range, the data fitted the equation developed by Belton and Evans for ideal mixtures.
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  • 128
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 1231-1234 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 129
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 1239-1243 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 130
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 1477-1483 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effect of drawing on the glass-transition temperature of amorphous poly(ethylene terephthalate) has been studied. The Tg decreases to a minimum at a draw ratio of 1.5, then increases to a maximum at a draw ratio of about 2.0, and again decreases with increasing draw ratio. The relationship between the change of structure and Tg is discussed in terms of the configurational entropy and the rate of molecular motion in local-mode relaxation. On the basis of configurational entropy, the decrease of Tg at the beginning of drawing depends on the increase of configurational entropy, while at draw ratios above 2.0 it depends on the increase of entropy associated with intermolecular interaction. From the point of view of molecular motion, it is concluded that the change of Tg is determined by local oscillations in the amorphous region.
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  • 131
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 1537-1546 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Free electrophoresis, differential spectral UV analysis, and the determination of the coefficients of selective sorption were used to investigate, in aqueous solutions of halides, the behavior of two polycations, poly[1(2-hydroxyethyl)pyridinium methacrylate] and poly[1(2-hydroxyethyl)trimethylammonium methacrylate]: i.e., one species with and the other without a pyridine ring in the side chain. Electrophoretic data were used to estimate the length of the electrophoretic segment and the approximate charge of the polyion in solutions of the individual salts. A comparison of the data showed that the interaction is not due to the presence of the pyridine ring in the side chain and that the order of activity of the halide anions is the same for both types of polymers.
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  • 132
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 1565-1574 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: When isotactic polystyrene (i-PS) is crystallized from the melt or from the glassy state at rather large supercooling an additional melting peak appears on the curve during scanning in a differential calorimeter. The overall rate of crystallization deduced from the total peak areas as a function of crystallization time did not fit the Avrami equation well. When we omit the area of the additional melting peak in the kinetic analysis a much better fit is obtained. We also observed that no lamellar thickening occurs during isothermal crystallization. In view of the low degree of crystallinity of i-PS these results lead to the idea that a secondary crystallization process takes place within the amorphous parts of the spherulites resulting in this additional melting peak on the DSC curve. The large supercooling needed and the increase in peak area with increasing molecular weight make us suppose that intercrystalline links are probably responsible for the additional melting peak of bulk-crystallized i-PS. Electron microscopic studies of surface replicas of i-PS support this view.
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  • 133
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 1639-1648 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The theory of the preceding paper is compared with previously unpublished experimental results on the viscoelastic properties of two polystyrene fractions of molecular weight 1.9 × 106 and 1.2 × 106 in nitropropane, which is very nearly a theta solvent, and in toluene, a good solvent. At the concentrations used, around 1%, the theory predicts extensive departures from non-draining toward free-draining behavior; these effects are observed. The theory similarly fits experimental data of Johnson on a sample of polystyrene of molecular weight 860,000 in decalin and dioctyl phthalate in the same concentration range.
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  • 134
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 1697-1705 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: High-speed photographic studies in connection with photodensitometry were performed to study craze healing in ABS/MMA sheets occurring within 5 microseconds to 20 milliseconds after rupture. Observations on various parts of the deformed specimens, particularly at a plastic zone in the vicinity of a crack, show that there are two stages of healing; first, a relatively elastic stage, and second, a relatively viscoelastic stage. Results of the observation also indicate that the rate of healing is influenced by the magnitude of plastic strain to which the specimens were subjected. The healing mechanism near an advancing crack is discussed briefly.
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  • 135
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 1711-1725 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The problem of describing the composition heterogeneity of the products of reactions of substituent groups on a polymer chain when there are interactions between neighboring groups is considered. A Monte Carlo simulation method and a modified first-order Markovian approximation are proposed for obtaining composition distributions. The conditions of the mathematical experiment (the optimum length of the model chain and the size of the sample population) are found from a comparison of calculated parameters of the distribution of units with the exact values obtained by accurate analytical solution. These conditions depend upon the ratios k0:k1:k2 of rate constants for reaction of groups with neither, one, or both neighboring groups already reacted. The modified first-order Markovian approximation gives results close to those of the Monte Carlo simulation for fairly long chains (100 units or more). Results are summarized graphically for calculations of the composition heterogeneity for various k0:k1:k2 ratios. As an example of the application of the suggested theoretical approaches the quaternization of poly-4-vinylpyridine with benzyl chloride is considered. The individual rate constants were found from experimental kinetic data. The functions of composition distribution calculated with these constants (k0 = 5.8 × 10-4 l mole-1 sec-1, k1 = k2 = 1.7 × 10-4 l mole-1 sec-1) were compared with experimental data obtained by gel permeation chromatography. Fairly good coincidence was found between experimental and calculated data. The satisfactory description of both reaction kinetics and composition heterogeneity by the same constants enables us to conclude that the neighboring group effect is dominant in this reaction.
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  • 136
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 2119-2134 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The local modes refer to vibrational motions of the main chain in the glassy state which are thermally excited with a relatively large amplitude and are consequently strongly damped into relaxational motions by the intermolecular viscous force. This paper describes a theory of strengths of the dynamic mechanical and dielectric local mode relaxations, in the latter of which the correlation of dipole arrangement along the main chain is considered. The results are compared with the observed strength and its dependence on temperature and pressure, in particular for the dielectric β relaxation of poly(vinyl chloride). Satisfactory agreement is obtained between theory and experiment.
