Amounts Of Cellulose Nanofibrils Research Articles

Nanoparticle/Cellulose-Based Surface Enhanced Raman Scattering Hybrid Sensors

Surface-Enhanced Raman Scattering (SERS) sensors are versatile biosensors for detecting very low concentrations of molecules. Their molecular and chemical sensitivity crucially depends on the tailoring of their nanostructure. These sensors rely on noble metal or oxide cluster layers, with their crystallinity and nanostructure carefully tuned to enable a maximum of plasmonic hot spots and enabling charge transfer. Typically, such sensors are in thin film geometry. In order to optimize their nanostructure and optical properties of the metal or oxide clusters, cellulose nanofibrils (CNFs) as template for nanoparticle-biopolymer hybrid materials are readily employed due to their high mechanical strength and ability to establish nanoporous, scalable thin films via spray deposition.[1] In order to characterize their nanostructure during synthesis of the hybrid nanoparticle-CNF material, grazing incidence X-ray scattering (GIXS) is ideally suited due to its ability to observe the nanostructural changes during farication and optimization of the sensor materials. The resulting nanostructure is then directly correlation to the sensor capability of the hybrid materials. As a first example, we use the catalytic properties of CNF during thermal decomposition of silver nitrate as precursor for fabrication of size-tuned silver clusters on CNF to tune their optical band-gap. The correlation between hot-spot size and silver nanoparticle size for optimizing the SERS sensitivity is elucidated using GIXS, showing for the first time the optimum hot spot size.[2] In order to facilitate an equal distribution of hot-spots, we make use of the three-dimensional nanoporous structure of the CNF thin films by adding shell-free silver nanoparticles in aqueous solution, again applying spray deposition.[3] The nanoporosity allows for reducing drastically agglomerations of silver nanoparticles, detrimental to hot-spots. At the same time, the spectral position of the plasmon resonance is tuned by the amount of CNF as structural matrix. As a final example we extend these results to novel semiconductor metal oxide nanomaterial (SMON)-based sensors.[4] Here, titanium oxide is deposited via atomic layer deposition (ALD) on the nanoporous CNF network, preserving its three-dimensional morphology. We optimize the nanostructure, crystallinity and rutile-to-anatase ratio in order to obtain superior sensitivity of the hybrid titania/CNF thin films as SMON SERS substrates. The improvement of SERS activity relies on the cooperative modulation of the CNF network and the crystalline states of the deposited titania. To summarize, we present new routes for SERS sensors based on plasmonic and charge transfer properties of hybrid materials by tailoring the hybrid nanostructure.[1] Brett, C. J.; Ohm, W.; Fricke, B.; Alexakis, A. E.; Laarmann, T.; Körstgens, V.; Müller-Buschbaum, P.; Söderberg, L. D.; Roth, S. V. Nanocellulose-Assisted Thermally Induced Growth of Silver Nanoparticles for Optical Applications. ACS Appl. Mater. Interfaces 2021, 13 (23), 27696–27704. https://doi.org/10.1021/acsami.1c07544.[2] Santoro, G.; Yu, S.; Schwartzkopf, M.; Zhang, P.; Koyiloth Vayalil, S.; Risch, J. F. H.; Rübhausen, M. A.; Hernández, M.; Domingo, C.; Roth, S. V. Silver Substrates for Surface Enhanced Raman Scattering: Correlation between Nanostructure and Raman Scattering Enhancement. Appl. Phys. Lett. 2014, 104 (24), 243107. https://doi.org/10.1063/1.4884423.[3] Chen, Q.; Brett, C. J.; Chumakov, A.; Gensch, M.; Schwartzkopf, M.; Körstgens, V.; Söderberg, L. D.; Plech, A.; Zhang, P.; Müller-Buschbaum, P.; Roth, S. V. Layer-by-Layer Spray-Coating of Cellulose Nanofibrils and Silver Nanoparticles for Hydrophilic Interfaces. ACS Appl. Nano Mater. 2021, 4 (1), 503–513. https://doi.org/10.1021/acsanm.0c02819.[4] Chen, Q.; Betker, M.; Harder, C.; Brett, C. J.; Schwartzkopf, M.; Ulrich, N. M.; Toimil‐Molares, M. E.; Trautmann, C.; Söderberg, L. D.; Weindl, C. L.; Körstgens, V.; Müller‐Buschbaum, P.; Ma, M.; Roth, S. V. Biopolymer‐Templated Deposition of Ordered and Polymorph Titanium Dioxide Thin Films for Improved Surface‐Enhanced Raman Scattering Sensitivity. Adv. Funct. Mater. 2022, 32 (6), 2108556. https://doi.org/10.1002/adfm.202108556.

