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  • 1970-1974  (555)
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  • 1972  (555)
  • Physics  (555)
  • 101
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    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 721-740 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An unsaturated polyester resin and the styrene-crosslinked polyester were studied with laser Raman spectroscopy. Following the polyesterification reaction, Raman measurements showed that the polyester contained 55% fumarate and 45% maleate unsaturation. Additionally, the glycol fragment was indicated to exist as the gauche isomer. The 1213 cm-1 line is assigned to the glycol-ester linkage and can be measured to follow the conversion to polymer. After the crosslinking reaction, styrene was found to copolymerize preferentially with the fumarate unsaturation. There was no evidence of forming long-chain polystyrene crosslinks. Our results indicate that, after crosslinking, 41% of the fumarates have reacted with styrene and there is an average of two styrene molecules in each link.
    Additional Material: 11 Ill.
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  • 102
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 769-779 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Measurements are reported of the solubility and concentration of propane and propylene in polyethylene, at temperatures from -30°C to +30°C and pressures from 1.68 to 3.52 atm. Solubility of both gases in polymer depends on penetrant activity. Henry's law is not obeyed at high values of the penetrant activity, i.e., in the vicinity of the condensation point of the gas. The interaction between the solvent and the polymer is independent of pressure and a function of temperature. The propylene-polyethylene interaction seems to reach a maximum at 10°C within the range investigated. A physical mechanism, based on opposite effects of temperature upon polymer and penetrant, is suggested to explain the results.
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  • 103
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 835-845 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: From thin films produced by vacuum evaporation and condensation of polyethylene, single crystals were grown by subsequent heat treatment of the films in xylene. Extended molecular chains composing the crystals are approximately 150 Å in length, i.e., about 1.5 times the thickness of the crystal layers. Electron microscopic examination of the crystals revealed that they were morphologically similar to ordinary polyethylene and paraffin single-crystals, e.g., they sometimes exhibited a hollow pyramidal shape or typical spiral growth.
    Additional Material: 11 Ill.
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  • 104
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 847-856 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The interdependence of the enthalpic contribution A2, H and the entropic contribution A2, s to the second osmotic virial coefficient for a given polymer-solvent system has been investigated from the experimental and the theoretical point of view. Experimentally, the following common facts were observed for various systems at temperatures and pressures below the critical values for the solvent. Both the isobaric and isothermal dependences can be approximated over relatively wide ranges of A2, H by linear relations with a slope deviating only slightly, but in a characteristic manner from a value of -1. When the temperature is increased at constant pressure one moves along an isobar towards higher A2, H; when the pressure is increased at constant temperature, one moves along an isotherm in the opposite direction, i.e., towards lower A2, H. Theoretically this behavior can be described in a qualitative manner, starting from a relation derived by Patterson and Delmas on the basis of the Prigogine corresponding-states theory. The reasons for the lack of quantitative agreement are discussed.
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  • 105
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 863-875 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Folded-chain crystals of certain polyamides present some novel diffraction effects due to the small number of repeat units within the lamellar thickness. X-ray diffraction evidence is available in the complete range from low to wide angles. This information is interpreted in terms of the structure factor of an individual lamella together with the lattice factor appropriate for the stacking of lamellae. When due account is taken of the lattice factor, whose effect can be detected even at large angles, three features of the lamellar structure can be deduced. First, the evidence is in favor of the straight-chain stems traversing almost the total thickness of each lamella, implying sharp folds at the lamellar surfaces. Some consequences of this result on the interpretation of data obtained from annealed mats are mentioned. Second, the detailed determination of the stem structure demands that the majority of the folds in nylon 66 lie in the acid group. Third, there are regions of depleted electron density at the lamellar surfaces, though features of the crystal structure are still retained. This indicates the presence of some folds deeper in the crystal than the majority.
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  • 106
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 919-936 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Small-angle equatorial x-ray scattering from fibrous systems is often complicated by the effects of morphological organization and/or heterogeneities as well as by macromolecular structure and organization influencing this same region of scattering space. In previous work it was shown that closed form mathematical expressions could be obtained for the Patterson function, without prior assumptions about the scattering system, when the intensity data were purposely truncated. In this paper the use of these expressions to extract the physical parameters describing the scattering system is demonstrated by application to a model system. The expressions are also expanded to include lattice distortions and long range coherency. A second approach is presented for cases when the coherence is small, and finally the use of higher-resolution data is discussed.
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  • 107
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 937-944 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The heats of fusion of low-density polyethylene and chlorinated polyethylenes of varying chlorine content have been investigated by differential scanning colorimetry (DSC). Linear correlations are found between the chlorine content and the apparent heat of fusion, crystallinity, and the maximum specific heat measured in the temperature range 90-120°C. The effect of heat treatment on crystallinity is shown to be strongly dependent on the chlorine content of the polymers.
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  • 108
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 993-1011 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The adsorption of some polyacids, principally poly(acrylic acid), on nylon powder has been studied. In aqueous solutions at low pH the adsorption behavior of poly(acrylic acid) is controlled by adsorbate coil dimensions rather than by electrostatic effects. Less adsorption takes place from methanol solutions but the process is much more rapid than from water. Above a critical value, increase of adsorbate molecular weight leads to a reduced adsorption, the effect being particularly evidenced by aqueous solutions. Model compounds (propionic and glutaric acids) are rapidly adsorbed from both methanol and water, but give low specific absorptions. Adsorption of poly(acrylic acids) and model compounds, is reduced, but not eliminated, by modification of the nylon adsorbent through acetylation or methoxymethylation. The adsorption of poly(acrylic acid) on nylon is not readily reversible; however, partial neutralization will release preadsorbed poly(acrylic acid) from nylon powder. The adsorption behavior of copolymers of acrylic acid with N-vinylpyrrolidone is reported, as are brief studies on some other homopolyacids. The results are generally interpreted on the basis of sorption of the macromolecules into a swollen, flexible adsorbent.
    Additional Material: 8 Ill.
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  • 109
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1593-1607 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A theory which relates the change in the strength of absorption to the change in crystal orientation function is presented for the anisotropy of dielectric relaxation for the dipolar orientation change in an oriented crystalline polymer. Experimental measurements are presented for the α dielectric absorption of a stretched ethylene-carbon monoxide copolymer and compared with the orientation of crystals of this copolymer as determined by x-ray diffraction.
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  • 110
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1611-1613 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 2 Ill.
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  • 111
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1575-1585 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Young's modulus and mechanical damping of 15 organic liquids in polystyrene have been measured from 4°K to 250°K. The concentration was generally in the range from 10 to 15%, but the polystyrene-toluene system was investigated over the range from 0 to 16%. Some liquids cause the 40°K damping peak of polystyrene to disappear, other liquids do not. Seven of the liquids which cause the disappearance of the 40°K peak give rise to new large damping peaks at the temperature expected for the secondary glass transition temperatures of the liquids, that is, at 0.77 Tg of the liquids. Some of the liquids produced large unexplained damping peaks at temperatures above the expected glass transition temperatures Tg of the liquids. It is suggested that the γ peak in polystyrene is caused by styrene monomer.
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  • 112
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1615-1619 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 3 Ill.
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  • 113
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1621-1624 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 2 Ill.
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  • 114
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1625-1629 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 3 Ill.
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  • 115
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1639-1655 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The viscoelastic (VE) response of freeze-dried blends of polystyrene (PS) and poly-(2,6-dimethyl phenylene oxide) (PPO) has been studied as a function of composition, frequency, and temperature to examine the degree of rheological compatibility. When blended together, the relaxation processes of both molecular species exhibit the same temperature dependence. However, the temperature dependence of the VE response is a function of composition. It is shown that this behavior can be predicted from the measured glass transition temperatures by assuming the additivity of the free volumes of the components. The properties of the blends are compared at equal free volumes. The effective segmental friction factor is found to be independent of composition while the modulus of the rubbery plateau increases with PPO concentration. This result is interpreted as a change in the entanglement molecular weight Me of the blends. When the changes in Me are considered, the relationship between the zero-shear viscosity η0 and the 3.4 power of the weight-average molecular weight, commonly found for high molecular weight homopolymers, predicts the compositional dependence of η0 for the PPO-PS blends. It is concluded that the PPO-PS system forms a rheologically compatible blend.
