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  • Chemistry  (32)
  • pressure
  • pressure influence
  • 1985-1989  (18)
  • 1980-1984  (13)
  • 1965-1969  (3)
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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Rheologica acta 21 (1982), S. 505-507 
    ISSN: 1435-1528
    Keywords: Polystyrene solution ; viscosity ; pressure influence
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Colloid & polymer science 259 (1981), S. 1214-1220 
    ISSN: 1435-1536
    Keywords: Solutions of polystyrene ; demixing ; pressure ; viscometry ; solubility parameters
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Zusammenfassung Aus dem Viskositätszusammenbruch von Polymerlösungen, der mit dem Eintritt ins Zweiphasengebiet einhergeht, wurde die Druckabhängigkeit der Entmischungstemperaturen für Lösungen von Polystyrol (M = 600.000) in Cyclohexan, Cyclopentan, Diethylmalonat und 1-Phenyldekan bis 1000 bar bestimmt. Die Anwendung von Druck erhöht die Löslichkeit von Polystyrol in Cyclopentan und Diethylmalonat, erniedrigt aber die in 1-Phenyldekan; im Falle von Cyclohexan wird bei ca. 120 bar ein Druck optimaler Mischbarkeit beobachtet. Die Diskussion dieser Ergebnisse, zusammen mit Literaturangaben, zeigt, daß die Druckeinflüsse durch die gängigen Theorien nicht einmal qualitativ vorhergesagt werden können. Für eine einfache Abschätzung der Effekte kann jedoch der Abstand der (oberen) kritischen Entmischungstemperatur,T c, vom Schmelzpunkt des Lösungsmittels,T MP, herangezogen werden: Aus dem vorliegenden Material folgt, daßT c mit dem Druck steigt, wenn (T c —T MP)/T MP (K/K) kleiner ist als 0,20 und fällt, wenn ein Wert von 0,25 überschritten wird.
    Notes: Summary From the break-down in the viscosity of a polymer solution, associated with the entrance into the two phase region, the pressure dependence of the demixing temperatures of solutions of polystyrene (M = 600.000) in cyclohexane, cyclopentane, diethylmalonate and 1-phenyldecane was measured up to 1000 bar. The application of pressure increases the solubility of polystyrene in cyclopentane and diethylmalonate, but decreases that in 1-phenyldecane; in the case of cyclohexane, a pressure of optimum miscibility is observed at ca. 120 bar. The discussion of these findings, together with further information from the literature, demonstrates that current theories cannot even predict the pressure influences qualitatively. For an easy forecast of the effects, the distance of the (upper) critical solution temperature,T c from the melting point of the solvent,T MP, can, however, serve as a guideline: From the present material it can be concluded thatT c is increased by pressure if (T —T MP)/T MP (K/K) is less than 0,20 but decreased it if it exceeds 0,25.
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  • 3
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: From the break-down in the viscosity and from the increase of the intensity of the scattered light, associated with the entrance into the two-phase region, the pressure dependence of the demixing temperature of solutions of PVC 37 000, PVC 75 000 and PVC 100 000 in phenetole and PVC 75 000 in o-xylene was measured up to 1 000 bar. (The numbers in the codes of the PVC specimens are their approximate molecular weights.) The application of pressure increases the demixing temperatures of PVC in both solvents by about 1 K/100 bar. For a qualitative forecast of the pressure effects, the solubility parameter theory in combination with the corresponding states principle, and an empirical correlation to the relative distance of the critical demixing temperature to the melting point of the pure solvent were used. The results of both concepts are in accord with the experimental findings.
    Additional Material: 4 Ill.
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  • 4
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Investigations with ca. 100 organic liquids in a temperature range from -20°C to 90°C result in a survey of the solubility behaviour of PVC. The experimental results were compared with the predictions of the solubility parameter theory: Accepting δ = 9,75 (cal/cm3)1/2 as the solubility parameter for PVC, all solvents (except ketones in which PVC is soluble independent of their solubility parameters) are located within the range of δPVC ± 0,75. Only three of the 100 liquids examined turned out to be (endothermal) theta-solvents, namely the aromatic solvents o-xylene, phenetole and dimethyl phthalate. The theta-temperatures in o-xylene and phenetole were determined viscometrically by means of the temperature dependence of the Mark-Houwink exponent to be 84 and 88°C, respectively. Viscosity measurements were also performed in the temperature range of 25 to 60°C with solutions of PVC 75 000 in 10 thermodynamically good solvents used for rheological investigations. In all cases the intrinsic viscosities decrease slightly with increasing temperature, i.e., all solutions are weakly exothermal. The binary cluster integral, β, was determined (taking the monomeric unit as the statistical segment) and the polar contribution, βe, was calculated from Yamakawa's theory. The correlations between the non-polar part of (βn = β - βe) and the solubility parameter of the solvent, found by Utracki, were tested and found to be valid for the present systems, too.
    Additional Material: 4 Ill.
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  • 5
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Solutions of poly (decyl methacrylate) in isooctane (2,2, 4-trimethylpentane) show lower critical solution temperatures (LCST) that lie well below the thermal degradation of the polymer. The corresponding exothermal theta-temperature (from the Shultz-Flory plot) amounts to 210°C. The increase in solvent quality by pressure turns out to be very pronounced (d Tc/dp ≈ +1 K/bar). With solutions of the polymer in motor oils, high temperature demixing is unlikely to occur below their boiling point. The theoretical evaluation of published experimental data for 11 different systems exhibiting LCSTs demonstrates the following: Under the equilibrium vapour pressure of the solution high temperature demixing is generally observed withing the temperature interval between Tb, the boiling point of the pure solvent (1 bar), and 1,5 Tb. As Tc - Tb increases, the heats of mixing and the pressure influence on Tc increase, too.
