ABSTRACT
Forming membranes by tangential flow deposition of cellulose nanocrystal (CNC) suspensions is an attractive new approach to bottom-up membrane fabrication, providing control of separation performance using shear rate and ionic strength. Previously, the stabilization of these membranes was achieved by irreversibly coagulating the deposited layer upon the permeation of a high-ionic-strength salt solution. Here, we demonstrate for the first time the chemical cross-linking of carboxyl-containing TEMPO-oxidized CNCs by Ag(I)-catalyzed oxidative decarboxylation and the stabilization of CNC membranes using this post-treatment. Cross-linking of TEMPO-CNCs was first demonstrated in suspension via turbidity, dynamic light scattering, and storage (G') and loss (Gâ³) moduli measurements. Membranes were formed by filtering a 0.15 wt % TEMPO-CNC suspension onto a porous support, followed by permeation of the cross-linking solution containing AgNO3 and KPS through the deposited layer. Rejection for Blue Dextran with a 5 kDa molecular weight was 95.3 ± 1.9%, 90.6 ± 3.7%, and 95.9 ± 1.0% for membranes made from suspensions of TEMPO-CNC, desulfated TEMPO-CNC. and TEMPO-CNC with 100 mM NaCl, respectively. Suspensions with added NaCl led to membranes with improved stability and cholesteric self-assembly in the membrane layer. Membranes subjected to cross-linking post-treatment remained intact upon drying, while those stabilized physically using 200 mM AlCl3 solution were cracked, demonstrating the advantage of the cross-linking approach for scale-up, which requires drying of the membranes for module preparation and storage.
ABSTRACT
Cellulose nanocrystals (CNCs) of 180 nm length and 8 nm diameter were deposited on porous supports by tangential flow filtration followed by salt permeation to form ultrafiltration membranes. At a high enough shear rate on the support surface, CNCs aligned in the direction of flow, showing a nematic order. The shear rates for transition to the nematic phase determined from rheology analysis, polarized optical microscopy, and membrane performance were consistent with one another, at ca. 10 s-1. Permeating an AlCl3 solution through the shear-aligned CNC deposit stabilized the CNC layer by screening repulsive electrostatic interactions, and the stable CNC layer was obtained. On changing the surface shear rate from 10 to 50 s-1, the order parameter of CNCs increased from 0.17 to 0.7 and the rejection for Blue Dextran (5 kDa) increased from 80.4 to 92.7% and that for ß-lactoglobulin (18 kDa) increased from 89.6 to 95.4%. Hence, a simple and scalable method for controlling rejection properties of ultrafiltration membranes is developed, which uses aqueous CNC suspensions to form the selective layer.
ABSTRACT
In this study, we show that codeposition of temperature responsive microgels in the foulant cake layer and cleaning of the cake upon stimuli-induced size change of the microgels is an effective method of fouling removal. Humic acid in CaCl2 solution was used as a model foulant and poly( n-isopropylacrylamide) (p(NIPAm)) and poly( n-isopropylacrylamide- co-sulfobetainemethacrylate) (p(NIPAm- co-SBMA)) were used as temperature responsive microgels. Filtrations were done below the lower critical solution temperature (LCST) and temperature was increased to above the LCST for cleaning. As an extra cleaning a temperature swing of above, below and then again above the LCST was applied. P(NIPAm) was found to be ineffective in cleaning the foulant deposit despite the 20-fold change in its volume with temperature change at LCST. P(NIPAm- co-SBMA) microgels, on the other hand, provided high fouling reversibility on hydrophilic poly(ether sulfone)(PES)/poly(vinylpyrrolidone) (PVP) and hydrophobic PES membranes. Better fouling reversibility with these microgels was observed at low and high solution ionic strength. While the use of microgels alone increased fouling reversibility to some extent, even in the absence of temperature stimulus, 100% reversibility could only be obtained when a temperature switch was applied in the presence of microgels, showing the effect of microgels' volume change in cleaning.