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  • 116
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1631-1637 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The results of bulk modulus and density measurements on low-density polyethylene to 30 kbar are presented. From these data the pressure coefficient dTt/dp of the glass transition temperature is obtained, and a comparison is made with data calculated from Pastine's theoretical equation of state for polyethylene.
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  • 117
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1681-1689 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A simple form of nonisothermal free energy function A(λ1, λ2, λ3, T) for rubberlike materials results from postulating that the entropy is a separable symmetric function of the extension ratios λi along the principal strain directions and considering the fundamental properties of rubberlike materials, i.e., that rubber elasticity is associated primarily with changes in entropy and the variation of elastic tension with changes in temperature is linear. The explicit representation of A is reduced to the Valanis-Landel strain energy function for isothermal cases.
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  • 118
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Mechanical properties were correlated with glass transition temperatures for a series of random copolymers of methyl methacrylate with comonomers selected from the higher n-alkyl acrylates and N-n-alkylacrylamides. The plasticizing comonomers were the n-butyl, 2-ethylhexyl, n-octadecyl, and oleyl acrylates, and the N-n-butyl-, N-n-octyl-, N-n-octadecyl-, and N-oleylacrylamides. The complete range of compositions was investigated. However, the bulk of the data was obtained on compositions in the glassy region below the onset of the vitreous transition. In this region it was found that the decrease in tensile and flexural moduli and strengths with increase in internal plasticizer for all of the systems was directly proportional to the decrease in Tg. It was concluded that the additive contribution to the free volume made by each side-chain methylene group was alone responsible for the magnitude of the rate of change of properties. However, polar contributions of the amide group to stiffening the main chain exceeded those of the ester, so that the amides were less efficient plasticizers. An empirical equation was derived which described, with fair accuracy, the decrease in the mechanical parameters with composition for the amorphous copolymers. It was reasonably successful in predicting properties even into the composition range where the ambient testing temperature corresponded to or exceeded the transition temperature. In this transition region an accelerated decrease in the magnitude of the physical properties was observed. All samples exhibited brittle fracture except those tested in the transition region. Here the strain was largely irrecoverable flow. Side-chain crystallinity did not interfere significantly with the mechanical properties because moduli and strengths had already decayed to small values near the compositions where crystallinity commenced. Non-random copolymers of vinyl stearate and methyl methacrylate showed no internal plasticization, apparently because of macrophase aggregation.
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  • 119
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1691-1698 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Use of a new apparatus is described which enables infrared dichroism to be followed as a function of time following the rapid stretching of a sample. The apparatus is double beam in dichroism, in that the infrared beam is alternately polarized parallel and perpendicular to the stretching direction and the transmitted intensity is observed on an oscilloscope. Results are presented for the stretching of a low-density polyethylene sample by approximately 28% in a time of approximately 0.1 sec. The infrared dichroism is observed to change in times of the order of 50 to 100 msec after stretching, confirming the observation made by other techniques that crystal orientation changes during this time.
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  • 120
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1731-1741 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Single crystals of polyethylene are investigated by transmission electron microscopy. A pattern of lines is observed in the crystals. The properties of these lines suggest that the lines represent slip traces (slip steps) generated by the movement of dislocations in the polyethylene crystals.
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  • 121
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1743-1748 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A method is presented for measuring the change of the intensity of x-ray diffraction peaks of cellulose specimens as a consequence of humidity changes of the specimens. Measurements performed showed a decrease of this intensity after drying pulp specimens initially kept in humid air. Thus the order in cellulose decreased during drying.
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  • 122
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The method of free torsional vibrations was used to determine the temperature dependence of the storage and loss shear modulus of poly(2-hydroxyethyl methacrylate) samples swollen with ethylene glycol, formamide, n-propanol, and water. The measurements included the glassy region (starting with temperatures from -130 to -190°C) and the main (α) transition from the glassy to the rubberlike state. At a volume fraction of the low molecular weight compound vd 〉 0.2, the above systems exhibit, besides the α dispersion, only the secondary (βSW) dispersion, which is generally attributed to the relaxation motions of the hydroxyethyl groups of the side chains interacting with molecules of the diluent. If no separation of the diluent in a second phase occurs at the measurement temperatures, the temperatures of both dispersions decrease with increasing vd and approach the glass transition temperature of the low molecular weight compound. The concentration dependences of the dispersion temperatures were described by an equation derived elsewhere for the concentration dependence of the glass transition temperature. The results indicate that molecules of the diluent contribute significantly to the intensity of the βSW transition and simultaneously affect its limiting temperatures (for vd = 1 and vd = 0). Specific differences among the systems described above appear only at those temperatures where same of the low molecular weight compound separates into a crystalline or glassy phase.
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  • 123
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 71-87 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The modified Birnboim transducer and a computerized data acquisition and processing system (DAPS) for the measurement of viscoelastic properties of macromolecular solutions are described. The apparatus has a continuous frequency range from 0.01 to ca. 700 Hz and a viscosity range from 2 to ca. 30,000 poise (sample volume 1 to 1.5 cm2). Sample temperature is controlled to within 0.002°C from -30°C to +80°C. Working displacements are 102 to 104 Å. The DAPS is designed for precise determinations of the magnitudes and relative phasing of two sinusoidally time-varying electrical signals (0.02%, 0.02°, respectively, for signals 〉 2 V peak) from 10-2 to 105 Hz. Cross-correlation techniques are used for noise rejection. For frequencies below 30 Hz values of the storage (G') and loss (G″) components of the complex shear modulus (G*) of 1 dyne/cm2 are determined to within 10% and 4%, respectively, for liquids of moderately low viscosity. Proportionately higher measurement accuracies for typical values of G' and G″ and the wide frequency and viscosity ranges permit extrapolation to infinite dilution and studies of limited molecular flexibility for many polymer - solvent systems.
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  • 124
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 123-131 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The following quantities were measured on a number of ethylene-vinyl acetate (EVA) and ethylene-acrylic acid (EAA) copolymers: (1) the small-angle x-ray scattering invariant, (2) the overall density, and (3) the crystallinity. Assuming a two-phase structure, the separate values of the densities of the crystalline and amorphous regions can be calculated from these data. Of these, the crystalline density is compared with the value obtained from the lattice constants. A systematic difference is observed which is ascribed to the presence of comonomeric side groups in the crystalline regions. For the EVA and EAA samples, their concentration is at least 0.3 and 0.5 times the overall concentration, respectively. The amorphous densities are found to be higher than the values calculated from completely amorphous copolymers by extrapolation procedures.
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  • 125
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 201-219 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The present work is a continuation of a general study of the effect of pressure on gas and vapor permeation through nonporous polymeric membranes. Permeability coefficients have been measured for 1,1-difluoroethylene (C2H2F2) and fluoroform (CHF3) in polyethylene at penetrant pressures up to 35 atm and at temperatures between -18 and 70°C. The permeability coefficient P̄ for the 1,1-difluoroethylene - polyethylene system was found to increase with increasing pressure differential Δp across the membrane. Isothermal plots of log ΔP versus Δp are generally linear and can be represented by empirical relations of the form ΔP = P(0)exp{m Δp}, where P(0) and m are constants. The slope m of these isotherms decreases with increasing temperature. Plots of log P̄ versus Δp for the fluoroform - polyethylene system are also linear, but exhibit negative slopes, i.e., P̄ decreases with increasing Δp. An extension of Fujita's “free volume” theory of diffusion in polymers shows that the dependence of P̄ on pressure reflects how the free volume of the polymer is affected by this pressure. An increase in the penetrant pressure may result in two opposing effects: (a) the concentration of the penetrant dissolved in the membrane is increased, thereby increasing the free volume, and (b) the hydrostatic pressure on the membrane is also increased, which causes a decrease in the free volume. If the overall effect is an increase in the free volume of the polymer, then P̄ will also increase, and vice versa.
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  • 126
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 239-252 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: As a continuation of the preceding study on the folding behavior of short polymer chains, an iodine-terminated paraffin having 156 Å peak molecular length and a sharp molecular weight distribution was prepared. The paraffin could be crystallized in lamellae of two different thicknesses: (A) thickness close to half the chain length (the most readily obtained); (B) thickness intermediate between half chain length and fully extended chain. Case A corresponds to each chain folding once with equal stems and with ends at the surface. Degradation behavior revealed that the folds must be of closely equal length giving rise to an even fold surface. In case B the situation is more involved: here the chain ends must turn into the lattice. Adjacent reentry is a necessity throughout. In both cases the lamellar thickness could be increased by annealing up to complete chain extension.
