Integrated enzyme hydrolysis assisted cellulose nanofibril (CNF) fabrication: A sustainable approach to paper mill sludge (PMS) management.

The landfilling of paper mill sludge (PMS) has been restricted or even banned in many countries due to the raised concern about greenhouse gas (GHG) emissions and contamination of the soil and water, calling for a sustainable PMS management approach. The potential valorization of PMS to nanomaterials combined with traditional biorefinery was examined in this work. Three types of PMS-derived cellulose nanofibrils (CNFs) were prepared and evaluated: enzymatically assisted CNF (AU: with in-house produced enzyme and CT: with commercial enzyme), mechanically pretreated CNF (BT), and chemically pretreated CNF by TEMPO oxidation (TEMPO). It was found that enzyme-assisted mechanical fibrillation-derived CNFs had a comparable average diameter (27.9 nm for AU and 22.7 nm for CT) with that produced from mechanical pretreatment (26.5 nm for BT) and TEMPO oxidation pretreatment (20.0 nm for TEMPO), and they showed the best drainage properties among the three types of CNF. The CNFs resulting from enzymatic pretreatment reduced 15% of energy consumption compared to the mechanical method and had better thermostability than TEMPO oxidation method. In addition, the on-site produced enzyme showed similar performance to the commercial enzymes towards the CNF properties. These findings provide new insights into a promising integrated strategy in engineering CNF from PMS with on-site enzyme production as a novel and sustainable approach for PMS management and valorization.

Engineering cellulose nanopaper with water resistant, antibacterial, and improved barrier properties by impregnation of chitosan and the followed halogenation.

This work demonstrated a facile and sustainable approach to functionalize cellulose nanopaper (CNP) by impregnation of chitosan (CS) and the followed halogenation. It was found that the tensile strength of the functionalized CNP (CNP/CS-Cl) was enhanced by 38.3% and 512.6% at dry and wet conditions, respectively. Meanwhile, the total transmittance (at 550 nm) of CNP/CS-Cl was increased from 75% of pure CNP to 85%, with 35% decrease in optical haze. Moreover, the CNP/CS-Cl exhibited significant enhancement in barrier properties. Importantly, part of the amino groups on CS were transformed into N-halamines during the halogenation process, which endowed the CNP/CS-Cl with excellent antibacterial performance against both S. aureus and E. coli with 100% bacterial reduction after 10 min of contact. Thus, this work provides a simple and efficient approach to functionalize CNP with water resistance, high transparency, excellent antibacterial and barrier properties, which will expand the potential applications of CNP.

Multifunctional Cellulose Nanopaper with Superior Water-Resistant, Conductive, and Antibacterial Properties Functionalized with Chitosan and Polypyrrole.

Cellulose nanopaper (CNP) has been considered as a promising material with great application potential in diverse fields. However, the hydrophilic nature of CNP significantly limits its practical application. In order to improve its water resistance, we demonstrate a facile approach to functionalize CNP by impregnating it with chitosan (CS), followed by in situ polymerization of polypyrrole (PPy). The results indicate that the obtained CNP/CS/PPy shows excellent water resistance with the wet tensile strength of up to 80 MPa, which is more than 10 times higher than that of the pure CNP. Intriguingly, new features (e.g., electrical conductivity, antibacterial activity, and so forth) are achieved at the same time. The functionalized CNP/CS/PPy shows a high conductivity of 6.5 S cm-1, which can be used for electromagnetic interference shielding applications with a high shielding performance of around 18 dB. In addition, the CNP/CS/PPy exhibits good antibacterial activity toward Staphylococcus aureus and Escherichia coli, with the bacterial reductions of 99.28 and 95.59%, respectively. Thus, this work provides a simple and versatile approach to functionalize CNP for achieving multifunctional properties.

Effects of Non-covalent Functionalization and Initial Mixing Methods on SWNT/PP and SWNT/EVOH Composites.

We report that a simple, low-cost type of spray-freeze drying (SFD) significantly improves the dispersion of single-walled carbon nanotubes (SWNTs) in thermoplastic polymers. Conventional SFD requires costly specialized equipment and large amounts of material, both of which are impediments to laboratory research on nanomaterial composites. Our method uses more readily available equipment and can be adapted to use milligrams to grams of material. A household spray bottle containing an aqueous nanomaterial dispersion is used to spray the dispersion into a dish of liquid nitrogen. The resulting material is then lyophilized in a standard laboratory freeze dryer. The usefulness of this simplified method was explored by comparing the properties of polypropylene (PP) composites produced by this method to those produced by a previously reported rotary evaporation method in which the dispersion is vacuum-dried onto the polymer. The role of the initial dispersion state was explored by using pristine SWNTs as well as SWNTs stabilized by two common SWNT stabilizers: polyvinylpyrrolidone (PVP) and sodium dodecyl sulfate. Based on rheological, thermal, and morphological characterization, the porous friable structures produced by SFD resulted in better SWNT dispersion compared to composites produced by a previously reported rotary evaporation method. However, the PP/PVP-SWNT nanocomposites produced by both methods contained large aggregates. To verify that this aggregation behavior was the result of thermodynamic incompatibility between PP and PVP, ethylene vinyl alcohol (EVOH) nanocomposites containing PVP-SWNT were also produced using the SFD method. The results of this research show how a low-cost alternative to SFD along with careful consideration of compatibility is a promising approach to produce nanocomposites.