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  • 137
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 2157-2161 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 138
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    Keywords: Physics ; Polymer and Materials Science
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  • 139
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 2209-2251 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Stress crazing is studied in three forms of crystalline, isotactic polypropylene (PP): (1) smectic/nonspherulitic, (2) monoclinic/nonspherulitic, and (3) monoclinic/spherulitic PP. Optical and scanning electron microscopy as well as stress - strain measurements are used to characterize crazing behavior in these three forms as a function of temperature (-210 to 60°C) and of the gaseous environment (vacuum, He, N2, Ar, O2, and CO2). Forms 1 and 2 are found to craze much like an amorphous, glassy polymer in the temperature range between -210 and -20°C, irrespective of environment. The plastic crazing strain is large close to the glass-transition range (ca. -20°C) of amorphous PP and in the neighborhood of the condensation temperature of the environmental gas. Near condensation, the gas acts as a crazing agent inasmuch as the stress necessary to promote crazing is lower in its presence than in vacuum. A gas is the more efficient as a crazing agent, the greater is its thermodynamic activity.Spherulitic PP (form 3) crazes in an entirely different manner from an amorphous, glassy polymer, showing that the presence of spherulites influences crazing behavior much more profoundly than the mere presence of a smectic or monoclinic crystal lattice. Below room temperature, crazes are generally restricted in length to a single spherulite, emanating from the center and going along radii perpendicular, within about 15°, to the direction of stress. They never go along spherulite boundaries. Gases near their condensation temperature act as crazing agents much as in nonspherulitic PP. Above room temperature the crazes are no longer related to the spherulite structure, being extremely long and perfectly perpendicular to the stress direction. Apparently the crystals are softened enough by thermally activated segmental motion to permit easy propagation of the craze. The morphology of the fracture surfaces and its dependence on temperature and environment is described and discussed. Concerning the action of gases as crazing agents it is argued that the gas is strongly absorbed at the craze tip, where stress concentration increases both the equilibrium gas solubility and the diffusion constant. Hence, a plasticized zone is formed having a decreased yield stress for plastic flow. This is considered to be the main mechanism by which the gas acts as a crazing agent. In addition, reduction of the surface energy of the polymer by the adsorbed gas eases the hole formation involved in crazing.
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  • 140
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 2267-2280 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effects of swelling and annealing treatments on viscoelastic behavior were studied in melt-crystallized and solution-crystallized samples of isotactic polypropylene (iso-PP) over the temperature range -150 to 150°C. The log E″ versus T curves exhibited α, β, and γ peaks in order of decreasing temperature. The β peak of the melt-crystallized sample shifted to higher temperatures after annealing, but was not affected by swelling. The α peak of melt-crystallized polymer was affected by swelling treatments. It increased in height and shifted to lower temperatures almost linearly with the volume fraction of absorbed solvent. The magnitude of the shift was independent of the solvent species - toluene, p-xylene, tetralin, carbon tetrachloride - however, it depended significantly on the temperature at which the sample had been heat treated. For solution-crystallized polymer, no peaks in log E″ were observed in the temperature range of the β peak of melt-crystallized material, but the α peak appeared larger and broader, and at higher temperature than the corresponding peak in the melt-crystallized polymer. After swelling or annealing, the low-temperature component of the α peak of the solution-crystallized sample decreased in height and at the same time a new loss peak appeared at -55 and 0°C, respectively, is swollen and annealed samples. In particular, in the case of annealing treatments, the high-temperature component of the α peak shifted to still higher temperatures. From these results on the solution-crystallized sample it can be deduced that the segmental motions in the amorphous phase are very strongly constrained by surrounding crystalline phases as compared with those in the amorphous phase of the melt-crystallized sample, and the constraints imposed on the segmental motions are released to a great extent by both treatments. Finally, swelling effects on the γ peak were examined. The γ peak of the melt-crystallized sample decreased in height after swelling. On the other hand, the γ peak of the solution-crystallized sample separated into two peaks, which might be attributed to the mechanical relaxations in the crystalline and amorphous phases.
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  • 141
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 2091-2110 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A model is proposed to account for the orientation of crystals in spherulites upon deforming a polymer. The model assumes affine deformation of the spherulite accompanied by three processes of crystal reorientation within the spherulite. These are tilting of molecular chains with respect to the plane of the lamellae, characterized by a parameter K, twisting of the lamallae about the spherulite radii described by η, and rotation of the b crystal axis about the c axis characterized by a third parameter, P. Values of these parameters are fitted to measured orientation functions and compared with experimental measurements of the azimuthal variation of the intensities of the 110 and 200 crystal reflections from low-density polyethylene. Good agreement is found between the experimental and theoretically predicted intensity variation. Time-dependent experiments under relaxational and vibrational conditions are also treated by the theory.
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  • 142
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 2153-2155 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 143
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 2163-2167 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 144
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 175-185 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Rotational isomeric-state theory has been applied to investigate chain configurations of a polyester prepared from 4′,5-(1,1,3-trimethyl-3-phenylindan) dicarboxylic acid and 2,2-bis(4′-hydroxyphenyl) propane (POLA polyester). Independent conformations for each repeat monomer unit of the chain have been assumed in the calculations of the unperturbed dimensions. Rotations about the oxygen-phenylene-carbon (O—φ—C) bonds are considered to be free with twofold symmetric potentials. The trans and cis conformations of the carbonyl-phenylene-carbon (O=C—φ—C) and the indan-carbonyl residues are assumed to have equal probability. Two rotational states, trans and cis, are assigned to the ester C—O bonds. Calculation of the reduced unperturbed dimensions (〈r02〉/M)∞ with conformations thus assigned for the bonds in the repeat unit, and comparison with experiment (0.72 ± 0.02 Å2/g) indicate that the conformation in the ester C—O bonds is predominantly trans. An equation for the conformational potential as a function of rotational angle about the ester C—O bond has been formulated using data on potential barriers for low molecular weight compounds. This equation, yielding a potential difference between the cis the trans isomers of 2.5-3.0 kcal/mole, is in good agreement with the prediction made from the calculation of the unperturbed dimensions where a cis/trans ratio of 0.01 for the ester C—O bonds was obtained.
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  • 145
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 223-238 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The structure of poly(N-methyl laurolactam) has been studied in the solid state and in solution. In oriented, annealed monofilaments, the chain exhibits a distorted extended planar zigzag conformation. Upon orientation, an increase in crystallinity and a slight shift of the large d spacing in the diffraction pattern to a higher value is observed. In the crystalline regions of the polymer, the amide groups are proposed to have the anti conformation, whereas the amorphous regions may consist of both the syn and anti forms. Differential scanning calorimetry and thermal mechanical analysis showed multiple melting endotherms which probably result from partial melting and reorganization of small, imperfect crystallites. In solution, nuclear magnetic resonance spectroscopy showed the presence of a conformational equilibrium of the syn and anti amide groups in the polymer chains. The effect of thermal and mechanical treatments on certain infrared group frequencies of the amide moieties was studied and correlated with other pertinent analytical data.