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  • 127
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 221-238 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Short aliphatic polymer chains of different lengths were prepared by degrading polyethylene samples of appropriately chosen initial fold lengths to the chain lengths which correspond to a single chain traverse through the lamella. The resulting dicarboxylic acids were either used as such for further crystallization experiments or were first converted into diiodides to remove polar endgroups. The resulting short polymers all crystallized by chain folding even if the chains (peak of distribution) were only 1.5-4 times the length of a traverse through the lamella. In the diiodides the fold length varied continuously with crystallization temperature, as is usual in high molecular weight material, but with the dicarboxylic acids such variation, while observable, was only small. The effect of the molecular weight on the fold length due to its influence on supercooling at a given crystallization temperature has become apparent. Renewed degradation with nitric acid and subsequent GPC analysis of the degradation products confirmed the folded nature of the chains in the above crystals. This analysis combined with experiments on the reactivity of chain ends has led to the picture that each chain folds completely, once, twice etc. so that both folds and ends are in the surface zone but are located at varying heights, as appropriate to the overall layer thickness for the molecular weight distribution in question. This picture is consistent with other concurrent work.
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  • 128
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 253-264 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effect of iodine sorption on the small-angle x-ray diffraction intensity is discussed in terms of the distribution of iodine sorbed in the amorphous regions of polymers. The change in the intensity of the peak corresponding to long periods is measured as a function of the iodine uptake in drawn, and annealed poly(ethylene terephthalate) films. A linear relation with slope K is observed between the square root of relative intensity and iodine uptake. The slope K varies with annealing conditions. Theoretical values calculated for models of the distribution of iodine in amorphous regions, are compared with the observed K. Results can be interpreted on the basis of a “concave” distribution of iodine, i.e., with sorption sites more numerous near a crystal surface than in the interior of an amorphous region.
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  • 129
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 323-337 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Glass transition temperatures were determined for a homologous series of unsubstituted lactone monomers varying in ring size from four to sixteen atoms. Examination of these transitions as a function of ring size shows a maximum in Tg for the seven-atom ε-caproalctone ring. This behavior is interpreted on the basis of a conformational change in lactones which occurs in rings containing seven to nine atoms. The Tg values of polylactones derived from these cyclic esters were determined and correlated with Tg values of the monomers. Except for the anomolous ε-caprolactone and the strained fourmembered lactone, an apparently constant difference between monomer and polymer Tg is observed. Treatment of the polylactones as methylene copolymers permits extrapolations of the Tg values to obtain that of polyethylene. Two values suggesting the γ and β transitions of polyethylene are obtained.
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  • 130
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 369-373 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 131
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 433-448 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Measurements are reported for the dielectric loss factor of the SCMC solutions over the frequency range 2 MHz to 50 MHz as a function of concentration of SCMC, concentration of added sodium chloride, molecular weight, and temperature. The results are in general agreement with those of other workers and are interpreted in terms of ionic theories in which motion of the diffuse counterions is the dominant feature.
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  • 132
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 507-517 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A new typical orientation pattern of polyethylene has been observed in extruded, melt-drawn composites containing 10% polyethylene and 90% polystyrene. In these composites, the polyethylene phase is dispersed in the polystyrene matrix as thin, long ribbons (width 1000 Å, thickness 500 Å). The b axis of the crystallites is found oriented preferentially along the long dimension of the ribbons, i.e., in the extrusion direction. The a and c axes of the crystallites show no preferred orientation. This texture pattern is attributed to the fact that, in view of the small cross section of the polyethylene phase, crystallization can proceed only along the long axis of the ribbons. Since the b axis is the direction of fastest growth in polyethylene (and the radial direction in a spherulite), most polyethylene unit cells are oriented with their b axes in the long dimension of the ribbons.
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  • 133
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 489-497 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Proton spin-lattice relaxation times of solvent molecules were measured on ternary mixtures of a polymer and two solvents by the adiabatic rapid-passage method. The selective adsorption of a good solvent was verified by this experimental technique for the systems benzene - cyclohexane - polystyrene(PS), benzene - carbon tetrachloride - poly(methyl methacrylate)(PMMA), and chloroform - carbon tetrachloride - PMMA. The number of molecules of adsorbed benzene per monomeric unit of PS was estimated to be about four, which is almost identical with that determined previously by thermodynamic measurements. The number of molecules of benzene and chloroform adsorbed on PMMA were also determined to be about five and four, respectively. It was found that the interaction between chloroform and PMMA has the greatest effect on the molecular motion of the solvent, whereas the benzene - PS interaction is weak.
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  • 134
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 499-505 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The healing of scratches on the surface of vitreous selenium was observed over a period of nine weeks, and from the data the solid surface tension of vitreous Se is estimated to be (100 ± 20) dyne/cm at 38.8°C, about the same as that of the liquid at the melting point. This value is three times as large as the critical surface tension determined from contact angle measurements, which indicates that for vitreous Se in contact with organic liquids, the solid - liquid interfacial tension is about two-thirds as much as the solid surface tension. The present method of measurement can probably be used to determine the solid surface tension of other polymers, and by measuring the healing of scratches on a solid immersed in a liquid the method could be used to determine the solid - liquid interfacial tension.
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  • 135
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 527-539 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The extrema in the unpolarized and the horizontally polarized angular scattering patterns are used as a basis for size-distribution analysis of polymer latex systems composed of single, spherical, optically isotropic particles. The method of analysis is similar to that recently proposed for vertically polarized scattered light and the polarization ratio, where the modal diameter and a distribution width parameter are determined from the experimental angular scattering pattern and prepared theoretical diagrams obtained by Mie theory calculations. The method of analysis, based on all four scattering functions, is illustrated by use of a Dow polystyrene latex sample.
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 569-570 
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    Keywords: Physics ; Polymer and Materials Science
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  • 137
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 741-745 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Commercial and fractionated samples of poly(ethylene glycol) and a sample of Dextran were used as standards to show the limitation of a cellulose acetate membrane for osmotic pressure determination of molecular weight in an aqueous system. The leakage of this membrane was much greater in the aqueous system than in organic solvents.
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  • 138
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 761-765 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 139
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 781-810 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The mechanical properties of poly(ethylene terephthalate) are examined to see if the quantitative morphological criteria previously used to define the structural state of isotactic polypropylene will lead to similar quantitative structure-property correlations when applied to PET. Tenacity, thermal shrinkage in oil and air, tensile modulus, dynamic loss modulus, long spacings, and small-angle x-ray intensities are included in the study. All of the data were obtained from the open literature. In all cases the physical properties correlate simply and quantitatively with the internal structure of the PET, and the character of the correlations leads to new insights into the nature of the internal mechanisms controlling the observed properties. The study shows that only by considering the structural state of a polymer, and not its fabrication parameters, can general, simplifying, quantitative, structure-property correlations be achieved.
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 519-526 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Starting from the Lorentz-Lorenz equation, Heller, a few years ago, advanced a method for calculating the partial specific volume of a substance in a dilute solution from the refractive index increment of the solution and the specific refraction of the solute. It is shown that this method, based on graphical extrapolation, can be considerably simplified. Further, a method is indicated by which the partial specific volume of a substance over the whole range of concentrations can be calculated in an analogous manner. The method is checked and elucidated with reference to some experimental examples.
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  • 141
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 549-563 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The structures of copolymers of ethylene and chlorotrifluoroethylene have been studied by infrared, nuclear magnetic resonance, and x-ray diffraction techniques. Copolymers varying in ethylene composition from 80 to 50 mole-% were prepared at a number of different temperatures with a peroxide catalyst system. Compositions of 50/50 mole ratio were found to be semicrystalline and to have melting points as high as 241°C. These materials were found to be copolymers with a high degree of one-to-one alternation. They were similar in structure to 1:1 copolymers which had been reported previously by other workers who used a triethylboron catalyst system. The x-ray evidence indicated that the copolymers prepared with the peroxide catalysts were not stereoregular. A hexagonal unit cell with a theoretical density of 1.70 g/cc was determined for the alternating one-to-one copolymer by x-ray techniques. A value of 262°C was determined for the melting point of the theoretical 100% alternating one-to-one copolymer. Values of ΔHƒ = 4500 cal/mole and ΔSƒ = 8.4 cal/deg-mole were also calculated for the alternating 1:1 copolymer. The preferred conformation of the material appears to be a “kinked” structure with the crystalline phase having ethylene units in one chain lining up opposite chlorotrifluoroethylene units in the adjacent chain. Polar association which can occur between fluorine and hydrogen atoms in this arrangement may account in part for the relatively high melting point of the alternating one-to-one copolymers.
