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  • 1
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 21 (1977), S. 1607-1613 
    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: Hydrolyzed cellulose-polyacrylonitrile graft copolymer is a polyelectrolyte gel suspension with a high viscosity in water. It is a closely packed swollen gel particle suspension in the appropriate concentration range and has similar rheological properties to other thickeners of this type. Viscosities η in either water or salt solution are reduced to a single master curve by use of the reduced viscosity function η/cQ, where c is weight fraction of polymer and Q is swelling volume in excess solvent of the same ionic strength. The effective molecular weight between crosslinks, Mc, determined from shear modulus, corresponds to Mc values for other closely packed gel thickners of similar η/cQ. Among all examples of this class of thickener, the plateau values of η/cQ, which occur at cQ 〉 2, are approximately inversely proportional to Mc.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 18 (1974), S. 2747-2761 
    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: Hydrolyzed starch-polyacrylonitrile (H-SPAN) graft copolymers form highly viscoelastic mixtures with water, even at concentrations less than 1% by weight. In many ways these mixtures behave like ordinary polyelectrolyte solutions, but dilution experiments revealed that linear reduced viscosity-concentration plots could not be obtained even under ostensibly isoionic dilution conditions. This result, combined with a determination of gel content from centrifugation studies, led to the conclusion that high viscosity H-SPAN water mixtures consist of swollen, deformable gel particles closely packed in intimate contact. Under high dilution or at high ionic strength conditions, the gel particles no longer are tightly packed, solvent is present in excess, the viscosity drops precipitously, and the thickening action effectively disappears. For comparative purposes, a commercial thickening agent (Carbopol 941) was examined and found to act in the same way. All reduced viscosity-concentration curves obtained by dilution, either with salt solutions or water, can be shifted to a single normalized reduced viscosity plot. This shift is done by using as the concentration variable the quantity cQ, where c is the polyelectrolyte concentration and Q is the swelling which the gel particles undergo in an excess of solvent at the corresponding total ionic strength of the solution of concentration c.
    Additional Material: 8 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 21 (1977), S. 113-122 
    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: When used as a thickening agent in aqueous suspension, hydrolyzed starch-polyacrylonitrile graft copolymer (H-SPAN) has broadly variable rheological properties, such as viscosity, storage modulus, and stress overshoot characteristics. A series of H-SPAN preparations with variable swelling ratio Q were made by pretreating portions of stock material. As 1% suspensions in water, they had viscosities η that were non-Newtonian. At a constant shear rate, η of the suspensions depended on Q and had a sharp maximum in the midrange of Q. In terms of reduced concentration cQ, where c is weight fraction of polymer, the highest η occurred when cQ was approximately 2. With isoionic dilution, each suspension had a constant reduced viscosity function, η/cQ, provided cQ 〉 2. The value of η/cQ fell rapidly when cQ approached 1. All thickeners of the closely packed gel-particle type so far examined have this relation of the reduced variables. The shear modulus calculated from measurements of primary normal force and corrected for solvent swelling, according to theory for rubber for elasticity, was essentially constant for each suspension measured during isoionic dilution to cQ = 2. The density of crosslinks calculated from the modulus was extremely low for all samples. The variable rheological properties of the preparations resulted primarily from differences in their low effective crosslink densities.
    Additional Material: 5 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 22 (1978), S. 1343-1357 
    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: A series of well-characterized starch-g-polyacrylonitrile (PAN) graft copolymers was prepared from corn starch which had been heated in water at temperatures up to 94°C to vary the extent of starch granule swelling and disruption. Graft polymerization onto gelatinized starch gave less frequent grafting of higher molecular weight PAN than comparable graft polymerizations onto ungelatinized starch. A graft copolymer was also prepared from gelatinized starch under high dilution conditions to give lower molecular weight grafted PAN and more frequent grafting. Graft copolymers were then saponified with sodium hydroxide to convert nitrile substituents to a mixture of carboxamide and sodium carboxylate. Saponified graft copolymers were only partially water soluble and consisted largely of highly swollen, insoluble gel, which was separated from solubles for the study of physical properties. Saponification mixtures were also dried to yield highly absorbent polymer films. With the exception of the graft copolymer prepared under high dilution conditions, the physical properties of saponified graft copolymers depended on whether or not the granules of starch were gelatinized before graft polymerization. Compared with saponified graft copolymers derived from ungelatinized starch, those prepared from gelatinized starch gave films that absorbed larger amounts of aqueous fluids. Also, the gel fractions from these saponified gelatinized polymers exhibited higher water swelling, lower shear modulus, and a lower reduced viscosity function (η/cQ). The saponified graft copolymer prepared from gelatinized starch under high dilution conditions more closely resembled those prepared from ungelatinized starch, suggesting that molecular weight of grafted PAN and the grafting frequency rather than starch granule pretreatment might be the most important factor which influences properties.
