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  • 1
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The design of a fully automatized chromatograph based on Phase Distribution Chromatography (PDC) is presented and some of the most important results of the measurements shown. PDC represents a dynamical phase separation as column method: the separation of the polymer components in a PDC-column is based on thermodynamic-kinetical interactions of the mobile phase (the polymer to be analyzed) below the theta temperature of the system by a gel of the same high polymer situated on the surface of small glass beads. The sigmoidal shape of the measured PDC calibration curves can be explained by introducing a dynamical flow-equilibrium in the system sol/gel which highly differs from the thermodynamic equilibrium at low temperatures of the column.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Phase distribution chromatography (PDC) is demonstrated to be a powerful method for the correct determination of narrow molecular weight distributions. This is shown by comparing the molecular weight distributions (MWD) of polystyrenes obtained from PDC measurements with those obtained by Baker-Williams fractionation and by gel permeation chromatography. Four problems are formulated and analyzed which are closely connected with the calculation of the MWD from a measured PDC-elution curve at temperatures below the theta point of the system. Thus, the theory of PDC outlined previously is tested.
    Additional Material: 7 Ill.
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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: A phenomenological theory of the Phase Distribution Chromatography (PDC)-separation effect is outlined and a theoretical equation for the measured PDC-calibration curves is given. Assuming a reversible-thermodynamical equilibrium in the polystyrene-PDC-column, only a relatively small part of the measured PDC-calibration curves could be explained: namely those running below their tangents. In order to explain the whole sigmoidal shape of the experimental curves, a theory of steady state in the system sol/gel was developed assuming deformation of the polymer coil near the gel front due to the stress related to the velocity gradient. The resulting dynamical flow-equilibrium differs highly from the reversible-thermodynamic one at suitable low column temperatures. It leads to two typical calibration regions explaining the resolution power of the PDC-column as a function of temperature. Analysis of the first one (reversible-thermodynamical) starts with a three-parameter partition function and leads to two contributions of the heat of transfer of a P-mer from the gel into the sol of the column. These results are compared with those of Schulz, von Günner and Gerrens, and of Schulz and Horbach. In this way a physical interpretation of the three parameters in the partition coefficient of the P-mer in the system gel/sol of the PDC-column can be given.
    Additional Material: 6 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 2845-2861 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dynamical region of the measured calibration curves is investigated using the results of the theory published previously. The kinetic constants of the flow-equilibrium are calculated from the measurements according to two different models for a spontaneous polymer diffusion of the transported P-mer from sol into gel of the Phase Distribution Chromatography (PDC)-column. The corresponding lateral concentration profiles in the gel are found by analytical integration of Fick's second law under the corresponding boundaries. An energetic model of this flow-equilibrium is stated, giving the activation enthalpy and -entropy of the rediffusion of the polymer from gel into sol after some retardation time in the gel. The influence of the gel mass of the column on its resolution is briefly investigated. Since the measurements show that the resolution of the PDC-column vanishes in the vicinity of the theta point, spreading phenomena in the column can be investigated by means of analysis of the corresponding PDC elution curves. The results give a basis for the numerical computation of the molecular weight distribution of narrowly distributed polystyrenes from PDC elution curves at sufficiently low column temperatures. The PDC-separation effect is opposite to that of gel permeation chromatography (GPC).