Eco-friendly food packaging based on paper coated with a bio-based antibacterial coating composed of carbamate starch, calcium lignosulfonate, cellulose nanofibrils, and silver nanoparticles

Traditional paper-based packaging commonly needs to be coated to achieve sufficient mechanical and barrier performances. In this research, a bio-based coating for paper was developed from carbamate starch (Sc), calcium lignosulfonate (CL), and cellulose nanofibrils (CNF). Controlling the electrostatic and hydrogen-bonding interactions among the components of the coating was conducive to tailoring the structure and performance of the coated paper. When the degree of substitution (Ds) of Sc was 0.10, the amount of CL was 1.00 g, and the amount of CNF was 0.65 % of the weight of Sc, the paper coated with the resulting 0.10Sc-1.00CL-0.65CNF coating exhibited increased hydrophobicity and excellent mechanical, air-barrier, and UV-light-barrier properties. After the addition of 0.10 % of silver nano-particles (AgNPs) to the 0.10Sc-1.00CL-0.65CNF coating, the paper coated with the resulting 0.10Sc-1.00CL-0.65CNF-0.10AgNPs coating exhibited good antibacterial activity against Escherichia coli and Staphylococcus aureus. The coated paper was used as the packaging for cherry tomatoes stored under ambient conditions. Due to the synergistic preservation effects of the Sc-CL-CNF coating and AgNPs, the shelf life of the cherry tomatoes was at least 7 days. The coated paper described herein has the potential for applications in the food packaging sector.

Effect of cellulose nanofibrils on vancomycin drug release from chitosan nanocomposite films

Overuse of antibiotic drugs usually leads to the further development of resistance to targeted bacteria. In this context, a controlled release system could be a solution to achieve higher drug efficiency without overdosing and drug resistance. In this work, nanocomposite films based on chitosan (CHI) reinforced with cellulose nanofibrils (CNF) for antibiotic release were prepared and characterized. Several nanocomposite films containing vancomycin hydrochloride and different amounts of CNF (5, 10, and 20 wt%) were prepared by the solvent casting method. Spectroscopic (FTIR), thermal (TG), morphological (SEM), mechanical, and swelling analyses of the films were performed to study the effect of nanofibers content on the nanocomposite properties. A good dispersion of CNF and the model drug was observed in the CHI matrix. FTIR spectroscopy confirmed the interaction between the film components (CNF and CHI). Film swelling capacity decreased with an increase of CNF content in the film formulation, whereas stiffness and tensile strength of the film increased. In addition, vancomycin release at pH = 7.4 was studied, and it was observed that controlled slower release could be achieved by tuning the CNF content in the chitosan film. The results confirm that these films could be useful for pharmaceutical purposes where the controlled release of drugs is required.

Self-crosslinked polyvinyl alcohol/cellulose nanofibril cryogels loaded with synthesized aminophosphonates as antimicrobial wound dressings.

Microbial infection is the most common obstacle in the wound healing process, leading to wound healing impairment and complications and ultimately increasing morbidity and mortality. Due to the rising number of pathogens evolving resistance to the existing antibiotics used for wound care, alternative approaches are urgently required. In this study, α-aminophosphonate derivatives as antimicrobial agents were synthesized and incorporated into self-crosslinked tri-component cryogels composed of fully hydrolyzed polyvinyl alcohol (PVA-F), partially hydrolyzed polyvinyl alcohol (PVA-P), and cellulose nanofibrils (CNFs). Initially, the antimicrobial activity of four α-aminophosphonate derivatives against selected skin bacterial species was tested and their minimum inhibitory concentration was determined based on which the most effective compound was loaded into the cryogels. Next, the physical and mechanical properties of cryogels with various blending ratios of PVA-P/PVA-F and fixed amounts of CNFs were assessed, and drug release profiles and biological activities of drug-loaded cryogels were analyzed. Assessment of α-aminophosphonate derivatives showed the highest efficacy of a cinnamaldehyde-based derivative (Cinnam) against both Gram-negative and Gram-positive bacteria compared to other derivatives. The physical and mechanical properties of cryogels showed that PVA-P/PVA-F with a 50/50 blending ratio had the highest swelling ratio (1600%), surface area (523 m2 g-1), and compression recoverability (72%) compared to that with other blending ratios. Finally, antimicrobial and biofilm development studies showed that the cryogel loaded with a Cinnam amount of 2 mg (relative to polymer weight) showed the most sustained drug release profile over 75 h and had the highest efficacy against Gram-negative and Gram-positive bacteria. In conclusion, self-crosslinked tri-component cryogels loaded with the synthesized α-aminophosphonate derivative, having both antimicrobial and anti-biofilm formation properties, can have a significant impact on the management of uprising wound infection.