    Additional Material: 4 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 24 (1979), S. 2031-2040 
    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: A series of gels differing in ionic content was prepared by derivatizing starch with varying amounts of carboxymethyl add-on. Some derivatives were lightly crosslinked with epichlorohydrin to reduce soluble material and increase the amount of gel. The gel fraction of each batch was isolated, and viscosity η, shear modulus G, and swelling in water and salt solution were then determined. One gel suspension, examined in more detail, was demonstrated to behave as a closely packed gel thickening agent, thereby warranting use of the three reduced functions: reduced concentration cQ (c is weight concentration of polymer, Q is swelling capacity in excess fluid), η/cQ, and G/c1/3. At cQ greater than about 2, η/cQ, and G/c1/3 reach constant plateau values, as is typical of other examples of closely packed gel thickeners. In a comparison among the gel suspensions, plateau values of the reduced viscosity function were nearly proportional to the apparent crosslink density G/c1/3, in agreement with other closely packed gel thickeners, but were not affected by ionic content of dry polymer. The water swelling capacities of the different gels ranged from 47 to 150 g/g and were correlated with both ionic contents and apparent crosslink densities, but the effects of these variables were less than suggested by theory.
    Additional Material: 4 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 27 (1982), S. 4377-4386 
    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: Rheological properties and swelling were examined in a series of concentrations of particles of crosslinked polyacrylate gels in water or salt solutions. The modulus during steady shear Gs = 2τ2/P11-P22 was determined from shear stress τ and primary normal force difference P11-P22 in a cone-and-plate rheometer. Gs was nearly constant with shear rate for the gel particles in the closely packed condition. The dynamic storage modulus G′ determined by ecentric rotating disc rheometry increased with increasing frequency for all concentrations. The apparent equilibrium shear modulus Ge determined by stress relaxation agreed closely at all concentrations and ionic strengths with the corresponding values of Gs, and hence Gs is considered a good estimate of equilibrium shear modulus for this gel material.
    Additional Material: 9 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 23 (1979), S. 1897-1900 
    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
    Additional Material: 5 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 11 (1972), S. 2591-2600 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: X-ray investigation of a crystalline complex between dimethyl sulfoxide (DMSO) and amylose indicates a sevenfold helical structure having an orthogonal unit cell: a = 30.23 Å, b = 28.18 Å, and C = 7.91 Å (helix axis). This helical amylose results from precipitation of amylose in DMSO solutions under suitably dry conditions using toluene as a precipitating agent. Analyses show a molar ratio of 0.95:2:0.4:0.08 for DMSO, amylose glucose units, water, and toluene, respectively. DMSO and amylose combine in at least two crystalline conformations, sixfold and sevenfold helices. The amount of water present influences the resulting conformation. The existence of the sevenfold helical solid indicates that the amylose sevenfold helix has greater stability than previously recognized by conformational energy calculations. In general, potential energy calculations cannot be correct that ignore the influence of guest molecules and their effects upon the maltose residue conformation and that lead to a sixfold helix as the most probable structure.
    Additional Material: 1 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1133-1144 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A centrifugal technique was used to determine the swelling, Q (g swollen gel/g dry polymer), of crosslinked polyacrylate gel particles in water. Both centrifugal force and time of centrifugation affected the magnitude of Q but under constant centrifuge conditions it was found that Q-1 was proportional to μ1/2, μ being the ionic strength. The viscoelastic properties of water dispersions of these gel particles were measured as functions of concentration and ionic strength. Viscosity data were reducible to a normalized master curve by plotting (ηsp/cr) versus cr, where cr is a reduced concentration defined as cQ. Values of shear modulus, G, computed from the first normal stress difference measured at various concentrations and ionic strengths also fell on a single curve when plotted against the reduced concentration, cQ. Comparison of these results with those obtained earlier on a similar polyacrylate dispersion, but one in which as much as 20% of the polyacrylate is in a soluble, uncrosslinked form, shows that the soluble fraction has little effect on the magnitude of the viscosity and, moreover, that the presence or absence of the soluble fraction does not affect the transient stress overshoot phenomenon. As in the earlier work, high absolute values of viscosity occur when cQ ≧ 1, that is when the dispersion consists of close-packed deformable gel particles in intimate contact with little or no interstitial solvent present.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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