    Additional Material: 4 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 2539-2551 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The viscosity of solutions of poly(decyl methacrylate)s, PDMA, in 1-pentanol (thermodynamically poor solvent) and in toluence or isooctane (good solvents) was measured up to shear rates of 3 · 104s-1 by means of rotational viscosimeters. The observed pronounced shear thinning is for all solutions well described by the theory of Graessley, with the extension, introduced by Ito. Two parameters, resulting from the evaluation of the flow curves on the basis of the above theory, are discussed: τ0, a characteristic relaxation time of the polymer chain, is found to be in the range of ms. ηfric, a frictional parameter, independent of shear rate, amounts upto 50% of the zero-shear viscosity for the measured solutions. Both, τ0 and ηfric, increase with decreasing solvent quality, increasing molecular weight, and increasing concentration, in accord with theory. A comparatively sharp downward bend, separating two power-law regimes, shows up with moderately concentrated solutions, as the shear rate exceeds about 103 to 104 s-1. This transition is tentatively interpreted as an orientation of the long side chains of PDMA.
    Additional Material: 12 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 2169-2181 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: By means of data from critical demixing and vapour pressure measurements and by inverse gas chromatography, including the results of published light scattering measurments, a consistent picture is obtained for the entire dependence of the Flory-Huggins parameter χ on the weight fraction w2 of the polymer and on the temperature T for the system tert-butyl acetate/polystyrene. Within the entire T-range (ca. 0°C - 140°C), χ increases stronger than exponentially with w2, the rise being the larger the larger χH (the enthalpy contribution to χ) becomes in the limit of infinite dilution. At sufficiently high temperatures (≳ 50°C), χH changes its sign from negative to positive as w2 is raised. This behaviour, as well as the general shape of χ(w2) is in qualitative accord with the results of the corresponding-states theory as developed by Flory et al.
    Additional Material: 5 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 189 (1988), S. 1613-1625 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An apparatus for turbidimetric measurements of demixing temperatures under shear flow is presented, and the results of experiments with trans-decahydronaphthalene/polystyrene (TD/PS) solutions, investigating molecular weights ranging from 100 kg/mol to 1770 kg/mol, are compared with viscometric data. It is found that the sign and magnitude of shear effects depend on molecular weight (Mw), polymer concentration (c2), and shear rate (\documentclass{article}\pagestyle{empty}\begin{document}$ \dot \gamma $\end{document}). For the first time, it was possible to study a solution which exhibits shear dissolution at low shear rates but shear demixing at high shear rates.
    Additional Material: 11 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1801-1818 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In order to investigate the influences of different end-groups on oligomer miscibility with other substances, oligo(propylene glycol)s bearing —OH groups (OPG-OH) studied in the previous paper2, were acetylated at both ends (OPG-AC). The limits of miscibility of OPG-AC with oligo(dimethylsiloxane) (ODMS) were measured turbidimetrically. A simple and reliable method for the determination of the critical points from turbidity data is presented. The observed upper critical temperatures (Tc) increase with degree of oligomerization of ODMS (ranging from 1 to 5), whereas Tc shows a minimum when the degree of oligomerization of the OPG-AC is raised (from 1 to 57,5). For lower mol. wt. oligoglycols, the Tc-values of ODMS/OPG-AC are lower by ca. 50 K as compared with those of ODMS/OPG-OH. The different end-groups play a minor role with respect to the pressure influences (up to 1 500 bar the miscibility increases in all cases). For OPG-AC the chain length of optimum miscibility with a given ODMS is found at considerably lower values than for OPG-OH. The theoretical evaluation of the experimental material on the basis of the lattice theory yields a reduction in the enthalpies of mixing up to 10% and an increase in the volumes of mixing (〈0) up to 50% when —OH is replaced by —AC. For the treatment of end-group effects, the solubility parameter theory, when combined with the concept of molar attraction constants, presents several advantages: In particular it is possible to describe the phase separation behaviour of the different oligomer mixtures simply by means of solubility parameters and molar volumes of the different segments and end-groups and to forecast the presence or absence of a chain-length of optimum miscibility.
    Additional Material: 11 Ill.
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  • 10
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A new Continuous Polymer Fractionation method, called CPF, is described. The polymer to be fractionated is dissolved in a solvent/non-solvent mixture, and this solution (feed) is extracted continuously by a second liquid (extracting agent), which contains the same solvent components as the feed. In the case of PVC, the fractionation was carried out with a pulsed counter current extraction apparatus and THF/water was used as solvent/non-solvent mixture. Fractionation is achieved by the fact that the molecules are distributed over the counter current phases according to their chain length; the feed leaves the column as gel and the extracting agent as sol. First some explorative experiments were made in order to determine suitable working parameters, like frequency and amplitude of pulsation, compositions of feed and extracting agent and the ratio of flow. With the so obtained parameters, preparative experiments were carried out, yielding five PVC-fractions with molecular weights ranging from 20 000 to 100 000 (GPC, LS) and non-uniformities, U = (Mw/Mn) -1, of about 0,2 (GPC) using a starting material with Mw = 67 000 and U = 0,95.
    Additional Material: 12 Ill.
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