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  • 146
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 2397-2397 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 147
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 2423-2436 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polyethylene was prepared by γ-ray-induced polymerization in the temperature range 0-180°C. The morphology and the physical properties of the polymer as polymerized were studied by electron microscopy, differential scanning calorimetry, and gel permeation chromatography. Aggregates of small lamellar crystals with irregularly growing faces were produced below 55°C. Aggregates of large spherical particles were formed above 60°C together with hemispherical particles which adhered to the substrate. A few lamellar crystals of triangular or amoeba-like shapes were also found above 55°C. The polymers formed below 55°C showed a sharp single endothermic DSC peak and a bimodal molecular-weight distribution, while the sample above 60°C had a double endotherm and a unimodal molecular-weight distribution. These facts suggest that the mechanism of crystallization during polymerization below 55°C is different from that above 60°C. The melting point, however, decreased continuously with increasing polymerization temperature and was much lower than that of extended-chain crystals. The results show that the polyethylene, as polymerized, is composed of folded-chain crystals irrespective of the reaction temperature.
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  • 148
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 2473-2491 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Densified glasses, formed from the liquid state by cooling at 5°C/hr under elevated pressures of up to 517 MN/m2, were studied by thermal analysis and dilatometry at ambient pressure. The materials studied were polystyrene, poly(methyl methacrylate), phenolphthalein, sucrose, and a 1 : 1 mixture by weight of potassium and calcium nitrate. Enthalpies of the densified glasses were found to be up to 2-6 J/g greater than the enthalpies of the glasses formed at atmospheric pressure. The major enthalpy and volume relaxation on heating the densified glasses was found to be not correlated The upper temperature limit of the glass-transition region remained constant for all glasses cooled at various pressures, while the lower temperature limit of the polymeric glasses decreased up to 55°C with increasing pressure. The interpretation of the data suggests that an additional, significant volume relaxation occurred on depressurization at room temperature for all glasses analyzed.
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  • 149
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 2535-2549 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The marked effects of chemical structure on the morphology of single crystals in linear aliphatic polyesters have been investigated. Drawn fibers and solution-grown crystals of poly(ethylene sebacate), poly(hexamethylene sebacate), and poly(decamethylene 1,16-hexadecanedicarboxylate) have been studied by small-angle and wide-angle x-ray diffraction. Electron microscopy, and broadline NMR provided supplementary information.The crystal disorder due to irregularity in the cross section of the molecule due to ester groups along the chain direction increases with increase of the methylene sequence length in the chemical repeat unit. On the basis of the x-ray data and electron microscopy, it is proposed that the nature of the fold surface of single crystals of a given polymer, especially a choice of (001) or (hkl) fold surface (flat lamellae or hollow pyramidal crystals), is determined by energetic competition effects between fold geometry and unit cell symmetry. A smooth increase of the long period with increasing crystallization and annealing temperature seems to be general behavior even when a pronounced stepwise increase might be anticipated.
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  • 150
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 2579-2581 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 151
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 75-80 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Data from the literature are analyzed to show that decay of the chain-end radical of PMMA in the regime of 80-130°C and 1-13000 atm occurs by two mechanisms operating in parallel. These processes are characterized by activation volumes of ca. 70 Å3 (I) and ca. ∼7.5 Å3 (II), suggesting that decay by process I occurs by chain-end diffusion and decay by process II occurs by unzipping of the polymer radical to the monomer.
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  • 152
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 97-114 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: New data are reported for the permeation of inert gases through polyethylene, polytetrafluoroethylene, and silicone and natural rubbers. Additional data are compiled from the literature. The relative solubilities of these gases are practically insensitive to chemical variations in the homopolymer. Hence variations in structure at the glass transition (Tg) and melting (Tm) temperatures that affect diffusion also unambiguously affect permcation. Consequently an equivalence results between permeation at a given temperature for different polymers and permeation at different temperatures for a given polymer. Although the diffusion coefficient changes continuously with temperature, the Arrhenius parameters Do and Ed apparently change discontinuously at Tg and Tm. Their magnitudes and variations with atomic weight reach maxima at about Tg. These data indicate a dependence of the classical correlation between Do and Ed on polymer properties. A perturbed diameter for the permeant, specific for each polymer, is proposed for correlating the Do and Ed data. This correlation makes the changes observed at Tg and Tm more perceptible.
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  • 153
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 159-173 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Samples of poly(4,4′-isopropylidenediphenylene 1,1,3-trimethyl-3-phenylindan-4′,5- dicarboxylate) were fractionated by the column-elution, temperature-gradient technique. Selected fractions, covering a 10-fold range of molecular weight, were shown to have narrow molecular weight distributions by gel-permeation chromatography (GPC), i.e., M̄w/M̄n = 1.15 ± 0.10. The fractions were further characterized by viscometry, light scattering, and membrane osmometry. Characterization of the small samples (ca. 0.3 g) was facilitated by use of a low-volume light scattering cell. This allows measurements of refractive increment, light scattering, and viscosity to be performed on as little as 50 mg of sample. Molecular weights estimated by the GPC-viscometry technique were in good agreement with the values obtained by light scattering. Estimates of the perturbed coil dimensions (150-200 Å) were in satisfactory agreement with those observed experimentally. The polydispersities of the fractions, determined by osmometry and light scattering, were in fair agreement with GPC data; the latter are considered subject to less experimental uncertainty.
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  • 154
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 213-216 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 155
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 925-939 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The chemical and physical crosslink densities of irradiated polybutadiene were determined using a precise and consistent method. This method included the use of a statistical theory of crosslinking modified to include chain reactions and the use of Langley's theory for calculating the number of trapped chain entanglements. The number of crosslinks formed per unit radiation dose, G(X), was measured for a series of polybutadienes containing various isomeric forms of unsaturation. The physical crosslink density and the molecular weight between entanglements were determined from measurements of the compression modulus of swollen samples.