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 577-584 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A study of rat-tail tendon fibers, about 200 μ in diameter, by scanning electron microscopy of fractured specimens reveals that these crimped fibers are largely made up of cylindrical units, about 10 μ in diameter. These, in turn, are made up of the well-known collagen fibrils, ca. 0.1 μ in diameter, which have been observed previously by transmission electron microscopy and small-angle x-ray diffraction. Both the 10-μ and 0.1-μ cylindrical units were found to be arranged parallel to the macroscopic fiber axis rather than helically about it, as has been often proposed in the past. Significant improvement in resolution of the fracture surfaces was obtained by dehydration of the tendon. Microscopy of undehydrated tendon fibers undergoing solubilization by dilute aqueous acetic acid confirmed the results obtained by fractography.
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 615-629 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The energy of the ground state, charge distribution, and bond orders were calculated by a MO method in the SCF-CNDO/2 approximation for various configurations of the monomer, dimer, and trimer model of both the associated and dissociated reaction center of an anionic acetylene polymerization. According to the results of these calculations, cooperation of π and σ bonds leads to a charge delocalization which increases with growing chain length and is the reason for kinetic deactivation of the center. Propagation is stopped, probably by a cooperative effect of the kinetic and thermodynamic factors.
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  • 144
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 673-683 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The shrinkage phenomenon in bovine achilles heel tendon was studied calorimetrically as a function of water content of the tendon. The transition temperature was found to increase from 67°C to 98°C as the water content decreased from 53% by weight to 26% by weight. The enthalpy change was found to increase with increasing percentages of water. The data is interpreted by considering the possibility of water binding to the polar sites on the solute molecule which become free after the transition. A calculation is carried out in which the melting shifts are taken to be related to the free energy of binding. The increase in enthalpy with an increase in water content is shown to have a semiquantitative interpretation in terms of the structural aspects of water.
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  • 145
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 699-713 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Results from the dilute solution characterization of polyfluoroalkoxyphosphazenes in Freon ether (E2) solutions are reported. Anomalous viscosity data suggest that polymer aggregation sometimes occurs in E2 and may be caused by the presence of relatively few anomalous polar groups on the polymer backbone. Since small amounts of acetone added to the E2 solutions inhibit aggregate formation, samples are also characterized in an E2-acetone mixed solvent. Light scattering and osmometry indicate that E2 and E2-acetone (9.09% by volume) are theta solvents for the polymers. High molecular weights (M̄w 〈 3 × 106) and unusually broad molecular weight distributions (M̄w/M̄n 〈 16) are found. One polymer is fractionated by extracting solutions in 1,1,2-trichloro-1,2,2-trifluoroethane with acetone. Although the samples are highly polydisperse, intrinsic viscosities correlate with number-average molecular weights satisfying the Mark-Houwink relation with the exponent a ≈ 1/2. The z-average mean-square radius of gyration increases linearly with molecular weight so that 〈S2〉g/M̄w ≈ 0.098. Because of the large polydispersity and unknown form of the distribution function, a quantitative interpretation of characterization results relating dilute solution parameters to polymer skeletal structure is not possible. The tentative conclusion is that the fluoroalkoxy-substituted phosphazene polymers are relatively linear and therefore that the broad distribution of molecular weights must be due to some polymerization mechanism other than branching.
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  • 146
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1789-1797 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In the crazing of glassy amorphous polymers, wetting ability and penetration of the fluid are the important practical parameters governing the activity of the fluid. Higher molecular weight and the presence of polar groups in the fluids result in an increase in the critical stress for craze initiation in polystyrene and polycarbonate. The Eyring treatment of the craze process can describe fairly well the temperature and strain rate dependence of the critical stress. The parameters involved in the Eyring theory suggest that the crazing takes place by a molecular motion of lower energy than does macroscopic yielding.
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1749-1756 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polypropylene fibers prepared by quenching in ice-water were drawn at 25, 80, 120, and 140°C to a draw ratio between 6 and 8 at draw rates 0.05, 0.5, 5, and 50 cm/min. The long period increases almost linearly with the draw rate for drawing at 25°C and decreases for drawing at higher temperatures. The effect in the latter cases is an annealing effect. As a consequence of the shorter exposure of the drawn fibers to the high temperature at higher draw rate, the long-period growth proceeds for a shorter time and hence results in a smaller increase of long period. At 25°C, however, the long-period growth is negligible. The increase of long period with draw rate is the consequence of higher adiabatic heating as calculated from the energy input during the plastic deformation which transforms the spherulitic into the fibrous structure. One concludes that the long period established during this transformation depends on the maximum temperature reached in the micronecking zone and not on the macroscopically observed temperature of the sample in the neck.
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1775-1787 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Mooney's version of the molecular theory of polymer networks has been generalized to the case when the external strain applied in the isotropic state is different from that at network formation. As in the theory of equilibrium behavior of the polymer networks, this generalization allows inclusion in the viscoelastic functions of effects connected with the temperature dependence of internal energy of the chains and with the strain effect of the solvent. From viscoelastic functions thus generalized, it is possible to derive a relation for calculation of the monomeric friction coefficient. It also suggests the possibility of superposing data obtained at various temperatures, degrees of swelling, and condition of network formation.
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1837-1839 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1799-1809 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effect of hydrostatic pressure on the crystal structure of PTFE has been studied up to pressures of ca. 25 kbar by x-ray diffraction. The experimental method uses opposed diamond anvils of small surface area as transmitters of pressure with MoKα x-radiation propagating through these anvils. A small specimen of oriented polymer is held in place with a molybdenum gasket. Pressures are measured by change in lattice spacing of sodium chloride included with some specimens. It is found that above 4.5 kbar the PTFE changes to a high-pressure phase in which the molecules have transformed from their normal helical arrangement to that of a planar zigzag and that the planes of the molecules all lie parallel to one another. Further changes in the diffraction pattern on increase in pressure are attributed to slip and twinning in the high-pressure phase rather than to another phase change.
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1757-1774 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Three types of domain structures, namely spherical, rodlike, and lamellar, of A-B and A-B-A (or B-A-B) block copolymers cast from solutions are discussed on the basis of a criterion that the structures originate at a critical micelle concentration as a result of microphase separation of the block segments and the micelles formed maintain their structures into the solid state without reorganization. It is concluded that the micelles shrink mostly in the direction perpendicular to the interface between the two phases within the micelles because of the appreciable orientation of the block segments in this direction. In other words, the spherical micelle shrinks isotropically to form a spherical domain having a diameter proportional to the 2/3 power of the degree of polymerization (molecular weight) of the corresponding block segment. Rodlike and lamellar micelles, on the other hand, shrink anisotropically to form rodlike and lamellar domains such that the diameter and the thickness of the respective domains are roughly proportional to the 1/2 power of the degree of polymerization of the corresponding block segment.
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 265-272 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Flow birefringence experiments on aqueous solutions of poly(vinyl alcohol) and of methyl cellulose show that the optical anisotropy changes markedly during aging of the solution. The same effect can be obtained by adding alcohol to fresh aqueous methyl cellulose solutions. The flow birefringence was measured as a function of the velocity gradient on solutions with and without alcohol during the course of aging. The phenomena are attributed to intermolecular and intramolecular interactions between exposed hydroxyl groups of the polymer chains, as these are affected by a change in the degree of hydration during aging or by the addition of a strong hydrophilic agent such as an alcohol. Association or crystallization of the ordered polymer chains may occur and lead to a supermolecular structure in the solutions. By following Sadron's theory and making use of a polar diagram, it was concluded that, after aging or mixing with the additive, the solutions become optically heterogeneous and contain two different components with optical polarizabilities of the same [in poly (vinyl alcohol) solutions] or opposite (in methyl cellulose solutions) sign.