Mechanical Enhancement of Composite Bricks Using Kenaf and Oil Palm Cellulose Nanofibrils

The application of nanocellulose has been adapted as fillers in composite bricks. Raw kenaf and oil palm empty fruit bunch were treated through chemical treatment and high intensity ultrasonication process to produce cellulose nanofibrils (CNF). One control brick without CNF and ten CNF composite bricks were fabricated. The composite bricks used different amount of CNF which were 40 - 200 ml mixed with filtered sand, portland cement and pebbles. Physical and mechanical characterization was done by using field emission scanning electron microscopy (FESEM) and universal testing machine (UTM) on CNF and composite bricks. FESEM showed the fibril diameter were ranges from 30 - 80 nm for kenaf and 20 - 60 nm for oil palm. The compression tests showed that control brick, 40 ml kenaf CNF composite brick and 40 ml oil palm CNF composite brick were cracked at force 39.01 kN, 50.46 kN and 42.16 kN respectively. Kenaf CNF composite brick has the highest value of Young’s Modulus which is 28.92 N/mm2, followed by oil palm CNF composite brick with 27.8 N/mm2 and control brick (Malaysia Standard) with 25.8 N/mm2. Kenaf and oil palm CNF can increase the strength of the bricks because of enhancement in their mechanical properties.

Influence of cellulose nanofibrils on the rheology, microstructure and strength of alkali activated ground granulated blast-furnace slag: a comparison with ordinary Portland cement

This paper reports on the effect of cellulose nanofibrils (CNFs) on the fresh-state properties of alkali activated ground granulated blast-furnace slag (GGBS). Surface functionalized (oxidized) CNFs were added to alkali activated GGBS water suspensions (hydraulic pastes). The rheological behaviour of the pastes was compared with OPC and interpreted based on the CNF-mineral surface interaction, and on the CNF-water interaction and swelling. The water dispersion of CNFs with different surface functionalization degrees resulted in gels of different viscosity and yield stress, due to their different hydrophilicity and water adsorption properties. On increasing the CNFs surface oxidation degree, the viscosity of the CNF water dispersion decreases and the CNF water adsorption increases, while the viscosity of fresh pastes increases because of the reduced amount of available mixing water. In the hardened state, the hydraulic pastes show differences in mechanical strength related to the type and the amount of CNF influencing the porosity of the matrix as evidenced by the microstructural investigation performed by X-ray microtomography. The presence of higher amounts of CNFs induces the formation of porous agglomerates that may act as stress concentrators due to the swelling ability of nanofibrils.

Stabilization of the emulsion of Alkenyl Succinic Anhydride (ASA) in water using cellulose nanofibrils

Alkenyl Succinic Anhydride (ASA) is sizing agent that is applied as an aqueous emulsion during the papermaking process to improve paper’s hydrophobicity. However, its application becomes difficult as the emulsion quickly destabilizes due to the coalescence phenomenon and the high reactivity of ASA with water. In this work, we used cellulose nanofibrils (CNFs) to increase the stability of the ASA emulsion over time. Small amounts of CNFs added to the emulsion helps to increase its storage life by almost 3 times, by means of stabilizing the average droplet size and reducing the amount of hydrolyzed ASA. The time extension allows higher flexibility of the sizing processes. In this work, we identify the negative impact that the temperature and the presence of metal ions in water have on the quality on the optimal ASA emulsion, resulting in a reduction in their effects for both factors with the presence of cellulose nanofibrils.

Nanocellulose-Based Hybrid Materials for UV Blocking and Mechanically Robust Barriers.