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  • 156
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 1089-1107 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The change of free enthalpy and the chemical potential of solvent for mixing of solvent with crosslinked structures formed by stepwise reactions of the polycondensation type has been derived by an adaptation of the quasichemical equilibrium method. Each monomer unit is supposed to bear a different number of crosslinkable contact points, the coupling of which gives rise to chemical bonds, and of uncrosslinkable contact points, involved in interactions with the solvent, which may be of different type. The results are used to analyze the effect of network topology on the parameters of the swelling equation, particularly on a parameter characterizing the network composition. This parameter may be obtained from analytical data or by using the crosslinking statistics; and model calculations show how it varies with monomer conversion.
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  • 157
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 1127-1135 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A diffusive gas-transport isotope effect is used to estimate the size of the free volume element above and below the glass transition for poly(ethyl methacrylate) and poly(vinyl fluoride). The cavity size, as measured by the hydrogen probe molecule, is apparently larger in the glassy region for both polymers than it is above Tg. It is postulated that the number of free volume elements essentially decreases below Tg, so that the total free volume, which is the sum of all such elements, is smaller below the glass transition, in accord with density measurements on bulk polymers.
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  • 158
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 1145-1162 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Electron microscope studies are reported for crystals of linear polyethylene formed in dilute solution from very sharp low molecular weight fractions. Emphasis is placed on molecular weights in the range of 1.1 × 103 to 15.1 × 103. The dependence of the crystal habit on the crystallization temperature is very similar to that which has been found for the higher molecular weight species. However, the demarcation temperature for the crystallization of the different morphological forms is very molecular weight-dependent. The conditions under which interfacial dislocation networks form can be clearly defined. The molecular weight must be less than 3000, so that these structures are restricted to very small chain lengths. However, not all crystallization conditions within this allowable molecular weight range yield such dislocations. The formation of interfacial dislocation networks are shown to occur only under very special circumstances. Their occurrence clearly cannot be offered as evidence, as has been done in the past, for a regular, chain-folded interfacial structure.
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  • 159
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 1889-1898 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The molecular motion of unsintered polytetrafluoroethylene (PTFE) was studied by dynamic viscoelastic measurements. From results for variously heat treated suspension polymerized (molding powder) PTFE, the following conclusions are drawn. Molding powder, as received, has a high degree of crystallinity according to calorimetric results and lower magnitude of the γ relaxation, but the behavior of the β relaxation suggests that the crystals are disordered more than those of the sintered PTFE. The β relaxation peak for an emulsion polymerized PTFE (fine powder) occurs at a higher temperature and is sharper than that for the molding powder, so that the crystals of the fine powder are better ordered than that for the molding powder. The behavior of the β relaxation for the radiation induced-polymerized PTFE is affected by polymerization conditions, particularly concentration of emulsifier. It is concluded from the results for the unsintered PTFE polymerized by various methods that the nature of crystalline state is decided during the course of simultaneous polymerization and crystallization. Molding powder as received has a relatively high magnitude of relaxation between 30°C to 180°C, but with little temperature dependence in this temperature range. This relaxation is diminished by gamma-ray irradiation. Since the molding powder has a complicated morphology, the relaxation in this temperature range is attributed to inter-particle friction rather than a relaxation associated with motion on the molecular level.
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  • 160
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    Keywords: Physics ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Solution properties of poly[1(2-hydroxyethyl)pyridiniumbenzene sulfonate methacrylate] and poly[1(2-hydroxyethyl)trimethylammoniumbenzene sulfonate methacrylate] were studied. Within a certain concentration range of some added low molecular weight electrolytes, phase separation occurs. The dependence of intrinsic viscosity on molecular weight was determined and the steric factor estimated for both polymers. For nonaqueous solvents, an extrapolation of the dependence of the refractive index increment of the polymer on the refractive index of the solvent leads to an apparent refractive index of the polymer, different from the refractive index determined directly by the immersion method. Some peculiarities of light scattering in solutions with no electrolyte added are mentioned.
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  • 161
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 1979-1991 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Craze and crack growth have been studied in polycarbonate. The results are correlated by a stress intensity factor derived from fracture mechanics. A new model taking creep into account is proposed to explain the experimental results. Theoretical predictions derived from the model are compared with experimental results. Fair agreement is obtained.
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  • 162
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 2291-2308 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: To describe the characteristic crystalline structure of polyolefins, Pennings first proposed a model consisting of a combination of an extended chain crystal (a “shish”) and folded chain crystals (“kebabs”). In Pennings' model the “shish” forms first during a crystallization process under stress and then later the “kebabs” overgrow this “shish” structure epitaxially. Because we had some doubts about such a mechanism, we undertook a series of experimental studies on linear polyethylene, particularly in regard to the crystallization process from a solution under shear. Our conclusion is that the crystals grow first by a screw dislocation mechanism, like whiskers, and then later these are deformed by the shear stress to form the shish kebab structures.
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  • 163
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 2319-2330 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A new, more realistic optical model of a dilute polymer solution is used to calculate the intrinsic birefringence. A general formula is derived valid for an arbitrary equilibrium distribution function of particles in the system. Besides the contributions due to the polymer and solvent, the resulting relation for intrinsic birefringence also contains terms reflecting the effect of orientation of solvent surrounding the polymer chain and the contribution of optical interactions between polymer segments and molecules of solvent. A detailed discussion of the optical interactions in an isotropic solvent reveals that the problem may be transformed in the first approximation into that of interactions between excess dipoles; however, any separation of the macroform and microform effects has no theoretical justification. It is shown that the microform effect depends on a detailed optical model of the statistical segment, and this effect is calculated for two simple models. The expression suggested by Tsvetkov cannot be applied to a segment consisting of anisotropic monomers.