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 317-322 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The bandwidth at one-half maximum intensity of the Raman-active C=O stretching vibration was found to correlate with density in poly(ethylene terephthalate). This correlation is valid for unoriented as well as highly oriented materials. It is suggested that a number of rotational states of the terephthalate segment occur in the amorphous polymer. Crystallization causes a resonance-stabilized planar conformation.
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 357-368 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The enthalpy of dissociation of poly(acrylic acid) and of poly(methacrylic acid) in water and in 0.5N NaCl at 25°C has been measured over a wide range of degrees of neutralization of the polyelectrolytes. In the case of poly(methacrylic acid) the calorimetric data permit the direct evaluation of the enthalpy of conformational transition of the polymer. For this transition, with the aid of standard free energy data derived from potentiometric titrations, the change in entropy was also estimated. The relative accuracy of the thermodynamic data, and the possibility of deriving therefrom information on the mechanism of transitions of the type, globular coils → expanded coils for partially hydrophobic synthetic polyelectrolytes in aqueous solution are discussed.
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  • 155
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    Notes: On the basis of our own experimental and some literature data, the contributions of slow relaxation mechanisms to the shear modulus, (GeN  -  Ge), and the parameter C2 of the Mooney-Rivlin equation have been examined for lightly crosslinked poly(butyl methacrylate), poly(butyl acrylate), poly(2-hydroxyethyl methacrylate), and some rubber networks. For the rubbers, increasing degree of crosslinking caused a decrease in GeN  -  Ge and an increase in C2; for the other networks, both GeN  -  Ge and C2 diminished with increasing crosslinking. The effectiveness of the crosslinking polymerization, and also the absolute values of the physical crosslinking degree, decreased in the order of poly(2-hydroxyethyl methacrylate), poly(butyl methacrylate), and poly(butyl acrylate). The values of the equilibrium compliances J of the networks studied, obtained by various methods, have also been compared, and good agreement has been found.
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 375-376 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 473-488 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The structure of granular polytetrafluoroethylene has been studied by electron microscopy. On the basis of the texture of surfaces resulting from fracture a model of the structure is proposed which suggests that PTFE consists of extended chain crystals with both inter- and intra-lamellar noncrystalline regions. The effects of γ-radiation on the structure have been investigated by examining the texture of irradiated fracture surfaces and also the texture produced by post-irradiation fracture. The irradiations have been performed in vacuo and in oxygen. In both atmospheres PTFE undergoes degradation with a concurrent increase in crystallinity. However, the texture of the surfaces of high crystallinity PTFE, prepared by radiation, differs markedly to the texture of fracture surfaces of high crystallinity PTFE prepared by thermal annealing. It is proposed that radiation causes rupture of bonds in the interlamellar (chain fold) and intralamellar regions, resulting in the production of chain ends and interlamellar links. Due to scavenging of the free radicals, interlamellar linking is pobably a minor process with irradiation in oxygen. These chemical changes cause modifications to the extended chain lamellar crystals and consequently alterations to the physical properties of the polymer.
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  • 158
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 747-754 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The electrical conductivity of a series of semiconducting polyazophenylenes was studied as a function of temperature and molecular weight in the temperature range 293-493°K and for molecular weights between 9500 and 62800. The compounds studied included poly-2,4-diminotoluene and poly-2,5-diaminotoluene. The temperature dependence of conductivity obeys the exponential law σ = σ0 exp {-Ea/kT}. All of the compounds studied show a break in the conductivity curve at a temperature of about 380°K with the slope of the curve greater at temperatures above 380°K. The activation energies Ea determined from the higher slopes are in the range 0.63-0.89 eV, and the corresponding σ0 values are in the range 10-4-10° (ohm-cm)-1. Both Ea and σ0 show a tendency to increase with increasing molecular weight such that the compensation law was valid. Activation energies and σ0 values determined from the (smaller) slope below the temperature of the break point showed a tendency to decrease with successive measurements on new samples. This indicates some kind of orientation effect, and conclusions concerning the properties of the material on basis of results below the break point are therefore difficult.
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  • 159
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 811-822 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The rate equations for the thermal decomposition of a polymer by a random scission reaction followed by rapid depolymerization of a constant number of monomer units from both fragments together with rapid evaporation of low molecular weight species are solved by using a different approach from that used by previous workers. The results obtained are more specific and differ slightly from previous treatments.
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  • 160
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 887-907 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Diffusion and tensile creep measurements were made for systems of poly(-n-butyl methacrylate) (PBMA) and sorbed ethanol, MEK, or benzene at 23°C. Rates of penetration of an inert spherical indenter into PBMA also were investigated and compared with the tensile creep behavior of the polymer. Creep measurements for various volume fractions of penetrant sorbed at equilibrium revealed that master curves, resulting from a time-concentration superposition procedure, could be constructed for each penetrant. At long times, these master curves, particularly that for ethanol, show deviations from the corresponding time-temperature superposition master curve. These deviations are interpreted in terms of probable long-range entanglement coupling governed in part by the partially specific nature of polymer-penetrant interactions. Parameters calculated by a free-volume theory, describing both diffusion and tensile-creep data, indicate that MEK is a more efficient plasticizing agent than the other penetrants and requires less local free volume for diffusion. Analysis in terms of the free volume concept was not attempted for the case of ethanol, where specific polymer-penetrant interactions are more important.
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  • 161
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 945-956 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The contribution of entanglements to the relaxation modulus of four samples of cis-polyisoprene has been studied in detail. The average number of chain atoms between neighboring entanglements has been calculated according to the theory of Chompff et al. Relaxation spectra and modulus produced by the entanglements were also calculated from the theoretical model. Good agreement was achieved between the modulus measured experimentally and the values predicted theoretically.
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  • 162
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    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 961-973 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The electron microscope study of the isothermal epitaxial crystallization of PBLG on 001 cleavage surface of NaCl or KCl from 0.01% chloroform solution with various n-octane contents has shown that the epitaxial growth process could be divided in two stages. In the first stage a rapid growth of a lamellar layer 20-40 Å thick could be observed; the PBLG molecules in αhelix conformation are oriented along 〈110〉 substrate directions. The dimensions and perfectness of alignment of these lamellae along the 〈110〉 direction depends on the molecular weight of the PBLG. In the second stage of PBLG epitaxial crystallization the relatively slow thickening of some initial lamellae takes place and one can observe many types of secondary structures. With increasing thickness of the epitaxial structures and increasing molecular weight of the PBLG the degree of orientation in relation to 〈110〉 substrate direction diminishes. The two growth stages in PBLG epitaxial crystallization are related to different kinds of orienting and attracting forces of the alkali halide substrate.
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  • 163
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 1917-1930 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A theoretical description of the ductile transition of glassy polymers in tensile creep is given. It predicts the delay time for plastic yield as a function of stress. The model assumes first-order rate expressions for the rate of change of loadbearing elements. The rate constants are given by a modification of the absolute reaction rate concepts of Eyring, where the energy barrier for breakdown of the bonding elements is asymmetric. This leads to an equation for the yield delay time as a function of the height of the energy barrier in the unstressed state, an activation volume, and a critical stress required to overcome the initial barrier asymmetry. The model has been compared to creep delay time experiments on polysulfone, polycarbonate, and poly(methyl methacrylate). It is able to predict the stress dependence for the onset of ductility in these materials with greater accuracy than previously reported equations.
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  • 164
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 1931-1939 
    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 study the effect of the molecular weight on the crystallinity and conformational changes of poly(β-benzyl L aspartate) in films, a previous study on high molecular weight samples has been extended to included polymers of low molecular weight, about 3.3 × 103. Films were prepared from chloroform solution by quick or slow evaporation at room temperature. The conformation and the thermal behavior were studied by means of infrared spectroscopy and differential scanning calorimetry. All films dried quickly are composed of polymer in the left-handed α-helical form. All samples studied which have molecular weights above 2.3 × 104 are similar in crystallinity and the left-handed α-helices in them crystallize to ω-helices during slow evaporation. In the low molecular weight region, however, the left-handed α-helices reverse to right-handed α-helices during slow evaporation, and the right-handed α-helices, in turn, reverse and crystallize to highly ordered ω-helices upon heat treatment, although there is some simultaneous conversion to the β-form. The transition temperatures of the quick-dried films for conversion from the left-handed α-helix to the ω-helix and from the ω-helix to the β-form increase linearly with increasing molecular weight up to about 2 × 104, but no large molecular weight dependence is observed beyond that region.