Nanocellulose (NC)-based hybrid coatings and films containing CeO2 and SiO2 nanoparticles (NPs) to impart UV screening and hardness properties, respectively, were prepared by solvent casting. The NC film-forming component (75 wt % of the overall solids) was composed entirely of cellulose nanocrystals (CNCs) or of CNCs combined with cellulose nanofibrils (CNFs). Zeta potential measurements indicated that the four NP types (CNC, CNF, CeO2, and SiO2) were stably dispersed in water and negatively charged at pH values between 6 and 9. The combination of NPs within this pH range ensured uniform formulations and homogeneous coatings and films, which blocked UV light, the extent of which depended on film thickness and CeO2 NP content, while maintaining good transparency in the visible spectrum (∼80%). The addition of a low amount of CNFs (1%) reduced the film hardness, but this effect was compensated by the addition of SiO2 NPs. Chiral nematic self-assembly was observed in the mixed NC film; however, this ordering was disrupted by the addition of the oxide NPs. The roughness of the hybrid coatings was reduced by the inclusion of oxide NPs into the NC matrix perhaps because the spherical oxide NPs were able to pack into the spaces between cellulose fibrils. We envision these hybrid coatings and films in barrier applications, photovoltaics, cosmetic formulations, such as sunscreens, and for the care and maintenance of wood and glass surfaces, or other surfaces that require a smooth, hard, and transparent finish and protection from UV damage.

Physical, mechanical, optical and biodegradability properties of polyvinyl alcohol/cellulose nanofibrils/kaolinite clay-based hybrid composite films

ABSTRACT The aim of this study was to investigate the physical, mechanical, optical and biodegradation properties of polyvinyl alcohol (PVA)/cellulose nanofibrils (CNFs)/Kaolinite clay (KC)-based hybrid composite films prepared by the solution casting method. CNFs were extracted from barley husk using the acid hydrolysis method. The average diameter of the CNFs was 17.5 nm and the length was more than 1100 nm. Water uptake of the composite films increased with the increase in the amount of CNFs in PVA matrix from 5% to 25%. While a significant reduction in water uptake was observed for KC-reinforced films, the optical transmittance changed a little with the addition of CNFs and a transmittance of 90% was observed for the film containing 5% CNFs. Tensile strength of the hybrid film containing 5% CNFs and 5% KC increased by 62% as compared to that of the PVA film. Soil burial test revealed that the PVA/CNF composite films exhibited high weight loss (%) in comparison with PVA/KC and PVA/KC/CNF composite films. The film containing 25% CNFs showed the highest weight loss of 46.54% after 75 days of burial in soil.

Lignin Particles for Multifunctional Membranes, Antioxidative Microfiltration, Patterning, and 3D Structuring.

We introduce a new type of particle-based membrane based on the combination of lignin particles (LPs) and cellulose nanofibrils (CNF), the latter of which are introduced in small volume fractions to act as networking and adhesive agents. The synergies that are inherent to lignin and cellulose in plants are re-engineered to render materials with low surface energy (contact angle measurements) and can be rendered water-resistant with the aid of wet-strength agents (WSAs). Importantly, they are most suitable for antioxidative separation (ABTS•+ radical inhibition): membranes with uniform porous structures (air permeability and capillary flow porosimetry) allow effluent oxidation at 95 mL/cm2, demonstrating, for the first time, the use of unmodified lignin particles in flexible membranes for active microfiltration. Moreover, the membranes are found to be nonfouling (protein adhesion and activity rate). The inherent properties of lignin, including UV radiation blocking capacity (UV transmittance analysis) and reduced surface energy, are further exploited in the development of tailorable and self-standing architectures that are almost entirely comprised of nonbonding LP (solids content as high as 92 w/w%). Despite such composition, the materials develop high toughness (oscillatory dynamic mechanical analysis), owing to the addition of minor amounts of CNF. Multifunctional materials based on thin films (casting), 3D structures (molding), and patterned geometries (extrusion deposition) are developed as a demonstration of the potential use of lignin particles as precursors of new material generation. Remarkably, our observations hold for spherical LPs since a much poorer performance was observed after using amorphous powder, indicating the role of size and shape in related applications.

