The self-aggregation of polyelectrolytes having N-alkyl-N, N-dimethyl-N-(2-hydroxypropyl)ammonium chloride pendant groups (alkyl ) octyl, dodecyl, or cetyl) randomly distributed along a polysaccharide backbone (dextran) was studied by steady-state fluorescence techniques using several free fluorescent probes or pyrenelabeled polymers and by viscometry. The onset, offset, and highest values of the fluorescence response of N-phenylnaphthylamine (NPN), pyrene (Py), and 1,6-diphenyl-3,5,6-hexatriene (DPH) were corroborated with NPN and DPH anisotropy and quenching experiments to describe the dynamic of hydrophobic microdomain formation and microdomain characteristics. The start of the aggregation process (critical aggregation concentration, cac) and the microdomain characteristics such as polarity, microviscosity, size, and number strongly depend on the alkyl chain length and the degree of substitution with cationic pendant groups. Fluorescence experiments with pyrene-labeled polymers and viscosity data suggest that microdomains are mainly formed by intramolecular hydrophobic associations, except for the polymers carrying octyl groups, where some intermolecular associations were revealed.
The interfacial behavior of poly(isoprene-b-methyl methacrylate) diblock copolymers (PI-b-PMMA), with similar PMMA blocks but differing in the percentage of PI segments, SP19 (5% PI) and SP38 (52% PI), was studied at the air-water interface. The surface pressure-area (pi-A) isotherms, compression-expansion cycles, and relaxation curves were compared with those of the PMMA homopolymer. The short hydrophobic PI block of SP19 does not contribute to the mean molecular area at low surface pressures and yet has a negative contribution (condensing effect) when the surface pressure increases. On the contrary, the long PI block of SP38 contributes considerably to the surface area from low to high surface pressures. The A-t relaxation curves compare well with those of PMMA at low surface pressures (pi = 2 mN.m-1), but not at intermediate and high pressures (pi = 10, 30 mN.m-1), where a clear dependence on the length of the PI block was observed. The quantitative analysis of the relaxation curves at high pressures shows both a fast and slow component, attributed mostly to the local and middle-to-long-range reorganization of PMMA chains, respectively. PI-b-PMMA diblocks and PMMA were further blended with PS. The PS and PMMA are immiscible at the air-water interface. The addition of PS does not change the pi-A isotherm of PMMA, but the copolymers blended with PS form films that are more condensed at low pressures. The Langmuir-Blodgett (LB) films transferred onto mica substrates were analyzed by atomic force microscopy (AFM). The LB films of single diblocks are uniform, while those of PI-b-PMMA and PMMA blended with PS show aggregates with variable patterns.
Biomass retention, required for high rate anaerobic wastewater treatment, can be accomplished coupling an anaerobic bioreactor with membrane filtration. However, low flux seems to be a common factor when operating anaerobic membrane bioreactors (AnMBRs). Modification of biomass properties may represent a strategy for improving membrane flux. The addition of flocculants was tested as a tool for flux increase. Six different products were tested in dead-end filtration experiments. Based on the results, two products were selected for cross-flow tests. The one presenting better performance (Nalco MPE50) was tested in a laboratory-scale continuous AnMBR. Results show that the flocculant was able to substantially increase flux. Indeed, the flux-increasing effect was observed for several weeks after flocculant addition. Therefore, the use of flocculants seems to be an interesting tool to cope with temporary increases in required flux.
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