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  • Articles  (64)
  • Chemistry  (64)
  • Analytical Chemistry and Spectroscopy
  • Atomic, Molecular and Optical Physics
  • Diphosphonates
  • Industrial Chemistry
  • 1970-1974
  • 1965-1969
  • 1955-1959  (64)
  • 1957  (64)
  • Physics  (64)
Collection
  • Articles  (64)
Keywords
Publisher
Years
  • 1970-1974
  • 1965-1969
  • 1955-1959  (64)
Year
  • 1
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 23 (1957), S. 211-221 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dielectric properties of polymer solutions are calculated on the assumption that each polymer molecule may be divided in N submolecules whose end-to-end distance shows Gaussian distribution. Electrical charges of alternating sign are attributed to the ends of these submolecules. The equations of motion are given for free-drained structures. From these equations of motion the diffusion equation in configuration space is constructed. The average dipole moment can be calculated by a simple integration procedure. It is found that there should be two dispersion regions, one at low frequencies proportional to 1/N2 and one at high frequencies independent of N. The high frequency maximum in the loss curve has a shape which is very nearly that for a process with a single relaxation time.
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  • 2
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 23 (1957), S. 315-329 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The sorption and permeation of benzene, acetone, and methanol in and through ethyl cellulose has been investigated from the point of view of hysteresis and time-dependence. The three sorbates are imbibed decreasingly in the order given, at any relative pressure, and so swell the polymer to different extents. The medium is one in which anomalous diffusion is to be expected. The study was made in the lower range of concentrations of penetrant. The initial isotherm of acetone at 50°C. lay below subsequent ones at the same temperature. The higher the temperature the smaller this difference tended to be, while the greater the pressure and so the amount imbibed the greater it became. Eventually “settled” reproducible isotherms were found. If the outgassed polymer, following lower temperature isotherms, was “annealed” at a higher temperature and then cooled again, the initial isotherm at 50°C. was more nearly approached. However, subsequent isotherm determinations at the same temperature again established the “settled” isotherm. Permeation rates were determined as a function of pressure under various treatments. Repeated permeation runs caused the permeability of the polymer to decrease to a “settled” value. This behavior may be ascribed to some orientation of polymer, by mass flow, during permeation. After establishing the settled permeability the polymer was outgassed and “annealed” at a higher temperature, and the permeability at the original temperature then lay below the “settled” value. Benzene, which swelled the membrane more than the other sorbates, showed more pronounced effects of the same kind as acetone. On the other hand methanol, which was least sorbed, showed less pronounced time- and history-dependence. Sorption always occurred more slowly than desorption. The various effects have been discussed in terms of a model of the polymer having rather stiff chains with some semipermanent interchain bonds, but other bonds more easily rearranged. The history-dependent effects can arise at temperatures well above the glass transition usually quoted for ethyl cellulose.
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  • 3
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 23 (1957), S. 443-450 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It is shown theoretically that phase separation may arise in solutions of polyelectrolytes due to electrostatic interactions alone. Two models are considered thermodynamically. In both models the free energy is represented as the sum of an entropy of mixing term and an electrostatic free energy term, while the van der Waals attractions are neglected. In the one model, electrically charged rigid cylindrical rods are in solution with an equivalent amount of counterions but without additional electrolyte. The free electrical energy, in this case, is given by the expression of Lifson and Katchalsky. In the other model the solution contains two types of macroions of opposite charge. The macroions are flexible coils carrying a number of univalent charges, the charge density being sufficiently low. The electrical free energy in this case may be approximated by the Debye-Hückel expression. For both models, it is shown that the decrease in the electrical free energy in a phase separation can, at given temperature and pressure, more than compensate for the increase in the entropy of mixing term. The effects of polymer concentration, dielectric constant, charge density, and salt content follow directly from the thermodynamic treatment of the models.
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  • 4
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 2 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 25 (1957), S. 385-401 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The viscosity of dilute solutions of PVA in toluene is investigated as a function of shearing stress in an Ubbelohde precision viscometer which permits determining the efflux time to within 3 × 10-3 sec. Various sources of error in capillary viscometry are discussed. Correction for drainage is made on the basis of a newly developed theory. In a first series of measurements uncorrected values of (t - t0)/t0c are shown to give an anomalous curve when plotted against c. In this series the effect of changes in concentration as a result of adsorption onto the walls of the dilution vessels is studied. The anomaly disappears when corrections are made for various sources of error and for non-Newtonian behavior in particular (second series). The thickness of the adsorption layer on the wall of the capillary is estimated from results in two viscometers with different bore. A comparison with direct measurements of adsorption on glass beads reveals that the average density of the polymer adsorbed is about 0.17 g./ml. The viscosity at low shearing stress is an even function of the shearing stress. The intrinsic viscosity is markedly dependent on shear rate, its value at high shear rates being about 40% of that of zero shear rate.
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  • 6
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 26 (1957), S. 47-55 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The conductivity of the potassium salts of carboxymethylcellulose (CMC) and poly-p-styrene sulfonate (PSS) in the presence of KCl shows a behavior which is in striking contrast to the results of a previously developed theory: when the total concentration of K plus Cl ions is kept constant, the conductivity decreases with increasing polymer content in the majority of cases. Qualitatively this can be explained by a theory of the relaxation effect. This theory makes use of the model of a porous sphere in which the counter ions completely compensate the charge of the fixed ions. The use of the Debye-Hückel approximation is avoided. The charge resulting from relaxation effects is treated as a surface charge.