Mechanical and thermal properties of rice straw cellulose nanofibrils-enhanced polyvinyl alcohol films using freezing-and-thawing cycle method

This study investigated effects of loadings of rice straw (Oryza sativa L.) cellulose nanofibrils (CNFs) defibrillated using the high-pressure homogenization technique on tensile property, glass transition temperature, and thermal stability of polyvinyl alcohol (PVA) matrix. CNF loadings had five percentage levels by weight of final composite, i.e. 0, 0.03, 0.08, 0.12, and 0.17%, respectively. A freezing-and-thawing cycle method cast PVA/CNF-mixed and PVA-only films. Experimental results showed that PVA films with 0.03% CNFs had average tensile strength of 50.8 MPa and modulus of 707 MPa, which were 32 and 21% higher than neat PVA ones, respectively. In addition, the glass transition temperature values of PVA/CNF-mixed film increased from 51.6% to 82.6% with increasing the amount of CNFs. The thermogravimetric analysis showed that PVA/CNF-mixed films had significantly higher thermal stability than PVA-only films. The shift of the O–H stretching vibration peak in PVA/CNF-mixed films indicated a good compatibility between CNFs and PVA matrix.

Viscoelastic properties of nanocellulose based inks for 3D printing and mechanical properties of CNF/alginate biocomposite gels

Inks for 3D printing based on cellulose nanofibrils (CNFs) or mixtures of CNFs and either cellulose nanocrystals (CNCs) or alginate were assessed by determining their viscoelastic properties i.e. complex viscosity and storage and loss moduli (G′ and G″). Two types of alginates were used, i.e. from Laminaria hyperborea stipe and Macrocystis pyrifera. Shape fidelity of 3D printed grids were qualitatively evaluated and compared to the viscoelastic properties of the inks. The biocomposite gels containing alginate were post stabilized by crosslinking with Ca2+. Mechanical properties of the crosslinked biocomposite gels were assessed. The complex viscosity, G′ and G″ of CNF suspensions increased when the solid content was increased from 3.5 to 4.0 wt%, but levelled off by further increase in CNF solid content. The complex viscosity at low angular frequency at 4 wt% was as high as 104 Pa·s. This seemed to be the necessary viscosity level for obtaining good shape fidelity of the printed structures for the studied systems. By replacing part of the CNFs with CNCs, the complex viscosity, G′ and G″ were reduced and so was also the shape fidelity of the printed grids. The changes in complex viscosity and moduli when CNFs was replaced with alginate depended on the relative amounts of CNFs/alginate. The type of alginate (from either L. hyp. stipe or M. pyr.) did not play a role for the viscoelastic properties of the inks, nor for the printed grids before post stabilization. Replacing CNFs with up to 1.5 wt% alginate gave satisfactory shape fidelity. The effect of adding alginate and subsequent crosslinking with Ca2+, strongly affected the strength properties of the gels. By appropriate choice of relative amounts of CNFs and alginate and type of alginate, the Young’s modulus and rupture strength could be controlled within the range of 30–150 kPa and 1.5–6 kg, respectively. The deformation at rupture was around 55%. The alginate from L. hyp. stipe yields higher Young’s modulus and lower syneresis compared to M. pyr. This shows that the choice of alginate plays a significant role for the mechanical properties of the final product, although it does not influence on the viscoelastic properties of the ink. The choice of alginate should be L. hyp. stipe if high strength is desired.

Study of green nanocomposites based on corn starch and cellulose nanofibrils from Agave tequilana Weber

Global environmental pollution issues caused by synthetic materials and the lack of practical utilization of the local industrial lignocellulosic waste, force Mexican researchers to produce new biobased sustainable materials that use industrial waste as a source of components. Herein, we show the preparation and characterization of environmentally friendly starch-based nanocomposites reinforced with cellulose nanofibrils (CNF) extracted from Agave tequilana Weber. Tensile, bending and impact mechanical properties of dried and hydrated nanocomposites were studied. Moreover, the water absorption capacity of the nanocomposites were measured and evaluated. The mechanical properties improved because of the presence of a small amount of CNF (1 wt%). This work demonstrates the importance of the addition of a natural biomodifier in a starch matrix to achieve better mechanical properties. Most importantly, this study highlights that lignocellulosic waste from the tequila industry can have a practical application, which is being a source of natural nanoreinforcements for preparation of all-biobased sustainable materials.