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  • 164
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 2375-2391 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A systematic study of solution-grown polyethylene crystals in the electron microscope using dark-field imaging in several diffracted beams has warranted a detailed analysis of the moiré patterns recorded. Direct proof for the existence of tilt moiré patterns has been obtained for the first time, while parallel and tilt patterns have been positively distinguished. Consideration of the formation conditions and properties of moiré patterns in dark field has been extended to include interference between an electron beam diffracted in both participating crystals with one diffracted in only one of them. Examples of moiré patterns depending thus on double diffraction have been identified.
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  • 165
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 2409-2412 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Transient currents in poly(vinyl chloride) (PVC) are recorded after the application of a step-function electric field for various temperatures. By assuming the Fröhlich rectangular distribution function g(τ) of molecular relaxation times, the limits of relaxation times τ are evaluated. Values of the glass-transition temperature and activation energies of molecular motion determined from a plot of ln τ against 1/T are in satisfactory agreement with those obtained by other methods. By extrapolation to T = ∞, relaxation times are calculated which are in good agreement with those from dielectric loss measurements.
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  • 166
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 2437-2453 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The construction and principle of operation of small-angle light scattering apparatus for studies of supermolecular structure in thin polymer films is described. The apparatus can be used to study changes in spherulite structure during crystallization and changes in films subjected to steady or sinusoidal strain. Typical results with polyethylene films are given.
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  • 167
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 2507-2520 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In order to determine the conformation of poly(ethylene oxide) (PEO), 13C satellite spectra of PEO, 1,2-dimethoxyethane (DME), and dioxane were measured at various temperatures in various solvents, and analyzed. Relations between the coupling constants were derived from the linearity between the parameters N = JAB + JA′B and L = JA′B in AA′BB′ spectra of PEO and DME. The vicinal coupling constants for the individual rotational isomers were obtained from the above relations and the temperature dependences of N and L and the enthalpy differences were calculated in each solvent. The gauche rotamer is more stable than the trans isomer by 250-500 cal/mole in all cases examined.
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  • 168
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 2577-2578 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 169
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 2551-2565 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Crystallization and melting behavior of linear polyethylene under high pressures up to 6000 kg/cm2 has been investigated with a high-pressure dilatometer. Crystallization was carried out at a cooling rate of 1°C/min from the melt at each pressure. The samples were characterized by differential scanning calorimetry, density, and electron microscopy. Folded-chain crystals are formed in the low-pressure region below 2000 kg/cm2. Crystallization in the intermediate-pressure region between 2000 and 3500 kg/cm2 gives a mixture of folded-chain and extended-chain crystals. The extendedchain crystals are the more stable and predominate at increasing pressure. At high pressures above 4700 kg/cm2, two stages of crystallization and of melting can be observed. The phenomenon suggests that the two kinds of extended-chain crystals with different thermal stability, i.e., the ordinary extended-chain crystals and “highly extended-chain” crystals form through individual crystallization processes from the melt at high pressure.
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  • 170
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 1-6 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A series of poly(vinyl formal) membranes was synthesized by formalization of poly(vinyl alcohol) membranes. Representative pieces were selected for this study. Some cellulose acetate membranes cast from dioxane were used for comparison. The main experimental techniques employed included water absorption measurements and direct osmosis measurements. Aqueous solutions of sodium chloride at various concentrations were used for the studies of permeation through the membranes by direct osmosis.The plot of water permeability coefficient Pw versus volume fraction Vw of water absorbed in a membrane was interpreted in terms of the effect of two different types of absorbed water molecules. The individual diffusion coefficients were evaluated from asymptotic slopes of the curves. Similar analyses applied satisfactorily to data found in the literature.
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  • 171
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 23-34 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: DSC traces and specific heat data for poly(p-diphenyl acrylate) (PPBA) and poly(p-cyclohexylphenyl acrylate) (PPCPA) obtained by radical polymerization are reported. The results indicate the existence of a definite ordered phase and of a reversible firstorder solid-liquid transition in both polymers although x-ray diffraction studies showed that they are not crystalline in the conventional sense. The extent of the ordered phase present in each polymer is calculated, and the problems involved in such determination by thermal measurements are discussed. On the basis of the experimental results reported here in conjunction with the x-ray data, models are proposed for the morphology of these polymers.
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  • 172
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 81-87 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Stress-strain relationships are calculated for three models of the deformation of monocrystalline polytetrafluoroethylene, \documentclass{article}\pagestyle{empty}\begin{document}$ \rlap{--} ({\rm CF}_{\rm 2} \rlap{--} )_n $\end{document}. The physical models comprise either sliding one molecule or one plane of molecules parallel to the molecular chain axis past its stationary neighbors. The potential energy is calculated for each stage of deformation by semiempirical methods by use of 6-exp and dipole-dipole interactions. Application of Eyring's activated complex theory leads to stress-strain relationships. These are compared with results of friction measurements on PTFE.
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  • 173
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 115-130 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Effects of neutralization on butadiene-methacrylic acid copolymers have been studied. In Hycar CTB with 2% acid groups, small-angle x-ray scattering gives evidence of some cation clustering and leads to a value of the mean radius of 5.6 Å for the clusters and a value of the distance between them of 70 Å. When the concentration of salt is increased there is no appreciable change in the distance between clusters or in their size, but their number increases. The structure of clusters has been studied by electron paramagnetic resonance in copolymers neutralized with copper salts. The appearance of a line as in the monohydrated acetate salt permits one to define the structure of clusters consisting of two Cu2+ and four RCOO- ions with two H2O or RCOOH molecules. When the temperature is increased, the signal corresponding to Cu2+-Cu2+ pairs disappears. In high molecular weight butadiene methacrylic acid copolymers with 9% acid groups, we have found the ion pair clusters gathered into larger clusters. In dynamic mechanical properties, a relaxation peak appears at 340°K. We interpret this as due to breaking and possible re-forming of dipolar associations.
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  • 174
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 217-220 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 3 Ill.
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  • 175
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 265-287 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The predictions of a model presented previously are tested with data on five styrenebutadiene-styrene copolymers. Differential scanning calorimetry and laser light transmission are the primary tools, spanning 180-630°K, with some evidence supplied also by electron microscopy and mechanical properties. The existence of a first-order phase transition, characterized by a separation temperature Ts, is verified and found to be predictable by the model. Details of morphology, including transitions in microstructure in certain temperature ranges, are also reported and shown to be consistent with the theory.