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  • 7
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 23 (1957), S. 69-73 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An osmometer has been constructed in which the only possible transition from one cell to the other is through the vapor phase. In this way the problem of passage of solute is completely eliminated. In order to obtain a sufficient rate of transition of solvent, the distance between the cells has been made as small as possible. An osmometer with a vapor “membrane” of 0.05 mm. thickness is described and measurements with this osmometer are reported.
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  • 8
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 23 (1957), S. 57-68 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Simultaneous measurements of osmotic pressure and permeation of solute have been made for a nonfractionated polystyrene with a number of membranes of widely different permeability. It is shown that, even after many days, no real equilibrium is reached in an osmometer with a membrane permeable to part of the polymer. The theory of equilibria in such osmometers is developed and shows that, in first approximation, the distribution of permeating solute over the two osmometer cells is not affected by the presence of nonpermeating solute. In second approximation, this distribution is affected indeed, but in this approximation the osmotic pressure is not affected by this unequal distribution. Some short-time experiments also show that when the number of permeated molecules is negligible (t → 0) the contribution of a molecular species to the osmotic pressure is less than the value given by equilibrium thermodynamics if the membrane is not completely impermeable to that molecular species. This phenomenon is in accordance with the theory of permeability of membranes based upon nonequilibrium thermodynamics.
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  • 9
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 24 (1957), S. 57-61 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A study has been made of crystallization phenomena in nylon 66 occurring after fusion at temperatures just above the melting point. It appeared to be possible to obtain optically negative spherulites in nylon 66 by crystallizing at temperatures between 250 and 258°C., after fusion at temperatures above 258 but below 265°C. The radial growth rate of the negative spherulites has been determined and has been found to depend on the crystallization temperature. The optically negative spherulites have a higher optical melting point than the optically positive spherulites hitherto observed in nylon 66. Another type of spherulitic structure with spherulites of a fibrous appearance, of which the optical sign cannot be determined, is reported. An attempt is made to explain the data obtained on the basis of the generally accepted crystallization mechanism, valid for linear high polymers.
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  • 10
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 23 (1957), S. 601-616 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: In order to study the electroviscous effect, we have used very stable aqueous suspensions of carbon black, obtained after chemical treatment. These suspensions contain carbon black particles of approximately spherical form, perfectly rigid and carrying on their surfaces chemical groups, which give the particles a polyelectrolyte behavior. We have studied the viscosity of the solution when the dielectric constant ε of the medium has been changed, either by addition, to the water, of a solvent with a low dielectric constant, e.g., ethanol, or by changing the temperature. The influence on the viscosity of the medium by addition of a neutral salt (KCl) of a strong acid (HCl) and of a strong base (KOH) has also been considered. Besides these viscometric data a reversible flocculation of the sol has been observed when ε diminishes sufficiently, while no flocculation occurs in the presence of KOH, independently of the concentration of KOH. Such behavior has not been observed previously. As expected, in the presence of KCl flocculation occurs if the concentration is high enough; the precipitation is improved by HCl addition. The following conclusions may be drawn from these experiments: (1) The experimental data show an increase in viscosity, due to a “limited flocculation,” which influences not the apparent state of the sol but causes an increase of K. This phenomenon is followed by the flocculation of the sol when the dielectric constant is further decreased or when the ionic strength is further increased. A simple explanation is given for the “limited flocculation” and for the increasing viscosity which occur simultaneously. (2) When the electroviscous effect alone must be considered, Booth's theory gives a satisfactory explanation for viscometric data. (3) The data show that the sol stability depends strongly from the charge carried by the particles and on the thickness of the double layer as expressed by the parameter χ-1 of Debye.
    Notes: Nous avons utilisé dans notre étude de l'effet électrovisqueux des suspensions aqueuses de noir de carbone, très stables, obtenues après traitement chimique. Ces suspensions contiennent des particules de noir de carbone de forme approximativement sphérique, parafaitement rigides et qui portent en surface des groupements chimiques qui leur confèrent le caractère de polyélectrolyte. Nous avons étudié la viscosité de la solution lorsque l'on fait varier la constante diélectrique ε du milieu dispersant soit par addition à l'eau d'un solvant miscible de basse constante-diélectrique tel que l'alcool éthylique, soit par variation de la température. Nous avons également étudié l'influence sur la viscosité de l'addition au milieu de dispersion de sel neutre (KCl) d'acide fort (HCl) et de base forte (KOH). En dehors des observations viscosimetriques on a noté qu'il y a floculation reversible du sol lorsque l'on diminue suffisement ε, tandis que le sol ne flocule pas en milieu KOH, quelle que soit la concentration en KOH. Ces deux observations ne semblent pas avoir de précédent. Le comportement du sol en milieu KCl est classique, c'est-a-dire qu'il y a floculation pour des concentration suffisantes en sel. La floculation apparait plus vite par addition d'HCl que de KCl. On peut tirer de l'étude les conclusions suivantes: (1) Les résultats expérimentaux mettent en évidence un accroissement de viscosité provoqué par l'apparition de ce que l'on a dénommé la “floculation limitée” phénomène qui ne se manifeste pas sur l'état apparent du sol et que décèle seulement l'augmentation de K. Ce phénomène sera suivi de la floculation proprement dite si l'on continue à abaisser ε ou à augmenter la concentration ionique. On propose une explication simple de la floculation limitée et de l'accroissement de viscosité qui l'accompagne. (2) Dans le domaine où les sol est soumis au seul effet électrovisqueux la théorie de Booth permet une interpretation satisfaisante des résultats viscosimetriques. (3) Les résultats obtenus montrent que la stabilité du sol étudié dépend nettement de la grandeur de la charge portée par les particules et de l'épaisseur de la double couche approximée par le paramètre x-1 selon Debye.
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