Nanofibrillated Cellulose Templated Membranes with High Permeance.

One of the most challenging aspects of using nanofibrillated cellulose (NFC) for membranes production is their limited permeance. When NFC membranes are produced from aqueous suspensions, depending on their grammage, the permeances are in the range of a few decades of L/(hm2MPa) not matching satisfactory filtration times. We present a fast and sustainable solution to increase the permeances of such membranes through a combination of solvent exchange of the NFC suspension with ethanol and the use of a removable template, a mixture of calcium compounds (CC). The effect of the CC/NFC ratio was screened for various concentrations. The permeance of water could be increased by as much as 2-3 times as compared to nontemplated membranes. Further, the membranes showed the ability for penetration of water-soluble macromolecules, contaminant rejection of suspended solid particles, and thus fluids (such as orange juice) could be concentrated, with a view to applications in food industry.

Effect of Surface Charge on Surface-Initiated Atom Transfer Radical Polymerization from Cellulose Nanocrystals in Aqueous Media.

Cellulose nanocrystals (CNCs) with different charge densities were utilized to examine the role of electrostatic interactions on surface-initiated atom transfer radical polymerization (SI-ATRP) in aqueous media. To this end, growth of hydrophilic uncharged poly(N,N-dimethylacrylamide) (PDMAM) brushes was monitored by electrophoresis, (1)H NMR spectroscopy, and dynamic light scattering (DLS). Molecular weight and polydispersity of PDMAM brushes was determined by GPC analysis of hydrolytically cleaved polymers. Initiator and polymer brush grafting densities, and thus, initiator efficiencies were derived from elemental analysis. Higher initiator efficiency of polymer brush growth was observed for CNCs with higher anionic surface sulfate half-ester group density, but at the expense of high polydispersity caused by inefficient deactivation. PDMAM grafts with number-average molecular weights up to 530 kDa and polydispersity indices <1.5 were obtained under highly diluted monomer concentrations. The role of surface chemistry on the growth of neutral polymer brushes from CNCs in water is emphasized and a model of the interfacial region at the onset of polymerization is proposed. The results presented here could have implications for other substrates that present surface charges and for the assumption that the kinetics of Cu-mediated SI-CRP are analogous to those conducted in solution.

Characterization of Pores in Dense Nanopapers and Nanofibrillated Cellulose Membranes: A Critical Assessment of Established Methods.

Nanofibrillated cellulose (NFC) is a natural fibrous material that can be readily processed into membranes. NFC membranes for fluid separation work in aqueous medium, thus in their swollen state. The present study is devoted to a critical investigation of porosity, pore volume, specific surface area, and pore size distribution of dry and wet NFC nanopapers, also known as membranes, with various established techniques, such as electron microscopy, helium pycnometry, mercury intrusion, gas adsorption (N2 and Kr), and thermoporometry. Although these techniques can be successfully applied to inorganic materials (e.g., mesoporous silica), it is necessary to appraise them for organic and hydrophilic products such as NFC membranes. This is due to different phenomena occurring at the materials interfaces with the probing fluids. Mercury intrusion and gas adsorption are often used for the characterization of porosity-related properties; nevertheless, both techniques characterize materials in the dry state. In parallel, thermoporometry was employed to monitor the structure changes upon swelling, and a water permeance test was run to show the accessibility of the membranes to fluids. For the first time, the methods were systematically screened, and we highlighted the need of uniform sample treatments prior to the measurements (i.e., sample cutting and outgassing protocols) in order to harmonize results from the literature. The need for revising the applicability range of mercury intrusion and the inappropriateness of nitrogen adsorption were pointed out. We finally present a table for selecting the most appropriate method to determine a desired property and propose guidelines for results interpretation from which future users could profit.