Mechanistic study on demulsification of water-in-diluted bitumen emulsions by ethylcellulose.

In our previous study, ethylcellulose (EC), an effective, nontoxic, and biodegradable natural polymer, was found effective in dewatering water-in-diluted bitumen emulsions. In this study, the demulsification mechanism of water-in-diluted bitumen emulsions by EC is investigated. In situ experiments using a micropipet apparatus provided direct evidence on both flocculation and coalescence of water droplets in diluted bitumen by EC. The addition of EC was found to decrease naphtha-diluted bitumen-water interfacial tension significantly. At the molecular level, AFM imaging revealed disruption of the continuous interfacial films formed from surface-active components of bitumen by EC. Our study clearly indicates that the demulsification by EC is through both flocculation and coalescence of water droplets, attained by competitive adsorption of EC at the oil-water interface and disruption of the original protective interfacial films formed from the surface-active components of bitumen.

Adhesion of colloidal polyelectrolyte complexes to wet cellulose.

The adhesion of wet regenerated cellulose to colloidal complexes formed between carboxymethyl cellulose (CMC) and polyvinylamine (PVAm) was evaluated by measuring the force to delaminate pairs of regenerated cellulose membranes bound together with polyelectrolyte complex. The most important parameter was the surface composition of the colloidal complex particles. High delamination forces corresponded to using complexes coated with excess PVAm whereas low adhesion was observed for both CMC coated complexes and complexes in which the PVAm was replaced with polymer bearing quaternary amine groups. Adhesion with complexes was highest at pH 4 and rather insensitive to pH from 6 to 9. Finally, mild TEMPO/NaBr/NaClO oxidation of the cellulose gave much stronger adhesion when PVAm was in excess but not with the CMC rich complexes.

Colloidal complexes from poly(vinyl amine) and carboxymethyl cellulose mixtures.

The phase behaviors of polyelectrolyte complexes formed from dilute solutions of poly(vinyl amine) (PVAm) and carboxymethyl cellulose (CMC) were determined as a function of overall composition and pH. The phase diagram included regions with soluble complexes, colloidal complexes, and macroscopic precipitates. Colloidal complexes were stable when either polymer was in sufficient excess to give electrosteric stabilization. The polymer mixing ratios giving complexes with an isoelectric point of 7 could be predicted from a simple model using the degree of ionization vs pH data for PVAm and CMC. The model failed at extreme pH values because not all added polymer was incorporated into the complexes. At pH 7, essentially all the added polymer was incorporated into the colloidal complex or precipitate, as long as the mixing ratio was within +/-10% of charge stoichiometry. The interaction of PVAm and CMC at pH 7 was endothermic, supporting the generally accepted viewpoint that the interaction of oppositely charged polyelectrolytes is entropy-driven. Although the colloidal complexes had a broad particle size distribution, the average particle size was rather insensitive to mixing ratio. By contrast, complex size was sensitive to electrolyte concentration with no complex formation when the NaCl concentration was > or =2 M.

Synthesis, properties and X-ray crystal structure of a new heteropolyacid supermolecular charge-transfer complex [(VB1)2DMFHPMo12O40.5DMF].

The title complex [(VB(1))(2)DMFHPMo(12)O(40).5DMF, VB(1) = vitamin B(1) (thiamine chloride), DMF = N,N-dimethylformamide] has been synthesized and characterized by elemental analysis, IR, UV-Vis, electron spin resonance, X-ray photoelectron spectroscopy and cyclic voltammetry methods. The X-ray crystal structure revealed that there is one independent molecule in the unit cell of the title complex that contains one mixed-valence heteropolyanion, two VB(1)(+) cations and six DMF molecules. The title complex possesses a centrosymmetrical arrangement in the unit cell, with the P atom at the symmetry center of the heteropolyanion and with eight O atoms surrounding the central P atom, such that two sets of PO(4) tetrahedra are formed. The PO(4) tetrahedra and MoO(6)(6-(7-)) octahedra are disordered in the heteropolyanion. The bond distances of P-O(a) and Mo=O(d) are in the ranges 1.57 (4)-1.70 (4) A and 1.61 (2)-1.67 (2) A, respectively.