Effect of Cellulose Nanofibrils on the Bond Strength of Polyvinyl Acetate and Starch Adhesives for Wood

Nanocellulose is a competitive reinforcement material for use in biocomposite structures and fibrous products. In this study, adhesive mixtures of dicarboxylic acid cellulose nanofibrils (CNF) were dispersed into commercial polyvinyl acetate (PVAc) and starch adhesives, which were applied to Norway spruce (Picea abies) to assess their performance in wood joining. Single-lap joints were prepared and tested with PVAc mixtures with 0 to 0.64 wt% CNF and starch glue mixtures containing 0 to 1.07 wt% CNF. CNF suspensions having three concentrations (0.64, 0.96, and 1.28%) were compared. The results showed that the optimum amount of CNF, 0.48% suspensions, added to PVAc increased the average lap joint strength (EN 205:2003) by 74.5% when compared to control specimens with pure PVAc. Correspondingly, 0.96% CNF suspensions also enhanced the strength of starch adhesive by 34.5%. Lower and higher CNF concentrations showed clearly inferior performance.

Impact of TEMPO-oxidization strength on the properties of cellulose nanofibril reinforced polyvinyl acetate nanocomposites

Nanocomposites of polyvinyl acetate (PVAc) reinforced with two different TEMPO-oxidized cellulose nanofibrils (CNF) were prepared by casting/evaporation method. These two sets of CNF, designed as CNF-O-5min (5min of oxidation) and CNF-O-120min (120min of oxidation), are different by their surface charge, geometrical characteristics and crystallinity index. The weight fraction of CNF was changed from 1 to 10wt%. The mechanical and thermal properties of the nanocomposite films were studied by dynamic mechanical thermal analysis (DMTA), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and tensile tests, and their morphology was investigated by scanning electron microscopy (SEM). For all nanocomposites, increasing amounts of CNF led to a significant increase in the mechanical properties (increase in Young’s modulus and tensile strength) and in the water uptake. On the other hand, the lost of transparency became very significant when the weight fraction of CNF exceeded 3wt%. The comparison between the two sets of CNF showed that PVAc/CNF-O-5min nanocomposite films had a tendency to display higher tensile strength and elastic modulus than those of PVAc/CNF-O-120min films. In addition, the water uptake is higher for PVAc/CNF-O-120min. Finally, the thermal stability analyses for PVAc/CNF films show that shorter and more charged fibrils (CNF-O-120min) appear to slightly increase the thermal stability compared to other larger and less charged fibrils (CNF-O-5min). All these results are discussed in connection with the CNFs characteristics.

Formulation and Composition Effects in Phase Transitions of Emulsions Costabilized by Cellulose Nanofibrils and an Ionic Surfactant.

Cellulose nanofibrils (CNF) offer great prospects as a natural stabilizer of colloidal dispersions and complex fluids for application in food, pharma, and cosmetics. In this study, an ionic surfactant (sodium dodecyl sulfate, SDS) was used as emulsifier of oil-in-water and water-in-oil emulsions that were further costabilized by addition of CNF. The adsorption properties of SDS in both, CNF dispersions and emulsions, as well as the influence of composition (CNF and SDS concentration) and formulation (ionic strength, oil, and CNF types) on the phase behavior were elucidated and described in the framework of Windsor systems. At low salinity, the phase transition of emulsions containing CNF and SDS at low concentrations was controlled by molecular transfer in the oil-in-water system. Irregular droplets and "bi-continuous" morphologies were observed at medium and high salinity for systems containing high CNF and SDS concentrations. Water-in-oil emulsions were only possible at high salinity and SDS concentrations in the presence of small amounts of CNF. The results revealed some subtle differences in CNF interfacial activity, depending on the method used for their isolation via fiber deconstruction, either from microfluidization or aqueous counter collision. Overall, we propose that the control of emulsion morphology and stability by addition of CNF opens the possibility of developing environmentally friendly complex systems that display high stability and respond to ionic strength following the expectations of classical emulsion systems.

Mechanical Properties of Composite Hydrogels of Alginate and Cellulose Nanofibrils.

Alginate and cellulose nanofibrils (CNF) are attractive materials for tissue engineering and regenerative medicine. CNF gels are generally weaker and more brittle than alginate gels, while alginate gels are elastic and have high rupture strength. Alginate properties depend on their guluronan and mannuronan content and their sequence pattern and molecular weight. Likewise, CNF exists in various qualities with properties depending on, e.g., morphology and charge density. In this study combinations of three types of alginate with different composition and two types of CNF with different charge and degree of fibrillation have been studied. Assessments of the composite gels revealed that attractive properties like high rupture strength, high compressibility, high gel rigidity at small deformations (Young’s modulus), and low syneresis was obtained compared to the pure gels. The effects varied with relative amounts of CNF and alginate, alginate type, and CNF quality. The largest effects were obtained by combining oxidized CNF with the alginates. Hence, by combining the two biopolymers in composite gels, it is possible to tune the rupture strength, Young’s modulus, syneresis, as well as stability in physiological saline solution, which are all important properties for the use as scaffolds in tissue engineering.

