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  • 1
    ISSN: 1520-5835
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    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: Blends of crystallizable poly(vinyl alcohol) (PVA) and poly-(N-vinyl-2-pyrrolidone) (PVP) of different molecular weights were prepared from aqueous solutions by evaporation and studied by Fourier-transform IR spectroscopy. When the molecular weight of one of the polymer components increases, the PVP content at which crystallinity in PVA is no longer observed decreases. The wide band representing hydroxyl stretching splits into four components at welldefined frequencies which are assigned to (1) multiple hydroxyl-hydroxyl bonding in organized PVA regions, (2) hydroxyls which are simply bonded to carboxyl, (3) hydroxyls doubly bonded to two carbonyls or to one carbonyl and one hydroxyl, and (4) simple hydrogen-hydrogen bonding in amorphous PVA regions. When the PVP content increases, the relative intensity of the bond of di-hydrogen-bonded hydroxyls remains quasi-invariant, while that of multiple hydrogen bonds in PVA decreases, and that of simple hydroxyl-carbonyl bonds increases correspondingly. It appears that the higher the molecular weight, the more effective the hindrance of PVP crystallization. An explanation of the mechanism leading to the formation of different structures in the blends is proposed on the basis of these results. It stresses the importance of the role of chain dynamics in an entangled chain network, which greatly affects the kinetics of crystallization of PVA during the drying step.
    Additional Material: 10 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 437-448 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Blends of crystallizable poly(vinyl alcohol) (PVA) with poly(N-vinyl-2-pyrrolidone) (PVP) made from aqueous solutions appear to be miscible in the whole composition range according to DSC results. A large negative value of the interaction parameter between the two polymers was found from melting point depressions. IR spectroscopy evidenced compatibility of the two polymers on a molecular level. DSC, density and IR results all show a proportion of pure PVA crystallites in blends, which decreases with increasing PVP content and becomes nil at about 50 wt.-% of PVP. However, close examination of the hydroxyl stretching region of the blends indicates the presence of organized regions of PVA beyond this limit. According to IR results, the sequence of decreasing hydrogen-bonding power should be the following: multiple hydroxyl-hydroxyl bonding in organized PVA regions, hydroxyl-carbonyl bonding between the two polymers, and simple hydrogen-hydrogen bonding in amorphous PVA regions. It appears that the PVA component can be held in the amorphous state by hydrogen bonding with the PVP component when there is a sufficient amount of the latter in the blend. The amorphous part of PVA is compatible with PVP, but the crystallizable part is not in its most stable form.
    Additional Material: 9 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 2097-2100 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
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  • 5
    ISSN: 1022-1344
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The measured transient permeation kinetics of acetic acid from a water-acetic acid mixture through poly(vinyl alcohol) films could not be accounted for by the Fick law with a constant diffusion coefficient. A new calculation procedure was developed on the basis of simulation results of the Fickian kinetics in which the diffusion coefficient was assumed to increase exponentially with the local permeant concentration. A fast and reliable fitting procedure, which was set up on a Personal Computer, involves an iterative numerical adjustment of (a) the value of the limiting diffusion coefficient D* (i.e., difusion of the permeant in dry polymer) using the onset part of the permeation rate followed by (b) the value at the upstream face of the plasticization term (argument of the exponential function) using the shape of the experimental curve. The values obtained from fitting the model to the transient kinetics showed that the limiting diffusion coefficient increases drastically, but the plasticization term changes little, with increasing temperature.
    Additional Material: 11 Ill.
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  • 6
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dense membranes made of poly(vinyl alcohol) (PVA) and poly(N-vinyl-2-pyrrolidone) (PVP) blends of different compositions were studied in gas-sweeping permeation of a water-ethanol mixture containing 10 wt.-% of water. When the PVP content increases, the steady-state permeation flux and the water content in the permeate show sudden changes at ca. 30-40 wt.-% of PVP in the membrane: the flux increases drastically, while the water selectivity of the membrane falls to a much lower level. The diffusion coefficients of both water and ethanol, as determined from the permeation flux changes in the transient regime, exhibit a large increase when the PVP content exceeds 30 wt.-%, and this accounts for the flux increase. The fall in the permeation selectivity is shown to be due to a strong decrease in the sorption selectivity. The threshold of the change corresponds approximately to the PVP content at which PVA crystallites no longer exist in the blend. A further study on the states of water in the blend membranes by differential scanning calorimetry made it possible to relate these changes with a change in the interactions of water with hydrophilic sites in the polymer blend when the PVP content changes.