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  • 176
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 445-454 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The fundamental vibrational frequencies of an isolated chain of cis-1,4-polybutadiene have been calculated. Infrared and polarized Raman data are used in the force constant refinement routine. The assignments of the vibrational frequencies are discussed in terms of the potential energy distribution.
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  • 177
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 35-49 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A theoretical study is presented of the dependence of the vapor permeability of suitable nonhomogeneous polymer membranes on the sense of flow This is based on a simple model of a binary membrane in which the component phases A, B are either intimately mixed, with the composition of the mixture varying continuously across the membrane, or formed into a laminate AB. The influence of various parameters (which represent either properties of the component phases or the experimental conditions) on the magnitude of these flow reversal effects has been investigated. The results have proved useful as an indication of the capability of such membrane valves and of the conditions for optimum performance, as well as for the understanding of the behavior of experimental systems.
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  • 178
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 89-96 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(ethylene 2,6-naphthalene dicarboxylate) exhibits thermally stimulated chemiluminescence after exposure to ultraviolet radiation and oxygen. The chemiluminescence spectrum is essentially the same as the fluorescence spectrum of the polymer with a maximum intensity at 430 nm. Upon heating, the decay of the luminescence follows a first-order law with an activation energy of 26.3 ± 0.3 kcal/mole. A comparison of the ultraviolet absorption spectra of the polymer before and after exposure to ultraviolet light and oxygen indicates that the naphthalene ring is oxidized. Heating the polymer above 80°C causes decomposition of the initial photo-oxide to produce luminescence.
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  • 179
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 145-158 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The behavior of individual spherulites on uniform deformation of bulk polyethylene is studied with a model consisting of a spherical spherulite and a homogeneous matrix having the properties of the polymer. On the basis of this model, the nonaffine or inhomogeneous deformation in the spherulite is found to be primarily due to the curvilinearly anisotropic property or, more specifically, the spherically isotropic property of the spherulite. In the case of uniaxial stretching, mechanical interactions between spherulites are also to some extent responsible for the microinhomogeneous deformation. Details of the predicted deformation mode are compared with experimental observations reported in the literature and reasonable agreement is attained between theory and experiment for lightly drawn samples.
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  • 180
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 201-212 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It has been reported in earlier papers that aromatic additives can reduce the rate of radiation-induced degradation of poly(methyl methacrylate) (PMMA), depending on the concentration, the distribution, and the resonance of the aromatic system. In the present work, the temperature dependence is studied, together with the influence of molecular mobility, which is determined by the physical state of the system. For this purpose, PMMA containing benzene, biphenyl, naphthalene, anthracene, phenanthrene, pyrene, or benz[a]anthracene, was γ-irradiated at room temperature and also, except with naphthalene and biphenyl, in the temperature range -80 to 160°C. The changes in degradation rate were related to the first excited singlet state and to the resonance energy of the additives. The results suggest that at low temperatures both electron scavenging and transfer of excitation energy occur. At temperatures between the γ transition and the glass transition, the significance of energy transfer compared with electron scavenging increases, whereas the inhibitory effect decreases. Above the glass transition temperature the inhibition decreases more rapidly. This is related to scavenging of radical chain fragments, due to increasing molecular mobility, which causes a decrease in recombination rate. This sensitization of degradation competes with the inhibition by energy transfer and electron scavening, and may prevail at temperatures above 185°C. The opposing effects of these mechanisms can be clearly shown with the system PMMA-benzene. In viscous mixtures, sensitization prevails even at room temperature.
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  • 181
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 255-263 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The rate-determining step of crystallization of macromolecules from melt and solution is shown to be molecular nucleation. Molecular nucleation is described by using classical nucleation theory. Good agreement is found between the molecular nucleus size and the critical length of the rejected species. Molecular nucleation has a higher free-energy barrier than secondary nucleation; it might thus lead initially to independent patches of each molecule on the crystal surface. A possible reason for secondary nucleation on extended surfaces is suggested.
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  • 182
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 289-293 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Much recent work has been carried out on the tear behavior of elastomers, both filled and unfilled, especially by workers at the Natural Rubber Producer's Research Association. By use of a criterion for tearing involving the concept of the tearing energy, the effects of variables such as test temperature, test rate, specimen geometry, and chemical nature of the elastomer have been investigated. The one variable which has not yet been studied is the specific effect of changes in the degree of crosslinking on tear behavior. By use of data published in the literature on the smooth tear behavior of unfilled SBR vulcanizates, it is shown that these data can all be superposed onto a common response curve when the proper normalizations are applied.
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  • 183
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 385-398 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Macromolecular chain scission under mechanical stress has been studied by infrared spectroscopy. The dependence of accumulation of chemical bond scissions on temperature T and uniaxial tensile stress σ has been investigated. The rate constant K for bond dissociation under mechanical stress has been found to obey the modified Arrhenius equation: K = K0 exp{ - (EA - ασ)/RA}. The quantitative connection between the rate constant for bond dissociation and mechanical lifetime τ has been established. Analysis of the experimental data indicates that the strength and mechanical lifetime of polymers is determined by the kinetics of mechanochemical scission of the main chains of polymer molecules.
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  • 184
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 901-911 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The 22.6-MHz Fourier-transform noise-decoupled 13C (carbon-13) NMR spectra of several ethylene-vinyl acetate (E-VA) copolymers were obtained. We found that triad information on monomer placement can be deduced from carbonyl resonances, triad and pentad information can be deduced from methine carbon resonances, and triad information is available from the methylene carbon resonances. The random comonomer distributions in E-VA polymerizations were demonstrated up to pentad placements. In addition, the use of model-compound data in the analysis of copolymer spectra was shown.