Steady-shear and viscoelastic properties of cellulose nanofibril\u2013nanoclay dispersions

We have investigated the steady-shear and viscoelastic properties of composite dispersions of cellulose nanofibrils (CNFs) with medium or high charge density and two different nanoclays, viz. rod-like sepiolite or plate-like bentonite. Aqueous dispersions of CNFs with medium charge density displayed significantly lower steady-state viscosity and storage modulus but higher gelation threshold compared with CNFs with high charge density. Dynamic light scattering (DLS) results showed that the apparent hydrodynamic radius of bentonite particles increased when CNFs were added, implying that CNFs adsorbed onto the amphoteric edges of the plate-like bentonite particles. The sepiolite network in CNF–sepiolite dispersions was relatively unaffected by addition of small amounts of CNFs, and DLS showed that the hydrodynamic radius of sepiolite did not change when CNFs were added. Addition of CNFs at concentrations above the gelation threshold resulted in drastic decrease of the steady-shear viscosity of the sepiolite dispersion, suggesting that the sepiolite network disintegrates and the rod-like clay particles are aligned also at low shear rate. The relative change in the rheological properties of the clay-based dispersions was always greater on addition of CNFs with high compared with medium charge density. This study provides insight into how the rheology of CNF–nanoclay dispersions depends on both the nanoclay morphology and the interactions between the nanoclay and nanocellulose particles, being of relevance to processing of nanocellulose–clay composites.

Preparation of porous sheets with high mechanical strength by the addition of cellulose nanofibrils

Porous sheets with high mechanical strength were prepared with natural pulp fibers (hardwood and softwood bleached kraft pulp) and polyethylene terephthalate (PET) by adding cellulose nanofibrils (CNF) through a wet-laid forming method. The structure and mechanical properties of the porous sheets were investigated in this study depending on the type of mixed fibers, the CNF ratio, and drying methods (cylinder-drying and freeze-drying). The apparent density and porosity of porous sheets changed according to the morphology of the mixed fibers. PET fibers resulted in a sheet with a bulkier structure, whereas natural pulp fibers produced relatively dense sheets. Sheets with high porosity could be prepared by freeze-drying due to the inhibition of hydrogen bonds and low shrinkage during drying. Pore characteristics were evaluated in terms of air permeability and average pore diameter. The air permeability of porous sheets decreased as the amount of CNF increased. Mercury porosimetry showed that the average pore diameter in sheets ranged from 0.6 to 36.7 µm depending on the type and mixing ratio of fibers and drying conditions. Sheet tensile properties were improved by the addition of CNF and changed depending on mixing combinations and drying methods. The applicability of freeze-dried porous sheets as filter media was examined by evaluating the filtration efficiency and pressure drop. Porous sheets with a HwBKP/CNF combination showed a filtration efficiency of 99.944 %, which approached the efficiency of a high efficiency particulate air filter. However, further study is required to reduce the pressure drop during filtration for better use as an air filter.

Preparation and Viscoelastic Properties of Composite Fibres Containing Cellulose Nanofibrils: Formation of a Coherent Fibrillar Network

Composite fibres with a matrix of poly(ethylene glycol) (PEG) and cellulose nanofibrils (CNF) as reinforcing elements were produced using a capillary viscometer. Two types of CNF were employed: one based on carboxymethylated pulp fibres and the other on TEMPO-oxidized pulp. Part of the latter nanofibrils was also grafted with PEG in order to improve the compatibility between the CNF and the PEG matrix. The nominal CNF-content was kept at 10 or 30 weight-%. The composite fibres were characterized by optical and scanning electron microscopy in addition to dynamic mechanical thermal analysis (DMTA). Evaluation of the storage modulus indicated a clear reinforcing effect of the CNF, more pronounced in the case of the grafted CNF and depending on the amount of CNF. An interesting feature observed during the DMTA-measurements was that the fibrils within the composite fibres appeared to form a rather coherent and load-bearing network which was evident even after removing of the PEG-phase (by melting). An analysis of the modulus of the composite fibres using a rather simple model indicated that the CNF were more efficient as reinforcing elements at lower concentrations which may be associated with a more pronounced aggregation as the volume fraction of CNF increased.