Andreas Mautner

Nanopapers for organic solvent nanofiltration

Would it not be nice to have an organic solvent nanofiltration membrane made from renewable resources that can be manufactured as simply as producing paper? Here the production of nanofiltration membranes made from nanocellulose by applying a papermaking process is demonstrated. Manufacture of the nanopapers was enabled by inducing flocculation of nanofibrils upon addition of trivalent ions.

Cationic cellulose nanofibers from waste pulp residues and their nitrate, fluoride, sulphate and phosphate adsorption properties.

Cationic cellulose nanofibers (CNF) having 3 different contents of positively charged quaternary ammonium groups have been prepared from waste pulp residues according to a water-based modification method involving first the etherification of the pulp with glycidyltrimethylammonium chloride followed by mechanical disintegration. The cationic nanofibers obtained were observed by scanning electron microscopy and the extent of the reaction was evaluated by conductometric titration, ζ-potential measurements, and thermogravimetric analyses. The cationic CNF had a maximum cationic charge content of 1.2mmolg(-1) and positive ζ-potential at various pH values. Sorption of negatively charged contaminants (fluoride, nitrate, phosphate and sulphate ions) and their selectivity onto cationic CNF have been evaluated. Maximum sorption of ∼0.6mmolg(-1) of these ions by CNF was achieved and selectivity adsorption studies showed that cationic CNF are more selective toward multivalent ions (PO4(3-) and SO4(2-)) than monovalent ions (F(-) and NO3(-)). In addition, we demonstrated that cationic CNF can be manufactured into permeable membranes capable of dynamic nitrate adsorption by utilizing a simple paper-making process.

Direct Interfacial Modification of Nanocellulose Films for Thermoresponsive Membrane Templates

This letter proposes a strategy to construct tunable films combining the physical characteristics of cellulose nanofibrils and smart polymers for membrane applications. A functional membrane template was obtained by first fabricating a water stable film from cellulose nanofibrils and subsequently surface grafting it with a thermoresponsive polymer, poly(N-isopropylacrylamide). The behavior of the membrane template was dependent on temperature. The increment in slope of relative water permeance around the lower critical solution temperature of poly(N-isopropylacrylamide) increased from 18 to 100% upon polymer attachment. Although the membrane template essentially consisted of wood-based materials, the benefits of smart synthetic polymers were achieved.

Nitrate removal from water using a nanopaper ion-exchanger

Nitrates seriously affect drinking water quality. We herein present a process for the efficient removal of nitrates from water using a nanopaper ion-exchanger, which can be operated in flow-through conditions. The nanopaper ion-exchanger was produced from nanofibrillated cellulose obtained from fibre sludge, a paper-production waste stream, using a simple paper-making process. The cellulose nanofibrils were modified with quaternary trimethylammonium groups. The performance of these cationic nanopaper ion-exchangers was assessed with respect to their permeance and nitrate adsorption. Nitrates could be successfully captured onto the cationic nanopaper and thus rejected from contaminated water during dynamic filtration experiments. The ion-exchange nanopaper had adsorption capacities in the range of commercial available adsorbers but with the advantage of reduced contact time.

Phosphorylated nanocellulose papers for copper adsorption from aqueous solutions

Copper is a major problem in industrial wastewater streams, seriously affecting the quality of potential drinking water. Several approaches, including continuous membrane processes or batch-wise application of adsorbents, are in use to tackle this problem. Unfortunately, these processes suffer from their particular drawbacks, such as low permeance or disposal of saturated adsorbents. However, a combination of these processes could constitute a step towards a more efficient copper removal solution. Here, we present a nanopaper ion-exchanger prepared from cellulose nanofibrils produced from fibre sludge, a paper industry waste stream, for the efficient, continuous removal of copper from aqueous solutions. This nanopaper ion-exchanger comprises phosphorylated cellulose nanofibrils that were processed into nanopapers by papermaking. The performance of these phosphorylated nanopaper membranes was determined with respect to their rejection of copper and permeance. It was shown that this new type of nanopaper is capable of rejecting copper ions during a filtration process by adsorption. Results suggest that functional groups on the surface of the nanopapers contribute to the adsorption of copper ions to a greater extent than phosphate groups within the bulk of the nanopaper. Moreover, we demonstrated that those nanopaper ion-exchangers could be regenerated and reused and that in the presence of calcium ions, the adsorption capacity for copper was only slightly reduced.

