The temperature-dependence of xyloglucan (XG) adsorption onto smooth cellulose model films regenerated from N-methylmorpholine N-oxide (NMMO) was investigated using surface plasmon resonance spectroscopy, and it was found that the adsorbed amount increased with increasing temperature. This implies that the adsorption of XG to NMMO-regenerated cellulose is endothermic and supports the hypothesis that the adsorption of XG onto cellulose is an entropy-driven process. We suggest that XG adsorption is mainly driven by the release of water molecules from the highly hydrated cellulose surfaces and from the XG molecules, rather than through hydrogen bonding and van der Waals forces as previously suggested. To test this hypothesis, the adsorption of XG onto cellulose was studied using cellulose films with different morphologies prepared from cellulose nanocrystals (CNC), semicrystalline NMMO-regenerated cellulose, and amorphous cellulose regenerated from lithium chloride/dimethylacetamide. The total amount of high molecular weight xyloglucan (XGHMW) adsorbed was studied by quartz crystal microbalance and reflectometry measurements, and it was found that the adsorption was greatest on the amorphous cellulose followed by the CNC and NMMO-regenerated cellulose films. There was a significant correlation between the cellulose dry film thickness and the adsorbed XG amount, indicating that XG penetrated into the films. There was also a correlation between the swelling of the films and the adsorbed amounts and conformation of XG, which further strengthened the conclusion that the water content and the subsequent release of the water upon adsorption are important components of the adsorption process.
Hyperbranched polymers (polyesteramides) were used as a cationic fixing agent to remove dissolved and colloidal substances (DCS) from the water phase in a fiber suspension. The relative turbidity, electrophoretic mobility, and average diameter of the colloidal particles were determined as a function of polyelectrolyte concentration. The results indicated that maximum removal of DCS was achieved at about zero electrophoretic mobility of the suspension where the negative surface charges of particles were neutralized by the oppositely charged hyperbranched polymer. The amount of hyperbranched polymers needed to maximize DCS fixation on the fibers was higher than the amount of poly-DADMAC (diallyldimethylammonium chloride) needed to reach the same effect. This was found to be due to the lower molecular weight and lower charge density of hyperbranched polymers. The lower molecular mass allowed penetration of these polymers into pores of fibers that resulted in higher polymer consumption before removal of the dissolved and colloidal substances from the fiber suspensions. A lower charge density further resulted in a higher saturation adsorption of the hyperbranched polymer. Experiments with both DCS and model-latex particles showed that the initial increase in relative turbidity was due to the aggregation of particles before fixation to fibers. The results from quartz crystal microbalance with dissipation (QCM-D) experiments showed that the efficiency of hyperbranched polymer and poly-DADMAC was similar even if they had different structure. Therefore, this study highlights the importance of molecular mass and charge density of the polymers as well as the surface structure of polymer layers which in turn gives implications for development of new structures of fixing agents.
ABSTRACT:The water soluble cationic microgels (CMG), intramolecularly cross-linked cationic polymers of acrylamide (Am) and diallyldimethylammonium chloride (DADMAC), were synthesized with dispersion polymerization in the mixture of tert-butanol (TBA)/water in the presence N,N 0 -methylene-bisacrylamide (MBA) as the cross-linker, poly(N-vinylpyrrolidone (PVP) as the stabilizer and 2,2 0 -azobisisobutyronitrile (AIBN) as the initiator. The effects of monomer, cross-linker, initiator, and stabilizer concentration on both particle size and molecular weight of CMG were investigated. The well dispersed polymer particles were produced in the range of poly dispersity index 1.1-1.4 and the molecular weight distribution with bimodal. Additionally, the efficiencies of two CMGs in the clay deposition on the bleached kraft fibers were investigated and compared with commercially widely used cationic polyacrylamide (CPAM) and poly-diallyldimethylammonium chloride (poly-DADMAC). The experiments showed that the CMGs were found as the effective flocculation agents and their efficiencies depended on their molecular weight and charge density.
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