    Additional Material: 8 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Macromolecular Theory and Simulations 3 (1994), S. 379-387 
    ISSN: 1022-1344
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The description of the sorption mechanism of gases in glassy in glassy polymers is of importance for membrane-based gas separation processes as well as for packaging applications. Dual mode theory, postulating a Henry and Langmuir process to occur and leading to an equation with three adjustable parameters, is usually proposed in order to describe the isotherms. A simple mechanistic model, based on an unequal affinity between the gas molecules and the matrix regions occupied either by polymer or a previously sorbed gas molecule, is presented in this paper; in contrast to dual mode theory, this approach does not postulate the existence of microvoids in the glassy matrix. Integration leads to an equation with two adjustable parameters, which is shown to describe precisely already reported isotherms.
    Additional Material: 6 Ill.
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  • 8
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Membranes developed by modification of a cellulose acetate (CA) matrix were studied by means of the flow method CA matrix is modified by poly(4-vinylpyridine) (PVP), or an interpenetrating network (IPN) agent. The obtained diffusion coefficients, permeability coefficients and relaxation kinetic parameters for oxygen, carbon dioxide and water vapour enabled us to consider not only the transport properties of the membranes but also the influence of the relaxation processes on the membrane permeability and stability. The results show that the interactions between water molecules and polar groups on the polymer chains cause the membrane material to swell. This swelling process provokes an increase in the permeation flux of ca. 20-30%. Oxygen causes a consolidation of unstable membranes of the cellulose acetate matrix modified by IPN but not of blends with PVP. The consolidation process reduces the membrane permeability by ca. 38%, while carbon dioxide has no effects on the membrane properties. Membranes based on a modified cellulose acetate matrix have higher permeability than pure CA membranes.
    Additional Material: 10 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 44 (1992), S. 951-958 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: FT-IR spectra of Nafion 117, Raipore 1010, and PESS membranes loaded with different alkaline counterions and equilibrated with different liquid media were recorded by means of the attenuated total reflectance technique. The antisymmetric (vas) and especially the symmetric stretching vibrations (vs) of the sulfonate groups are affected by the presence of solvents in its local chemical environment. In the dry membrane the smaller the bare counterion, the higher the frequency of the symmetric vibration and the stronger the sulfonate-counterion interactions in the contacting ion pair. After equilibration with pure water, ethanol, and 2-propanol, the vs vibration shifts to a constant value corresponding to the solvated sulfonic grouping in the case of Nafion-Li+ membrane. In the cases of PESS-Li+ and Raipore-Li+ membrane only water can cause a similar shift. The greater affinity of the Nafion membrane to alcohols can be attributed to the stronger acidity of the corresponding sulfonic acid. In water-alcohol mixtures the variation of vs with water content indicates that the ion pairs in the PESS-Li+ membrane are progressively dissociated and solvated by increasing amounts of water in 2-propanol. Complete dissociation occurs at about 9 wt % water. Smaller shifts are observed with bigger cations, due to the weaker sulfonate-cation interactions.
    Additional Material: 7 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Polymer International 39 (1996), S. 251-260 
    ISSN: 0959-8103
    Keywords: water ; ethanol ; crystallinity ; concentration-dependence ; diffusion ; poly(vinylalcohol) membranes ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Solvent sorption and diffusion are the key processes that control membrane performances in membrane processes. The sorption characteristic of water and ethanol vapours in poly(vinylalcohol) (PVA) membranes of different crystallinity degrees was measured by microgravimetry and the diffusion characteristic was calculated from the sorption kinetics at different water activities by curve fitting. The sorption isotherms for water vapour in membranes of 28, 37, 44 and 56% crystallinity degrees at 40°C obey the Flory equation based on the polymer lattice model. When the sorption extent was corrected by assuming that only the polymer amorphous phase is accessible to the penetrant, a unique Flory χ interaction parameter, 0.3, was obtained for all samples except for the 28% crystallinity sample. For the latter sample, the lower χ value (0.18) obtained can be explained by a change in the sorption behaviour of the original crystalline domains which may undergo partial destruction. The diffusion coefficient increases with the average water content in the membrane according to an exponential relationship characterized by a limit diffusion coefficient and a plasticization coefficient. The higher the crystallinity of the membrane, the lower the values of the limit diffusion coefficient and the plasticization coefficient. The ethanol sorption was also well described by the Flory-Huggins equation. The limit diffusion coefficient for water was two orders of magnitude larger than that for ethanol.
    Additional Material: 9 Ill.
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