Noncovalent Surface Modification of Cellulose Nanopapers by Adsorption of Polymers from Aprotic Solvents

Basic adsorption of hydrophobic polymers from aprotic solvents was introduced as a platform technology to modify exclusively the surfaces of cellulose nanopapers. Dynamic vapor sorption demonstrated that the water vapor uptake ability of the nanopapers remained unperturbed, despite strong repellency to liquid water caused by the adsorbed hydrophobic polymer on the surface. This was enabled by the fact that the aprotic solvents used for adsorption did not swell the nanopaper unlike water that is generally applied as the adsorption medium in such systems. As case examples, the adsorptions of polystyrene (PS) and poly(trifluoroethylene) (PF3E) were followed by X-ray photoelectron spectroscopy and water contact angle measurements, backed up with morphological analysis by atomic force microscopy. The resulting nanopapers are useful in applications like moisture buffers where repellence to liquid water and ability for moisture sorption are desired qualities.

Better together: synergy in nanocellulose blends

Cellulose nanopapers have gained significant attention in recent years as large-scale reinforcement for high-loading cellulose nanocomposites, substrates for printed electronics and filter nanopapers for water treatment. The mechanical properties of nanopapers are of fundamental importance for all these applications. Cellulose nanopapers can simply be prepared by filtering a suspension of nanocellulose, followed by heat consolidation. It was already demonstrated that the mechanical properties of cellulose nanopapers can be tailored by the fineness of the fibrils used or by modifying nanocellulose fibrils for instance by polymer adsorption, but nanocellulose blends remain underexplored. In this work, we show that the mechanical and physical properties of cellulose nanopapers can be tuned by creating nanopapers from blends of various grades of nanocellulose, i.e. (mechanically refined) bacterial cellulose or cellulose nanofibrils extracted from never-dried bleached softwood pulp by chemical and mechanical pre-treatments. We found that nanopapers made from blends of two or three nanocellulose grades show synergistic effects resulting in improved stiffness, strength, ductility, toughness and physical properties. This article is part of a discussion meeting issue ‘New horizons for cellulose nanotechnology’.

Fully bio-based zwitterionic membranes with superior antifouling and antibacterial properties prepared via surface-initiated free-radical polymerization of poly(cysteine methacrylate)

This article proposes a strategy to prepare membranes that combine the network characteristics of micro/nanocellulose with grafted zwitterionic poly(cysteine methacrylate) (PCysMA) to develop fully bio-based membranes with antifouling properties. The surface characteristics of the membranes were studied, together with static adsorption of bovine serum albumin (BSA) and S. aureus for evaluating the antifouling properties of the membranes. Experimental data revealed a homogeneous modification that resulted in excellent antifouling properties with a reduction of 85% in biofilm formation and enhanced antimicrobial activity. Moreover, we introduced a novel method to determine the pore size of membranes in the wet-state and assess the antifouling performance in situ by synchrotron-based SAXS. This allowed us to observe in real-time the decrease in pore size upon adsorption of BSA during filtration, and how this phenomenon is strongly suppressed by grafting of PCysMA. The importance of this work lies in introducing a simple method to yield cellulosic membranes with superior antifouling properties, which could significantly increase their potential for water treatment applications.

Influence of relative humidity on the strength of hardwood and softwood pulp fibres and fibre to fibre joints

Cellulosic materials are highly sensitive towards environmental changes such as temperature and especially towards humidity. Besides morphological changes like swelling and/or shrinking, the mechanical properties of pulp fibres and fibre to fibre joints change as well. The current study sets to elucidate the changes and the extent to which elevated or decreased relative humidity (RH) influences the load bearing capacity of individual hardwood and softwood fibres and joints. The device used for the measurements is a micro bond tester with a custom-built humidity chamber in which the humidity can be controlled in a range from 25 to 95% RH. Individual fibres and joints have been tested at 30, 50 and 80% RH after equilibration time of 120 min. The breaking load of individual softwood fibres and joints displayed a maximum breaking load at 50% RH, with the values showing a decreasing trend towards higher or lower RH. In case of hardwoods, no change in the breaking load of either individual fibres or fibre to fibre joints has been observed at different RH.