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  • 165
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 1967-1978 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A closed-form solution for the stress distribution in a cylindrical elastic rod under finite torsion is given involving use of the logarithmic λ form of the strain-energy function proposed by Valanis and Landel. Experimental torque data on natural rubber which give support to the present solution over a large range of angles of twist are shown. It is also shown how torsion data may be used to determine the λ form for deformations that lie outside the range of applicability of the logarithmic function if certain conditions apply. A solution, also in closed form, is given by using another λ form proposed by Dickie and Smith on the basis of experiments on styrene - butadiene rubber.
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  • 166
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 1979-1997 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Thermoluminescence (TL) and thermally stimulated conductivity (TSC) glow curves in poly(vinyl chloride), polyethylene, polystyrene, polytetrafluoroethylene, and polyimide have been compared, and many similarities have been observed. Comparison with available NMR, dynamic mechanical loss, and dielectric loss, molecular mobility data shows that most TL and TSC peaks occur at temperatures similar to those assigned to the onset of specific molecular motions, suggesting that the peaks are due to the liberation of electrons from traps formed by the polymer chains themselves, e.g., potential wells or cavities due to chain entanglement in amorphous regions, or main-chain branching points. Peaks for which correlation with molecular motion is not apparent are tentatively assigned to liberation of electrons from traps centered on impurities. The TSC peak temperatures in PVC were not affected in any consistent fashion by the application of high-strength electric fields during the warming process, indicating that the electron traps are electrically neutral when empty and charged when filled; the direction of the TSC currents appears to be determined by temperature gradients existing within the samples. The TL glow-curves are generally in good agreement with the results of other workers. The dark dc conductivity of PVC not exposed to ionizing radiation rises sharply in the temperature region assigned to the β-relaxation process, suggesting that the electron mobility in that polymer is dominated by molecular chain motion, i.e., the interchain charge transport process is probably best described in terms of a hopping process.
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  • 167
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2025-2031 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The surface tension of polymers having long unbranched side chains was measured by a contact-angle technique. It ranges between 20-29 dynes/cm and is almost entirely due to dispersion forces. At the lower end of this range the side chains are attached to every other carbon atom of the main chain and the structure is characterized by extended alkyl side chains at right angles to the main chain with methyl groups forming the interface. As the spacing frequency of the side chains increases and the main chain becomes the site of other bulky groups, this structure becomes less ordered and the surface tension increases to the high twenties. The same effect, to a lesser extent, is observed when the length of the side chains is gradually diminished to 12 carbon atoms from 21. A sudden increase of the polar force contribution of the surface tension at 10-12 carbon atoms indicates collapse of the ordered side-chain structure.
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  • 168
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 1949-1966 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Crystallization during polymerization of p-xylylene from the gas phase has been studied between 200 and -196°C. From room temperature to -17°C the polymer crystal morphology changes in that the crystallinity decreases. In this range the process is thought to be of the successive polymerization and crystallization type. The morphology is in agreement with this mechanism, of the folded-chain β-polymorph type with proper epitactic orientation of the chains with respect to the support surface. At -78°C an intermediate, poorly crystallized polymer results. At 196°C the reaction is most likely of the simultaneous polymerization and crystallization type. The morphology is, in agreement with the changed mechanism, of a metastable, irregularly folded β-polymorph type with no orientation of the chains relative to the support surface. No significant changes in molecular weight were observed in the polymers produced between 26 and -196°C.
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  • 169
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2073-2083 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Conditions have been found for the etching of poly(ethylene terephthalate) with water so that the crystalline portions alone remain. Initial sample and hydrolysis products are analyzed by extraction of low molecular weight products; density, viscosity molecular weight, and endgroup determination; heating-rate-dependent thermal analysis; low-angle and wide-angle x-ray analysis; and electron microscopy. On hydrolysis of a 67% crystalline polymer at 180°C for about 300 min, almost fully crystalline extended-chain oligomers can be obtained with about 65% yield. The morphology of melt-crystallized poly(ethylene terephthalate) and the melting behavior of oligomer lamellae are discussed.
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  • 170
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2107-2124 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Structural changes occurring during the aging of polypropylene quenched from the melt have been investigated by measurements of gas transport parameters and mechanical properties. Major changes in diffusion and sorption behavior during the first 30 hr of aging at room temperature were found to be strongly dependent on the atomic size of the inert gas penetrants. Tensile mechanical properties increased with aging time, while resilience and mechanical damping showed more complex behavior. The interpretation of the combined results suggests that the aging process may involve molecular rearrangements generally comparable to those for secondary crystallization processes, but within domains comparable in size to that of the smaller penetrant species. The relaxation of a residual stress distribution related to nonuniform plastic flow during quenching may be superimposed on the rearrangement phenomena.
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  • 171
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2135-2153 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It is assumed that the intensity of the vibrational Raman scattering from each of the structural units (molecular segments or crystallites) in an oriented polymer solid is determined by a symmetric second-rank tensor. The distribution of orientations of the principle axes of the tensors is expanded in a series of generalized spherical harmonics, Zlmn(θ)e-imψe-inφ, and it is shown that relations among the coefficients in this expansion can be obtained from suitable intensity measurements using polarized radiation. If the orientation of the tensor axes within the structural unit is known (in the general case, for several Raman lines), then the coefficients Mlmn of a similar expansion for axes fixed in the units can be obtained for l, m, and n even and l ≤ 4. The limitation to even m follows from the assumption that the solid has at least orthotropic statistical symmetry but the limitations on n and l arise from the nature of the Raman effect. Some simple special cases are considered and some orientation-independent intensity sums are derived. It is shown that, with the simplifying assumption usually made, the theory of the polarized fluorescence method for determining molecular orientations is a special case of the theory for the Raman method.
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  • 172
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2167-2172 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The molecular reorientation occurring within deformation bands in one-way drawn polypropylene films has been studied by optical microscopy. The deformation bands formed at the yield stress in tension tests on specimens cut at various angles to the initial drawing direction. It is shown that the principal axes of the refractive index ellipsoid in the deformation band coincide with the principal axes of the plastic strain ellipsoid, provided that the strains are referred to the initial isotropic state, i.e., prior to the initial drawing process. This result is similar to the results obtained previously for poly(ethylene terephthalate), but differes somewhat from the results obtained by other workers for poly(vinyl chloride). A possible reason for these differences is discussed.
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  • 173
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2209-2222 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The rate at which PTFE transforms from the triclinic to the hexagonal phase has been measured under isothermal conditions. Samples in a series of decreasing density and crystallinity show increased isothermal rates of transformation. Observed kinetic data are interpreted on the basis of a modified Avrami-Johnson-Mehl treatment. A model for the transformation in which planes of helix-hand reversal propagate through the lattice is shown to fit the experimental results. The transformation rate is observed to be proportional to the total (001) surface area in the polytetrafluoroethylene specimens, suggesting that nucleation of the transformation takes place at grain boundaries.
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  • 174
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2231-2238 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Low-angle x-ray scattering methods have been applied to determine the parameters of the scattering materials in horn keratin. A low-angle camera of Kratky's latest design has been used for the experimental measurements. By treating the substance as a densely packed system, the evaluation of the parameters has been made after theories of Porod and Kratky. Pore analysis of the substance yields a specific inner surface of 4.7 × 10-1m2/cm3, a heterogeneity distance lc = 290.2Å and a reduced inhomogeneity length lr = 99.4Å. The volume of the pores has also been determined approximately.
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  • 175
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2249-2257 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Peroxide radical concentrations were measured from both PET and nylon 6 fibers mechanically stretched in air at room temperature and quickly quenched into liquid nitrogen. The radical concentrations depend on degree of stretching as well as conditions under which the fibers were made, i.e., morphology. Drawn fibers of PET and nylon 6 produced peroxide radical concentrations of the same order of magnitude at the breaking points. These results indicate that chain scissions occur both in PET and nylon 6 under mechanical stretching.
