title: Structural and rheological properties of hydrophobically modified polysaccharide associative networks.
abstract: The phase behavior of hydrophobically modified chitosans (HMCs) in aqueous solution has been investigated using scattering and rheology experiments. We observed four regions on the phase diagram of the associative polymer: (i) a supernatant phase (unimers phase) at low polymer concentration; (ii) a dilute solution of intermolecularly bridged flowerlike micelles at intermediate concentration; (iii) an associative gel phase at high polymer content; and (iv) a phase separation. In the present paper, we discuss the structural and dynamical properties of the HMC associative networks (c > c*) at a fixed hydrophobic degree of substitution of 2% and fixed alkyl side chains (stickers) length C8 (domains iii and iv of the phase diagram). As the polymer concentration is increasing, a connecting network is formed from the percolation of bridges between micellar aggregates. In this regime, small-angle neutron scattering and light scattering measurements show that -50-nm flower aggregates are acting like junction points in the network. The effect of the concentration, the stress, and the shear on the structure of the network is discussed. In particular, we observe bridge-to-loop transitions and then the formation of microgels or a low-connected network under shear. Therefore, our results are compared to recent theoretical models and to the results reported for telechelic systems.
authors.affiliation: Centre de Recherches sur les Macromolécules Végétales, UPR-CNRS 5301, University Joseph Fourier, BP 53, 38041 Grenoble, France.
authors.forename: Catherine
authors.initials: C
authors.lastname: Esquenet
authors.forename: Pierre
authors.initials: P
authors.lastname: Terech
authors.forename: François
authors.initials: F
authors.lastname: Boué
authors.forename: Eric
authors.initials: E
authors.lastname: Buhler
mesh_terms: D057927:Hydrophobic and Hydrophilic Interactions; D044367:Phase Transition; D011134:Polysaccharides / Q000737:chemistry*; D012212:Rheology; D012996:Solutions; D013050:Spectrometry, Fluorescence; D014783:Viscosity
chemical_list: D011134:Polysaccharides; D012996:Solutions