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  • 185
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 941-975 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Light-scattering, osmotic pressure, and viscometric studies on fractions of cellulose acetate (degree of substitution 2.45) in three solvents are described. The data yield the dependence of the mean-square radius of gyration 〈s2〉, the second virial coefficient Γ2, and the intrinsic viscosity [η] on molecular weight M and temperature. The results are interpreted to show that excluded volume effects on 〈s2〉 are negligible, even though Γ2 is large and dΓ2/dT is positive. The large experimental value of d In [η]/d In M is interpreted in terms of partial draining effects. Data on 〈s2〉 and [η] for other cellulose esters in the literature are similarly interpreted. Significant aggregation found in solutions of cellulose acetate in many solvents is discussed.
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  • 186
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 991-1000 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Thermoelectrets of poly(methyl methacrylate) were exposed to various atmospheres of known relative humidity between 0 and 100% and the thermal current spectra analyzed. The study of the decrease of the heterocharges as a function of the exposure time reveals important differences in stability between the three peaks of the spectrum; the two peaks appearing at low temperatures can be attributed to a uniform volume polarization, and the third peak observed at high temperature to a space charge polarization. The shift of the peaks indicates plasticization of the polymer by water vapor. This effect is reversible when the samples are exposed for a sufficiently long time to a drying atmosphere. The complex variations of the initial rise of the spectrum as a function of the exposure time show that the activation energy of the peaks probably depends upon the degree of hydration of the polymer.
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  • 187
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 825-848 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Internal viscosity models (IVM) for dilute-solution polymer dynamics differ in how they define the deformational force Fd which includes ϕ, the IV coefficient, and in how they treat polymer rotational velocity Ω. Here, the handling of angular momentum is shown to be crucial. A torque balance in simple shear flow at shear rate G leads to stress symmetry and specification of Ω(G) which differs greatly from the conventional Ω = G/2. This determines the G dependence of viscosity η and normal stress coefficient ζ. There are also implications of a transition in rotational behavior as ϕ approaches a critical value. Predictions of η(G), ζ(G), and η*(ω) are presented for two versions of Fd: one derived recently by the authors and one being most commonly used at present. Limiting cases for high and low ϕ, and for high and low G and ω, are discussed. Some differences exist between predictions of the two Fd models, but these are surprisingly minor.
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  • 188
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 891-899 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: If the counterion of a polyelectrolyte is not identical with any of the ions of a low molecular weight electrolyte added to the solution, the system may be regarded as a four-component system. Relations for the refractive index increments have been derived which allow the determination of the coefficient of selective sorption of the added electrolyte from the refractive index increments of the components independent of the original counterion of the polyelectrolyte. Equilibrium dialysis and differential refractometry were used to study the interaction of KCl, KBr and NaI with poly[-1(2-hydroxyethyl)pyridiniumbenzenesulfonate methacrylate] or with an analogous polymer containing a toluenesulfonate counterion in aqueous solutions. The coefficient of selective sorption increases in the series Cl- 〈 Br- 〈 I- from strongly negative to strongly positive values; the specific interaction of these counterions with the macroion increases in the same order.
    Additional Material: 1 Ill.
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  • 189
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 1575-1586 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A new technique was developed to study the molecular mechanics of highly oriented polypropylene during stress relaxation and creep. The polarized infrared spectrum was recorded while the polymer was under load. Stress relaxation effects were investigated during the two-stage process of fast decay followed by a slower “dynamic equilibrium” decay by examining the stress-sensitive 975-cm-1 band and the orientation-sensitive 899-cm-1 band. In the fast decay region, the aligned chains became more highly overstressed and the nonaligned chains quickly relieved themselves of their initial overstress. These findings suggest an exchange of stress from nonaligned to aligned chain segments, without much orientation change. Also, a rupture of very highly overstressed aligned chains is though to occur. In the slow decay region, the aligned overstressed chains showed a relief of stress accompanied by some disorientation or helix distortion. Creep, however, appeared to occur via a process which involved all chains regardless of alignment. It was found that the number of highly stressed bonds increased with time at the expense of the intermediately stressed bonds. Very little change in overall orientation was noted, which probably explains the observed crazing and void formation.
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  • 190
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 1607-1618 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dynamic mechanical properties have been determined and the β relaxation temperatures Tβ have been located for a series of copolymers of ethylene with norbornene, methylnorbornene, dicyclopentadiene, and octahydrodimethanonaphthalene. The Tβ values show discontinuous changes with changing comonomer content. The several levels of Tβ observed apparently can be associated with the sequence of close multiplets of norbornane moieties ranging from isolated units through pairs to triads and higher. For isolated norbornane units Tβ is around 10°C, while for pairs of these units, probably separated by a C2H4 unit, it is 55°C. The size of the norbornene-type comonomer has a small but measurable effect on these values of Tβ. The bearing of these results on the problem of defining a value of Tg for polyethylene is discussed.
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  • 191
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 1649-1666 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The morphology of solution-grown single crystals of syndiotactic polypropylene with different degree of stereoregularity is compared. A sector formation phenomenon, found in some monolayer single crystals, is discussed in terms of possible crystallographic fold planes, growth planes, and gemination planes. A correlation between thermodynamic and morphological properties such as apparent enthalpy of fusion, critical long spacing, critical annealing temperature, and the number of configurational chain defects along the macromolecule has been found. Two endothermic peaks are observed in the DSC thermograms of single-crystal aggregates of syndiotactic polypropylene. The low-temperature peak is attributed to melting of crystals or parts of crystals with incorporated chain defects. The high-temperature peak corresponds to the melting endotherm of more regular crystalline zones. The peak-area ratio seems to depend on the degree of stereoregularity.
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  • 192
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 1667-1696 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Several experimental techniques, including measurements of salt rejection, water flux, birefringence, and membrane opaqueness, were used to characterize the structure and performance of typical cellulose acetate desalination membranes. The results indicate that optimum salt rejection and water flux characteristics are related to the presence of molecular orientation effectively perpendicular to the membrane surface. An alignment-type flow mechanism involving water contained within the oriented structure is consistent with the observed structural and transport phenomena. The various membrane fabrication procedures apparently have significant effects on the development of molecular orientation in the thin surface layers of the membrane.