Towards lignin derived thermoplastic polymers.

Lignin is the second most abundant biobased material found on earth. It is produced mainly as a byproduct of pulp and paper industry and biorefineries. Despite its abundance, lignin valorization is not achieved on a large scale. Recently, there has been a growing demand for using the renewable and biodegradable raw materials in the commodity polymers. Potential use of lignin as a component in thermoplastic polymers is a promising approach for its value-added utilization. Given the vast applications of thermoplastic materials, there is lack of comprehensive review on lignin based thermoplastic polymers in literature. This review focuses on the utilization of lignin as functional and structural component of the thermoplastic polymers which requires structural modifications of lignin pertaining to the polymeric system. First, various lignin modifications were discussed in view of controlling the homogeneity, reactivity, processability and compatibility of lignin for successful thermoplastic copolymer synthesis and blend processing. Then, various copolymerization methodologies of lignin applicable for thermoplastic monomers are reviewed. Lastly, the lignin based thermoplastic blends are discussed which covers the lignin blends with various thermoplastic polymers and the chemical modifications required to improve its compatibility in polymer matrix. Some of the promising potential applications and future perspectives to achieve the goal of lignin-based commercial thermoplastics polymers are addressed.

Polypyrrole and cellulose nanofiber based composite films with improved physical and electrical properties for electromagnetic shielding applications.

Polypyrrole (PPy) and cellulose nanofiber (CNF) based conducting composite films were synthesized using two new approaches, in-situ polymerization of pyrrole onto cellulose nanopaper (PPy/CNP) and polyvinyl alcohol coated cellulose nanopaper (PPy/PVA-CNP). Significant improvement in the conductivity, tensile strength, water resistance, and electromagnetic shielding effectiveness (SE) was observed for these composite films compared to commonly used in-situ nanofiber (ISF) approach, where PPy is coated on nanofibers prior to film preparation. Maximum improvement in conductivity, SE and tensile strength of PPy/PVA-CNP compared to ISF films was attributed to highly uniform and compact PPy coating and reduced porosity. SE of -23 dB (thickness upto 138.4 µm) and tensile strength of 103.8 MPa for PPy/PVA-CNP films are the highest values found in the literature for PPy and CNF based composite films at a comparable thickness. These new approaches could enable a scalable preparation of flexible conducting composite films with superior physical and electrical properties for EMI shielding applications.

Sustainable valorization of paper mill sludge into cellulose nanofibrils and cellulose nanopaper.

As a kind of agro-industrial wastes, paper mill sludge (PMS) has posed serious environmental and economic challenges for disposal due to the more stringent regulations and diminishing land availability in recent years. The present study is aimed at providing a sustainable approach to efficiently convert PMS to cellulose nanofibrils (CNFs) and cellulose nanopaper (CNP) by formic acid (FA) hydrolysis pretreatment and the followed microfluidization. It is found that FA hydrolysis (4-6 h) could swell and shorten PMS fibers, and only two-pass microfluidization is sufficient to get uniform CNFs from the collected cellulose residual. Results indicate that the obtained CNFs show high thermal stability and crystallinity index, surface functionality (ester groups), as well as a high yield of over 75 wt.%. Notably, more than 90 % FA can be recovered and the hydrolyzed sugars could be potentially used to produce platform chemicals (e.g. lactic acid, furfural). Finally, transparent CNP is prepared from the CNFs suspension via a simple vacuum filtration technique. The resultant CNP shows good mechanical properties with the maximum tensile strength and toughness of 106.4 MPa and 6.62 MJ/m3, respectively. Therefore, the current work provides a green and sustainable method to valorize PMS for the production of valuable CNFs and CNP.

Transparent and Homogenous Cellulose Nanocrystal/Lignin UV-Protection Films.

In the context of valorization of lignin produced from the pulp and paper industries, biodegradable UV-protection films were prepared using lignin and cellulose nanocrystals (CNCs). Initially, CNC films were optimized for improving their transparency by studying the effect of various sodium hydroxide (NaOH) concentrations. Maximum (%) transmittance of CNC film was obtained for NaOH addition between 3 and 4 wt %. The optimized CNC suspensions were used for incorporating alkaline lignin (AL) and softwood kraft lignin (SKL) in various concentrations (1-10 wt %). Morphological characterization showed homogeneity of the lignin distribution in CNC/lignin films. Complete UV blocking was achieved at 10 wt % lignin (AL or SKL) in CNC films. Cross-polarized optical microscopy and scanning electron microscopic images of films showed some degrees of global alignment of CNC rods upon addition of NaOH, which remained unaffected by lignin addition. Lignin modification through acetylation reduced the lignin color and improved visible light transmission of films without significantly affecting the UV-absorption properties. Presence of lignin also enhanced the thermal and contact angle stability of the films. This work shows for the first time that CNC aqueous suspensions with and without containing lignin could be tuned through the addition of NaOH to produce transparent and homogenous films, providing a simple and green approach in engineering CNC/lignin UV-protection films.