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  • 1
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The small-angle x-ray scattering (SAXS) technique has been applied to investigate solution and gel structures of alginate in the absence and presence of two divalent cations: Ca(II) and Cu(II). We have observed a broad maximum in the scattering curve, a characteristic of polyelectrolyte, for the purified alginate sample. The scattering maximum disappears in excess of added simple salt and shifts toward the higher angle region with increasing alginate concentration. Concentration dependence of the position and intensity of the maximum follows power law relations with exponents close to those predicted by theory. Data analysis shows an increase in correlation length ξ and cross-sectional diameter d0, of polymer chains upon gelation and suggests that a dimeric structure is adopted in the junction zone, consistent with the “egg-box” model previously proposed. In the Ca(II)-alginate system, the molecular parameters ξ and d0 are found to have good correlation with the macroscopic properties of gelation, such as gel point determined by viscosity measurements. However, for the Cu(II)-alginate system there is no clearly transitional behavior observed in ξ and d0, implying that the junction zone may be replaced by a more uniformly distributed site binding of Cu(II) ions to the carboxyl groups of both mannuronate and guluronate residues, in confirmation of previous 13C-nmr results. © 1995 John Wiley & Sons, Inc.
    Additional Material: 14 Ill.
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  • 2
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 13C-NMR spectroscopic studies have been made on alginate solutions undergoing sol-gel transition induced by four different divalent cations: Ca, Cu, Co, and Mn. From the analysis of nmr spectra and relaxation times, we have found different interaction modes existing between the Ca-alginate systems and the transition metal (Cu, Co, and Mn)-alginate systems. In the Ca-alginate systems, there exists a specific interaction characterized by a strong autocooperative binding between guluronate residues and calcium ions, and all functional groups in guluronate residues are considered to involve the interaction with calcium ions. On the other hand, in transition metal (Cu, Co, and Mn)-alginate systems, sol-gel transition is characterized by a complex formation in which the carboxyl groups in both mannuronate and guluronate residues are coordinated to metal ions. The other functional groups, like hydroxyl groups, do not participate in the binding to metal ions. It is suggested by relaxation time measurements that from a microscopic point of view the sol-gel transition phenomena can be explained as a dynamic process in which the low frequency molecular motions are dominant and increase their proportions with the formation of three-dimensional cross-links. © 1993 John Wiley & Sons, Inc.
    Additional Material: 7 Ill.
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  • 3
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Several rheological properties of aqueous alginate solution have been investigated in the absence and presence of four divalent cations: Ca, Cu, Mn, and Co. The concentration dependence of viscosity in alginate solution without addition of divalent cations shows a similar behavior to that found for other polysaccharides and synthetic polymers. We have found that for Ca(II) -added systems, sol-gel transition curves for different alginate concentrations can be superimposed over the concentration range of this study by using a normalized parameter. Shear-thinning behavior has been observed for all the alginate solutions by addition of four divalent cations over sol-gel transition process. The values of exponent b in the power-law relation \documentclass{article}\pagestyle{empty}\begin{document}$ {\eta \propto \dot \gamma }$\end{document} were found in the range of -0.3 ∼ -0.6. It is suggested that a considerable portion of divalent cations remains in a cross-linking state even under shear flow. The results obtained from thixotropy measurements indicate the existence of a major framework formed in the gel-like and well-gelled samples, which can be maintained until shear rate (or shear stress) reaches a threshold value. © 1994 John Wiley & Sons, Inc.
    Additional Material: 15 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 31 (1993), S. 461-466 
    ISSN: 0887-6266
    Keywords: polymer blend ; phase separation ; spinodal decomposition ; nonlinearity ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Suzuki's scaling theory for transient phenomena is applied to the calculation of the kinetics of phase separation in the early-to-intermediate stage based on a nonlinear theory proposed by Langer, Bar-on, and Miller (LBM). Calculated results are compared with experimental data on light scattering from a polymer blend system. Deviations from predictions of Cahn's linearized theory in the early time range of phase separation can be explained well by the proposed method of calculation. Nonlinear effects are found to play an essential role in characterizing the light scattering behavior of phase separation in the intermediate stage. Time evolutions of the single-point distribution function of composition are calculated, and the results are in good agreement with those reported in digital imaging analysis experiments and computer simulations of the time-dependent Ginzburg-Landau equation. The influence of asymmetry of free-energy on the single-point distribution function is also investigated in this study. © 1993 John Wiley & Sons, Inc.
    Additional Material: 7 Ill.
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