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  • 193
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 1733-1741 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Simultaneous measurements of light scattering and electric birefringence on a crystallizing solution of poly(ethylene oxide) (PEO) are shown to lead to the determination of the radius, thickness, and number of crystals at the early stages of the crystallization process.
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  • 194
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 1753-1770 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A study has been made of the viscous properties of poly(para-benzamide) (PBA) solutions in dimethyl acetamide, which undergo a transition from an isotopic to an anisotropic (liquid-crystal) state at a definite concentration C*. The polymer solutions behave in many respects (as regards the concentration and temperature dependence of viscosity, etc.) like solutions of low molecular weight compounds forming a liquid crystal phase, although the transitions are less pronounced in the polymer solutions owing to their polydispersity. It is shown that the viscometric method, being extremely sensitive to C*, is convenient for determining phase diagrams of anisotropic polymer solutions. The values of C* as related to the molecular weight of PBA have been determined, and a general criterion for transition from isotropic to anisotropic solutions established; the latter has the form (CM̄)* ≈ 1.3 × 105 at 20°C. This criterion is in line with the condition for the formation of the liquid-crystal structure in a dispersion of rodlike particles as proposed by Flory.Generalized concentration dependences of viscosity have been plotted by reducing concentration to C* and viscosity, to the maximum viscosity at the phase transition point. In investigating the flow properties of PBA solutions we revealed the existence of a yield point in the range of low shear stresses, and an intersection of the flow curves of solutions of different concentration at high shear stresses, which excludes a generalized representation of the flow curves in reduced ordinary-type coordinates.
    Additional Material: 15 Ill.
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  • 195
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 1441-1456 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The theory of Franklin et al. is employed for the calculation of the maximum form birefringence of a polymer having lamellar morphology. The results confirm the experimental conclusion that for low-density polyethylene, the form birefringence approaches 3% of the total birefringence. The theory also predicts the parabolic dependence of the form birefringence on the refractive index of the amorphous phase. It may be applied to estimate the dynamic form birefringence and leads to a value of the dynamic strain-optical coefficient which is of the order of 2-15% of the total.
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  • 196
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 2195-2207 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It is shown that in the general theory of incompressible simple fluids with fading memory there are, for several types of nonsteady shearing motions, simple universal asymptotic relations between the shear stress S12 and the first normal stress difference N1 = S22 - S11. The kinematical situations considered include initiation of steady shearing, rest after steady shearing, and sinusoidal oscillation. In, for example, relaxation following cessation of a steady shearing flow with rate of shear κ, there holds, to within an error O(κ4): \documentclass{article}\pagestyle{empty}\begin{document}$ dN_1 (t)/dt = - 2_\kappa S_{12} (t). $\end{document} This and the other derived universal relations between N1 and S12 are either consequences of, or are closely related to a general asymptotic formula [B. D. Coleman and W. Noll, Revs. Mod. Phys., 33, 239 (1961), eq. (6.15)] expressing N1 as an integral of the product of the shear relaxation modulus and the square of the history of the relative shear strain.
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  • 197
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 2189-2193 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The thermal expansion contribution due to temperature-dependent π-electron delocalization is evaluated from spectral measurements on a single crystal polydiacetylene (poly-2,4-hexadiyne-1,6-diol bisphenylurethane). The observed temperature independence of backbone associated vibrations (less than ±1 cm-1 change in νC=C and νC≡C between 25 and 90°C) implies that thermal conformational fluctuations and equilibrium defect formation (which produce a negative thermal expansion coefficient) do not measurably affect π-electron delocalization. The separation of equilibrium defects is either much longer than that of nonequilibrium defects or much longer than required to appreciably limit π-electron delocalization in an effectively defect-free polymer. Arguments presented indicate that, in the experimental temperature interval, the observed thermal expansion coefficient in the chain direction is over an order of magnitude larger than the delocalization-associated contribution.
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  • 198
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 2281-2290 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The molecular relaxation behavior of poly(dimethyl siloxane) (PDMS) exposed to various gases pressurized to 207 megapascals (MPa) was investigated by pulsed nuclear magnetic resonance spectroscopy. For a gas of low solubility, such as helium, the gas acts only as a pressurizing medium allowing the effect of pressure on the glass transition to be determined. For gases of high solubility the gas acts not only as a pressurizing medium but also as a plasticizing agent, expanding the polymer lattice and increasing the frequency of molecular motions. The plasticizing effect of argon was found to increase the temperature dependence of the molecular correlation frequency.
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  • 199
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 2309-2317 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Crystallization processes occurring during polymer synthesis in a nonsolvent medium are discussed. It is concluded that in the case of heterogeneous polymerization of ethylene the polymer is produced as a supercooled liquid surrounding the catalyst particles. These particles then coalesce until a critical size is reached allowing a high nucleation probability. Thus coalescence coupled with polymerization, leads to crystallization at a relatively uniform particle size. Two less usual polymerization catalyst systems, VCl3 produced by a high-frequency discharge in VCl4 vapor, and the mixture of TiCl4 and Al(CH3)3 vapors (an apparently homogeneous system) are used to illustrate these concepts for polyethylene.
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  • 200
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    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 2331-2345 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetics of isothermal crystallization of polyethylene under high pressures ranging from 840 to 5300 kg/cm2 has been studied dilatometrically. The crystallization rate estimated from the half-time of the overall transformation increases markedly with pressure. The Avrami exponent n becomes smaller with increasing pressure. Values of n ≈ 2 for the crystallization at 840 and 1950 kg/cm2, and n ≈ 1 at 5100 and 5300 kg/cm2 were obtained. Differential scanning calorimetry and electron microscopy data are presented. It is concluded that extended-chain crystals grow rapidly, predominantly in one dimension, at high pressure. Relations between log k and Tm/T(ΔT) and Tm2/T(ΔT)2 are nearly linear. Here, k is the crystallization rate constant from an Avrami equation, ΔT = Tm - T, Tm is the melting point, and T is the temperature of crystallization. From the dependence of the slope of the straight line on the crystallization pressure it is concluded that the surface energy of crystal nuclei decreases with increasing pressure.
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