    Additional Material: 8 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
    Description / Table of Contents: Für das direkte und das inverse Problem der Lichtstreuung von verdünnten Polymerlösungen GAUSSscher Knäuel am Thetapunkt wird eine Lösung gefunden. Dazu werden theoretische Streufunktionen und ihre Ableitungen für die allgemeine Gammaverteilung des Molekulargewichts analytisch berechnet in Abhängigkeit von der Uneinheitlichkeit und vom Gewichtsmittel der Molekulargewichtsverteilung sowie für verschiedene Verhältnisse der statistischen Segmentlänge des Knäuels zur Wellenlänge des Streulichtes. Aufgrund der Analyse des Operators in der ZIMMschen Gleichung werden die Asymptote und die Tangente zu P-1Θ analytisch bestimmt und im Winkelbereich von 150° bis 180° miteinander verglichen. Streufunktionen von Mikrogelsystemen werden analytisch berechnet und diskutiert. Um die Molekulargewichtsverteilung (MGV) aus einem gegebenen ZIMM-Diagramm für GAUSSsche Knäuel am Thetapunkt zu berechnen, wird das zugehörige inverse Problem analytisch gelöst, wobei die benötigtenullte Näherung für die Segmentlänge des Knäuels aus viskosimetrischen Messungen genommen wird. Mit Hilfe dieser Methode können die MGV und die korrekte Segmentlänge theoretisch mit beliebig (vernünftig) hoher Genauigkeit berechnet werden. Die Rechnung zeigt jedoch, daß für die praktische Anwendung eine extrem hohe Meßgenauigkeit der Lichtstreuungsmessungen nötig ist.
    Notes: The direct and the inverse problem of the light scattering from dilute polymer solutions is solved for GAUssian coils at the theta point. Theoretical scattering functions and their derivatives are analytically calculated for the general gamma distribution of molecular weights as a function of the non-uniformity and the weight average molecular weight, and also for various ratios of the statistical segment length of the coil to the wave length of the scattered light. The asymptote and the tangent of P-1Θ are obtained by analysing the operator in the ZIMM equation and their mutual position is compared in the angle range 150° to 180°. The scattering envelopes of microgel systems are analytically calculated and discussed. In order to obtain the molecular weight distribution (MWD) from a given ZIMM diagram of GAUssian coils at the theta point, the corresponding inverse problem is solved analytically, the necessary zero approximation of the segment length being taken from viscometric measurements. With the help of the presented method the MWD and the correct statistical segment length of the coil can theoretically be computed with any reasonable accuracy. However, the calculation shows that for practical use extremely high accuracy of the light scattering measurements is necessary.
    Additional Material: 6 Ill.
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  • 6
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The molecular weight distribution (MWD) of a high polymer is calculated from a weakly perturbed Zimm-plot of the classical light scattering on dilute solutions of Gaussian polymer coils (theta state). A typical Zimm-plot is simulated corresponding to the measurements of high accuracy as would be obtained by using the laser photometer described by Hack and Meyerhoff. The accuracy as published by these authors for small dissymmetries is used. Two numerical methods for calculating the MWD are briefly described and tested, both using an empirical formula for the Laplace image of the calculated MWD.
    Additional Material: 1 Ill.
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  • 7
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The molecular weight distribution (MWD) of a high polymer is calculated from a weakly perturbed Zimm-plot of the classical light scattering on dilute solutions of Gaussian polymer coils (theta state). A typical Zimm-plot is simulated corresponding to the measurements of high accuracy as would be obtained by using the laser photometer described by Hack and Meyerhoff. The accuracy as published by these authors for small dissymmetries is used. Two inversion procedures are described in detail and tested, both of them avoiding the use of an empirical formula for the Laplace image of the calculated MWD. A complete numerical analysis of the results is given. The results are compared with those of the previous paper.
    Additional Material: 4 Tab.
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 1047-1057 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In a previous paper of the author the assumption was stated that the separation mechanism of phase distribution chromatography (PDC), based on a flow equilibrium (steady state) of the transported polymer between the mobile and the stationary phase of the polystyrene/cyclohexane PDC column, can be explained by means of a deformation of the sorbed polystyrene coils by the velocity gradient along the surface of the stationary phase of the column. In this paper this assumption is tested by means of the theory of rubber elasticity applied to the polystyrene coils sorbed on the surface of the polystyrene gel. The velocity gradient near the surface of the gel is estimated by means of the equations of Hagen-Poiseuille and the deformation of the coil caused by this gradient is calculated from experimental data. The results show that the deformation concept can explain the PDC separation mechanism found from the measurements and published previously.
    Additional Material: 1 Ill.
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