Deaggregation of cellulose macrofibrils and its effect on bound water.

The purpose of this study was to determine how to control and measure the hierarchical swelling in pulp fibers via electrostatic interactions and localized osmotic pressure. A eutectic solvent system was used to systematically increase phosphate groups in the cell wall. Increase in fiber charge led to an increase in swelling properties, as expected. At a charge value around 180-200 µmol/g the macrofibrils were found to deaggregate. This led to a large jump in mesoscale swelling, from 0.9 to 2.5 mL/g, and surface area, from 400 to 1000 m2/g. This deaggregation was confirmed with X-ray scattering and solute exclusion. A novel thermoporosimetry method was used in the study. This involved splitting the nonfreezing water into two subfractions, thus allowing a more complete analysis of pore structure and surface area. The hydrated surface area for the samples was in the range 1200-1400 m2/g, which agreed well with simulations of aggregated microfibrils. Adding charge to the pulp fibers had a nonlinear effect on handsheet strength properties. This suggests that hierarchical control of fiber swelling may be a useful approach to improve important property pairs such as strength/density in packaging and other commercially important fiber products.

Mapping Nanocellulose- and Alginate-Based Photosynthetic Cell Factory Scaffolds: Interlinking Porosity, Wet Strength, and Gas Exchange.

To develop efficient solid-state photosynthetic cell factories for sustainable chemical production, we present an interdisciplinary experimental toolbox to investigate and interlink the structure, operative stability, and gas transfer properties of alginate- and nanocellulose-based hydrogel matrices with entrapped wild-type Synechocystis PCC 6803 cyanobacteria. We created a rheological map based on the mechanical performance of the hydrogel matrices. The results highlighted the importance of Ca2+-cross-linking and showed that nanocellulose matrices possess higher yield properties, and alginate matrices possess higher rest properties. We observed higher porosity for nanocellulose-based matrices in a water-swollen state via calorimetric thermoporosimetry and scanning electron microscopy imaging. Finally, by pioneering a gas flux analysis via membrane-inlet mass spectrometry for entrapped cells, we observed that the porosity and rigidity of the matrices are connected to their gas exchange rates over time. Overall, these findings link the dynamic properties of the life-sustaining matrix to the performance of the immobilized cells in tailored solid-state photosynthetic cell factories.

The Influence of Physical Mixing and Impregnation on the Physicochemical Properties of Pine Wood Activated Carbon Produced by One-Step ZnCl2 Activation.

In this study, two different sample preparation methods to synthesize activated carbon from pine wood were compared. The pine wood activated carbon was prepared by mixing ZnCl2 by physical mixing, i.e., "dry mixing" and impregnation, i.e., "wet mixing" before high temperature carbonization. The influence of these methods on the physicochemical properties of activated carbons was examined. The activated carbon was analyzed using nitrogen sorption (surface area, pore volume and pore size distribution), XPS, density, Raman spectroscopy, and electrochemistry. Physical mixing led to a slightly higher density carbon (1.83 g/cm3) than wet impregnation (1.78 g/cm3). Raman spectroscopy analysis also showed that impregnation led to activated carbon with a much higher degree of defects than physical mixing, i.e., ID/IG = 0.86 and 0.89, respectively. The wet impregnated samples also had better overall textural properties. For example, for samples activated with 1:1 ratio, the total pore volume was 0.664 vs. 0.637 cm3/g and the surface area was 1191 vs. 1263 m2/g for dry and wet mixed samples, respectively. In the electrochemical application, specifically in supercapacitors, impregnated samples showed a much better capacitance at low current densities, i.e., 247 vs. 146 F/g at the current density of 0.1 A/g. However, the physically mixed samples were more stable after 5000 cycles: 97.8% versus 94.4% capacitance retention for the wet impregnated samples.

Effect of enzymatic treatment on Eucalyptus globulus vessels passivation.

Hardwood vessel elements generate problems in industrial uncoated wood-free printing paper operation, causing vessel picking and ink refusal. These problems are mitigated using mechanical refining at the cost of paper quality. Vessel enzymatic passivation, altering its adhesion to the fiber network and reducing its hydrophobicity is a way of improving paper quality. The object of this paper is to study how the enzymatic treatment by xylanase and by an enzymatic cocktail containing cellulases and laccases affect elemental chlorine free bleached Eucalyptus globulus vessel and fiber porosities, bulk, and surface chemical compositions. Thermoporosimetry revealed the vessel structure to be more porous, surface analysis showed its lower O/C ratio and bulk chemistry analysis its higher hemicellulose content. Enzymes had different effects on porosity, bulk and surface composition of fibers and vessels, affecting vessel adhesion and hydrophobicity. Vessel picking count decreased 76% for papers containing vessels treated with xylanase and 94% for the papers with vessels treated with the enzymatic cocktail. Fiber sheet samples had lower water contact angle (54.1º) than vessels rich sheets (63.7º), that reduced with xylanase (62.1º) and cocktail (58.4º). It is proposed that differences in vessel and fiber porosity structures affect the enzymatic attacks, eventually causing vessel passivation.