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  • 176
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2297-2300 
    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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  • 177
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2239-2248 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The flow curves of fractionated polydimethylsiloxanes of different molecular weights were obtained over a wide range of shear rates, from 3 × 10-1 to 4.3 × 106 sec-1, by use of a gas-driven capillary viscometer designed to decrease the experimental error in high shear rate region. Non-Newtonian flow can occur at molecular weights below the critical molecular weight Mc for the entanglement of polymer chain. The critical molecular weight M′c for the onset of the non-Newtonian flow is identical with that of the segment of viscous flow. For the polymer of molecular weights from M′c to Mc, the upper Newtonian viscosity increases with an increase in molecular weight. Above Mc, the upper Newtonian viscosity is almost independent of the molecular weight.
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  • 178
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2259-2280 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Photocurrents induced by ultraviolet illumination of poly(ethylene terephthalate) (Mylar) and polyethylene specimens supplied with aluminum electrodes in a sandwich configuration have been studied in the wavelength range 380-180 nm. A description is given of the precautions taken to ensure that artefacts such as photoelectric emission external to the specimen do not influence the measurements. In both materials, a fast and a slow transient are present. Measurements on polyethylene show that the magnitude of the response is linearly dependent on the light intensity and is essentially thickness independent. This behavior leads to difficulties in interpretation in terms of known conduction processes. In Mylar it is shown that hole injection from the positive electrode into the polymer is responsible for the observed currents, and evidence to associate a similar process with the effects in polyethylene is presented.
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  • 179
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2333-2342 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Transmission electron microscopy and electron diffraction were used to study the molecular structure of fibers drawn from polyethylene single crystals at 77, 293, and 383°K. The results suggest that the formation of the fibers occurs by a two-step process. The first step is the breaking off of single blocks of folded chains from the single crystals so that a “string-of-pearls” structure is obtained. If the temperature is sufficiently high this process is followed by the thermally activated rearrangement of the molecules in the drawn fibers so that a “bamboo” structure results.
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  • 180
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2397-2407 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polyethylene single crystals deformed on copper and NaCl single-crystal substrates by the method of Gleiter and Argon were examined in transmission electron microscopy attached to carbon film carriers constraining them to their deformed state and also after they have been removed from the deformed substrates and were allowed to relax. It was observed that the imposed shear strains can be accommodated by the polyethylene crystals by a combination of debonding from the substrate, elastic flexing, extensive inplane twinning and martensitic shear transformations, buckling, and tearing. No contrast effects suggestive of slip lines could be observed in dark field studies, and the gold droplet decoration technique failed to detect any unambiguous slip lines. From this it is concluded that the critical shear stress for slip is always higher than that for twinning and martensitic shear transformations, and that crystals will deform preferentially by these latter modes.
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  • 181
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2437-2452 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Based on an analogy with the growth of kink bands in oriented and annealed crystalline polymers, a mechanism is suggested for the deformation-induced spherulite-to-fibril transformation. Oriented and annealed material was employed as a model because it has roughly the same structure as the lamellar bundle of the spherulite. Under conditions that minimize the fibrillar quality and maximize the lamellar bundle quality, oriented and annealed crystalline polymers deform with the formation and growth of kink bands. The characteristics of kink bands are the sharpness of the kinks, occurring within zones ca. 100 Å wide, and mirror symmetry of the fibrils about the kink-zone planes. The spherulite-fibril transformation is suggested by analogy, then, to occur in the narrow zones that indeed are often found and to result in mirror symmetry of the chain axes about the transformation-zone planes, which may not exactly occur because of a tendency for the tie molecules to be pulled from the lamellae during drawing. The implications for the transformation are (a) that the microfibril backbones are derived from the tie molecules between lamellae and (b) though some unfolding occurs as blocks that were adjacent within the lamellae become separated, the crystals remain mostly intact during the transformation. The analog is supported by or at least is consistent with various other results, including those from morphological and small- and wide-angle x-ray studies.
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  • 182
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2453-2459 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The Rayleigh linewidth Γ of light scattered by dilute aqueous solutions of polystyrene latex spheres has been measured by using time-dependent photocurrent signal correlation with a precision typically of 0.5-1% over a range of scattering angles θ. With independent measurements of the diffusion coefficient D from D = lim K → 0 (Γ/K2), the diameter of the sphere d by means of electron microscopy, and the hydrodynamic shear viscosity η, we have confirmed the Stokes-Einstein relation D = kT/3πηd to within 1% if we take into account the effect of polydispersity on our Rayleigh linewidth data. We also find that dEM = 907 ± 56 Å for sample LS-1132-B as reported by the Dow Chemical Company differs from our dSB = 847 (±1.6%) Å ≈ dEM = 851 (±2%) by about 7%, which is outside the limits of error of our experiments. The subscripts EM and SB denote electron microscope and self-beating, respectively, while K ≡ (4π/λ)sin(θ/2) is the magnitude of the momentum transfer vector.
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  • 183
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2461-2473 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Samples of a phenol-formaldehyde polymer with a deliberately introduced flaw were fractured in tension. The appearance of the fracture surface near the flaw suggested the disruption of particles pre-existing in the polymer. At a greater distance from the flaw, a featureless surface was observed which was succeeded by one showing interference colors. At still greater distances, linear features were observed to be lying in the direction of crack propagation which, in most areas, were regular and evenly spaced. There were indications that these features were formed by the curling of a surface film. The above observations are interpreted as providing evidence that tensile fracture is accompanied by plastic defórmation at the fracture surface.
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  • 184
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 1999-2007 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The orientation of crystallites in a bundle of parallel cotton fibers was studied by x-ray diffraction. The intensity distributions of the 101 and 002 diffraction rings showed the distributions of (101) and (002) planes to be identical within the limits of accuracy. Therefore, the crystallites in the cotton fibers very likely had random orientation about their long axes. The orientation distribution of these axes was calculated by using the intensity distribution of the 002 diffraction ring. The cylindrically symmetrical density distribution J(β) thus obtained was multiplied by sin β to obtain the distribution of relative numbers of crystallites at given angles β to the long axis of the fiber. The average 〈β〉 was found to be in agreement with the value of 〈sin2β〉 measured from the 002 diffraction ring. The intensity distributions on the 101 and 002 diffraction rings showed small fluctuations. These fluctuations appeared much stronger in the J(β) and sin β J(β) distributions, indicating clear discontinuities in the pitch angle distribution.
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  • 185
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2009-2024 
    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 strain-induced crystallization of a crosslinked 89% trans-polypentenamer was studied as a function of temperature and strain by using a combined birefringence - stress relaxation technique. The crystallization rate was found to be extremely sensitive to both variables and was, within experimental error, a function of the degree of undercooling alone, the increase in crystallization rate with strain being a direct consequence of the melting point elevation. From the isothermal, isometric crystallization rates, the development of crystallinity in constant-rate-of-strain experiments was calculated and related to characteristics of the stress--strain curve and of the temperature-strain rate dependence of tensile strength. These calculations allow one to estimate under what conditions sufficient crystallinity may be expected for the attainment of high strength in absence of reinforcing fillers. Crystallinities measured in this work were of the order of 10% or less. A limited x-ray diffraction study confirmed the low order of crystallinity indicated by the stress-birefringence measurements. The relatively high precision of the latter makes this technique attractive for the estimation of small straininduced crystallinities in rubbers.
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  • 186
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2057-2060 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The density increment method has been used to measure the selective sorption coefficient of 2,2,3,3-tetrafluoropropanol (TFP) onto poly(methyl methacrylate) from the solvent mixture benzene-TFP (80:20 by volume). The results are in good agreement with the data obtained by the established refractive index increment method. The density increment method seems to be a promising tool for the characterization of polymer solutions in multicomponent solvents.
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  • 187
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2125-2134 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The validity of Silberberg's hypothesis concerning the conformation of branched polypeptides was tested by studies on solutions and on monolayers. The poly(α-amino acids) investigated consisted of poly-L-lysine backbones with side chains of poly(gamma;-benzyl L-gutamate) and poly(β-benzyl L-aspartate). In solution, the conformation was studied in the mixed solvent chloroform-dichloroacetic acid. Optical rotatory dispersion measurements demonstrated the existence of a helix-coil transition which is a function of the length of the side chain. A significant “transition curve” appeared between 9 and 15 residues. From the results, it may be assumed that the poly-L-lysine backbone is extended in a coiled conformation and the side chains are coiled or helical, depending on the number of glutamate residues. At the air-water interface, a discontinuity in the surface-pressure curve appears between 9 and 15 residues per side chain. The similarity with the results obtained in solution appears significant; however, this has to be confirmed with methods more specific for structural modifications.
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  • 188
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2155-2166 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A diffusion equation for the distribution of ionic impurities in a polymer under a dc field has been solved analytically for the conditions that neither injection nor absorption of impurity ions takes place at either electrode and that the ions do not interact. By using the solution of the diffusion equation, an ionic contribution to the complex dielectric constant is calculated. The most important results are as follows. (1) At high temperatures and low frequencies, the dielectric loss factor of the polymer decreases exponentially with the time elapsed after the application of the dc bias. (2) The dielectric constant is not greatly affected by the bias. (3) The ionic contribution to the loss factor in the absence of the dc bias is represented as ∊i″ = 4πνDq2/ωkT, where ν is the density of mobile ions, D the diffusion coefficient, q the charge of an ion, ω the angular frequency, k the Boltzmann constant, and T the absolute temperature. (4) A method is presented for distinguishing between the apparent activation energy for diffusion and that for generation of mobile ions.
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  • 189
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2173-2187 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Factors which affect and broaden molecular weight distributions are investigated for polymerizations in catalyst particles which are accumulating polymer, such as Ziegler polymerizations of olefins. Expressions for the Q value, or ratio of weight-average to number-average molecular weight, are derived for simple, but important linear models. These expressions are of the form Q = FSX for a kinetic scheme in which polymer chains have an infinite growing lifetime, and Q = 2FGSX for a kinetic scheme in which termination by hydrogen is dominant and each site produces many chains. The factors F, G, S, and X are equal to or greater than unity: F depends on particle geometry and the nature of diffusion and reaction; G depends on environmental history of the particle; S depends on the distribution of site activities; and X depends on the distribution of particle sizes. Effects of reactor type are also studied quantitatively.
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  • 190
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2223-2229 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Specific heats of a series of plasticized and unplasticized poly(vinyl chloride) compositions have been determined by a differential scanning calorimeter over the temperature range 200-400°K. The glass temperatures were higher and the specific heat values at 300°K lower with phthalate esters then with esters of aliphatic acids; those values were also higher and lower, respectively, with benzyl-containing esters than with the methyl or octyl esters. The data were treated by a computer technique and plotted. A mathematical expression was developed which would describe the curves obtained when specific heat was plotted against temperature, and provided values in each case for the glass temperature and the specific heat at the glass temperature and at 300°K, as well as other descriptive parameters.
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  • 191
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2189-2208 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Chain-backbone motion in glassy polycarbonate has been investigated both under isothermal stress, and also under zero stress during isothermal annealing of freely contracting film specimens. In both types of experiment, backbone motion was detected by measuring the change in infrared dichroism. The dichroism of absorption bands at 1364 and 2971 cm-1, which have transition moment vectors directly related to the chain-backbone orientation, was studied. Under tensile stress in the homogeneous region of deformation, changes of up to 2.2° in the mean chain-backbone orientation angle were measured at 23°C. With the onset of cold drawing a total orientation change of some 8° was observed. For the isothermal annealing experiments, a film specimen holder employing conductive heating with radiative losses was employed. It enables infrared measurements to be made while the temperature of the contracting specimen is maintained constant to ± 0.5°C. Oriented specimens were prepared by isothermal stretching of polycarbonate films to strains of the order of 100%. Changes in the mean chain-backbone orientation angle were observed during annealing of these oriented films at temperatures between 80°C and the glass transition (149°C). Chain motion proceeded during annealing, and chain segments were observed to move cooperatively. The temperature at which the polymer is prestretched has a pronounced effect on its subsequent relaxation during annealing: when the sample was stretched at 23°C. motions were detected during annealing at temperatures as low as 81°C, while, if it was stretched at 154°C, no motion was detected at annealing temperatures below 127°C. The data are discussed in comparison with theories of the glassy state that predict the absence of chain-backbone motion at temperatures significantly below the glass transition. A shift in frequency of the νa (CH3) absorption peak in stretched polycarbonate was measured by using polarized radiation. The effect was interpreted in terms of changes in the intermolecular bonding structure of the oriented polymer.
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  • 192
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2301-2304 
    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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  • 193
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2311-2312 
    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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  • 194
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 1903-1915 
    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 an interferometric method for determining partial specific volumes of macromolecules is briefly reviewed. The experimental technique developed in this laboratory is described. Detailed results are given on the partial specific volume of ovalbumin in aqueous solution and its dependence on pH and KCl concentration. The results are compared, as far as possible, with dilatometric results obtained in another laboratory. The contribution of a change in partial specific volume of the macromolecules and in the partial specific volume of the water associated with them to the results is analyzed, and the scope of a possible complication due to changes in molecular polarizability is pointed out.
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  • 195
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 1941-1947 
    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 Maxwell and of Wagner models with temperature-dependent elements is discussed. It is shown that these models can not be equivalent under nonisothermal conditions. It follows that the theory of equivalence of models does not apply to temperature-induced transients.
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  • 196
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2033-2039 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: This study concerns the influence of 3,4 and 1,2 addition in cyclic polyisoprenes on the extinction coefficients of the absorption bands at 890 and 910 cm-1 due to out-of-plane vibrations of =CH2 of the isopropenyl and vinyl groups (correspoding, respectively, to 3,4 or 1,2 addition). In contrast to analogous bands characteristic of 1,4 addition (especially in the case of cis-1,4 units of polybutadiene), the shape, position, and intensity of these bands are not influenced by changes in the structure of the macromolecular chain. The extinction coefficients of both bands did not change substantially, although the overall presence of both linear and cyclic forms varied over a wide range. It can be assumed, therefore, that the influence of configurational changes upon the intensity of the absorption bands of out-of-plane vibrations for double bonds is not a general phenomenon.
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  • 197
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2051-2056 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Broad-line NMR spectra have been obtained at 90 MHz in the temperature region 140-530°K for four aromatic polyamides: poly(1,3-phenylene isophthalamide), poly(1,4-phenylene terephthalamide), poly(4,4,-diphenylene terephthalamide), and poly(4,4,-diphenylene isophthalamide). For the latter three materials, a broad-line narrowing process occurs in the 210-370°K region. At temperatures above 340°K a complex line shape is observed for all samples. Possible causes of these processes are discussed, and comparison made with dynamic mechanical results.
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  • 198
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2041-2049 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The biaxial response, in combined torsion and tension or compression, of a highly crosslinked polyurethane elastomer has been measured at room temperature under equilibrium conditions with the Becker-Landel torsion-tension tester. Cylindrical specimens of four different aspect ratios were studied. Axial strains ranged from -33% to + 17%, and twists from 0 to 0.83 radians/cm. End effects were avoided by measuring both strains in the gage length at the center of the specimen. A small error in the twist parameter, probably arising from slight misalignment of the instrument, was unresolved. Within this error the normal forces and moments of all the specimens conformed to the neohookean (Mooney-Rivlin with C2 = 0) stored energy function for incompressible materials, and the moduli measured in extension and compression were equal.
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  • 199
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2093-2096 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 4 Ill.
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  • 200
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    Journal of Polymer Science: Polymer Physics Edition 10 (1972), S. 2061-2072 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dynamic viscoelastic properties of S - B - S block copolymers were measured in the tensile and shear deformation modes. Between the glass transitions of the polybutadiene and polystyrene domains the ratio of storage moduli E'/G' in tension and in shear for the same polymer varied from 3 to more than 30, depending on sample preparation. For films cast from good solvents this ratio was near 3; large ratios resulted from deposition from poor polybutadiene solvents or from compression molding. Above the polystyrene glass transition, E'/G' approached 3 for all samples. The effect is ascribed to various degrees of polystyrene domain connectivity. Electron micrographs confirm this interpretation. For morphologies of high polystyrene domain connectivity, the loss tangent in tension is heavily weighted by mechanical losses in the polystyrene phase; the loss tangent in shear is affected only moderately by differences in domain morphology.
    Additional Material: 9 Ill.
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