Biological activity of multicomponent bio-hydrogels loaded with tragacanth gum.

Producing hydrogels capable of mimicking the biomechanics of soft tissue remains a challenge. We explore the potential of plant-based hydrogels as polysaccharide tragacanth gum and antioxidant lignin nanoparticles in bioactive multicomponent hydrogels for tissue engineering. These natural components are combined with TEMPO-oxidized cellulose nanofibrils, a material with known shear thinning behavior. Hydrogels presented tragacanth gum (TG) concentration-dependent rheological properties suitable for extrusion 3D printing. TG enhanced the swelling capacity up to 645% and the degradation rate up to 1.3%/day for hydrogels containing 75% of TG. Young's moduli of the hydrogels varied from 5.0 to 11.6 kPa and were comparable to soft tissues like skin and muscle. In vitro cell viability assays revealed that the scaffolds were non-toxic and promoted proliferation of hepatocellular carcinoma HepG2 cells. Therefore, the plant-based hydrogels designed in this work have a significant potential for tissue engineering.

Tuning the Porosity, Water Interaction, and Redispersion of Nanocellulose Hydrogels by Osmotic Dehydration.

Osmotic dehydration (OD) was introduced as a method to reproducibly tune the water content and porosity of cellulose nanofiber (CNF) hydrogels. The hierarchical porosity was followed by electron microscopy (pores with a >100 µm diameter) and thermoporosimetry (mesopores), together with mechanical testing, in hydrogels with solid contents ranging from 0.7 to 12 wt %. Furthermore, a reciprocal correlation between proton conductivity and the ratio of water bound to the nanocellulose network was established, suggesting the potential of these systems toward tunable energy materials.

Willow Bark for Sustainable Energy Storage Systems.

Willow bark is a byproduct from forestry and is obtained at an industrial scale. We upcycled this byproduct in a two-step procedure into sustainable electrode materials for symmetrical supercapacitors using organic electrolytes. The procedure employed precarbonization followed by carbonization using different types of KOH activation protocols. The obtained electrode materials had a hierarchically organized pore structure and featured a high specific surface area (>2500 m2 g-1) and pore volume (up to 1.48 cm3 g-1). The assembled supercapacitors exhibited capacitances up to 147 F g-1 in organic electrolytes concomitant with excellent cycling performance over 10,000 cycles at 0.6 A g-1 using coin cells. The best materials exhibited a capacity retention of 75% when changing scan rates from 2 to 100 mV s-1.

Highly Porous Willow Wood-Derived Activated Carbon for High-Performance Supercapacitor Electrodes.

In this study, we present willow wood as a new low-cost, renewable, and sustainable biomass source for the production of a highly porous activated carbon for application in energy storage devices. The obtained activated carbon showed favorable features required for excellent electrochemical performance such as high surface area (∼2 800 m2 g-1) and pore volume (1.45 cm3 g-1), with coexistence of micropores and mesopores. This carbon material was tested as an electrode for supercapacitor application and showed a high specific capacitance of 394 F g-1 at a current density of 1 A g-1 and good cycling stability, retaining ∼94% capacitance after 5 000 cycles (at a current density of 5 A g-1) in 6 M KOH electrolyte. The prepared carbon material also showed an excellent rate performance in a symmetrical two-electrode full cell configuration using 1 M Na2SO4 electrolyte, in a high working voltage of 1.8 V. The maximum energy density and power density of the fabricated symmetric cell reach 23 W h kg-1 and 10 000 W kg-1, respectively. These results demonstrate that willow wood can serve as a low-cost carbon feedstock for production of high-performance electrode material for supercapacitors.

Co-exfoliation and fabrication of graphene based microfibrillated cellulose composites - mechanical and thermal stability and functional conductive properties.

The excellent functional properties of graphene and micro-nanofibrillated cellulose (MNFC) offer plenty of possibilities for wide ranging applications in combination as a composite material. In this study, flexible graphene/microfibrillated cellulose (MFC) composite films were prepared by a simple method of co-exfoliation of graphite in an MFC suspension by high-shear exfoliation. We show that pristine graphene, without any chemical treatment, was homogeneously dispersed in the MFC matrix, and the produced composites showed enhanced thermal, electrical and mechanical properties compared to a non-co-exfoliated control. The film properties were studied by XPS, XRD, Raman, SEM, FTIR, TGA, nitrogen sorption, UV-vis spectroscopy, optical and formation analysis tests. At 0.5 wt% loading, the specific surface area of graphene/MFC composites increased from 218 to 273 m2 g-1 while the tensile strength and Young's modulus for the graphene/MFC composites increased by 33% and 28% respectively. Thermal stability was enhanced by 22% at 9 wt% loading and the composites showed a high electrical conductivity of 2.4 S m-1. This simple method for the fabrication of graphene/MFC composites with enhanced controlled functional properties can prove to be industrially beneficial, and is expected to open up a new route for novel potential applications of materials based largely on renewable resources.