Unraveling the Rheology of Nanocellulose Aqueous Suspensions:A Comprehensive Study on Biomass-Derived Nanofibrillated Cellulose

The rheological properties of nanocellulose aqueous suspensions play a critical role in the development of nanocellulose-based bulk materials.High-crystalline,high-aspect ratio,and slender nanofibrillated cellulose(NFC)were extracted from four biomass resources.The cellulose nanofibrils and nanofibril bundles formed inter-connected networks in the NFC aqueous suspensions.The storage moduli of the suspensions with different concentrations were higher than their corresponding loss moduli.As the concentration increased,the storage and loss modulus of NFC dispersion increased.When the shear rate increased to a certain value,there were differences in the changing trend of the rheological behavior of NFC aqueous suspensions derived from different biomass resources and the suspensions with different solid concentrations.NFC dispersion’s storage and loss modulus increased when the temperature rose to nearly 80℃.We hope this study can deepen the understanding of the rheological properties of NFC colloids derived from different biomass resources.

A Glassy Carbon Electrode Modified with Cellulose Nanofibrils from Ammophila arenaria for the Sensitive Detection of L-Trytophan

L-tryptophan is an essential amino acid for human health. Nanofibrillated cellulose (NFC) from marram grass (Ammophila arenaria) extracted from plants harvested in the center of Tunisia was used for the first time for the modification of a glassy carbon electrode (GCE), for the sensitive detection of L-tryptophan (Trp). After spectroscopic and morphological characterization of the extracted NFC, the GC electrode modification was monitored through cyclic voltammetry. The NFC-modified electrode exhibited good analytical performance in detecting Trp with a wide linear range between 7.5 × 10−4 mM and 10−2 mM, a detection limit of 0.2 µM, and a high sensitivity of 140.0 µA∙mM−1. Additionally, the NFC/GCE showed a good reproducibility, good selectivity versus other amino acids, uric acid, ascorbic acid, and good applicability to the detection of Trp in urine samples.

Ultrathin and Flexible CNTs/MXene/Cellulose Nanofibrils Composite Paper for Electromagnetic Interference Shielding

As the rapid development of portable and wearable devices,different electromagnetic interference(EMI)shielding materials with high efficiency have been desired to eliminate the resulting radiation pollution.However,limited EMI shielding materials are successfully used in practical applications,due to the heavy thickness and absence of sufficient strength or flexibility.Herein,an ultrathin and flexible carbon nanotubes/MXene/cellulose nanofibrils composite paper with gradient and sandwich structure is constructed for EMI shielding application via a facile alternating vacuum-assisted filtration process.The composite paper exhibits outstanding mechanical properties with a tensile strength of 97.9±5.0 MPa and a fracture strain of 4.6±0.2%.Particularly,the paper shows a high electrical conductivity of 2506.6 S m?1 and EMI shielding effectiveness(EMI SE)of 38.4 dB due to the sandwich structure in improving EMI SE,and the gradient structure on regulating the contributions from reflection and absorption.This strategy is of great significance in fabricating ultrathin and flexible composite paper for highly efficient EMI shielding performance and in broadening the practical applications of MXene-based composite materials.

Morphological, Mechanical and Thermal Properties of Poly(lactic acid)(PLA)/Cellulose Nanofibrils(CNF) Composites Nanofiber for Tissue Engineering

Composite nanofiber membranes based on biodegradable poly(lactic acid)(PLA) and cellulose nanofibrils(CNF) were produced via electrospinning. The influence of CNF content on the morphology, thermal properties, and mechanical properties of PLA/CNF composite nanofiber membranes were characterized by field scanning electron microscopy(FE-SEM), differential scanning calorimetry(DSC), thermogravimetric analysis(TGA), and dynamic mechanical analysis(DMA), respectively. The results show that the PLA/CNF composite nanofibers with smooth, free-bead surface can be successfully fabricated with various CNF contents. The introduction of CNF is an effective approach to improve the crystalline ability, thermal stability and mechanical properties for PLA/CNF composite fibers. The Young's moduli and tensile strength of the PLA/CNF composite nanofiber reach 106.6 MPa and 2.7 MPa when the CNF content is 3%, respectively, which are one times higher and 1.5 times than those of pure PLA nanofiber. Additionally, the water contact angle of PLA/CNF composite nanofiber membranes decreases with the increase of the CNF loading, resulting in the enhancement of their hydrophilicity.

Sol-Gel Template Synthesis and Photocatalytic Activity of TiO_2 Nanofibrils Loaded on Al_2O_3 Template

TiO2 nanofibrils were prepared within the pores of alumina template membrane by use of sol-gel chemistry. The TiO2 nanofibrils have good crystallinity and size. There is agglomeration free among the particulates of TiO2 and the fibrils show high catalytic activity.

Silk nanofibril as nanobinder for preparing COF nanosheet-based proton exchange membrane

Two-dimensional covalent organic framework nanosheets(CONs)with ultrathin thickness and porous crystalline nature show substantial potential as novel membrane materials.However,bringing CONs materials into flexible membrane form is a monumental challenge due to the limitation of weak interactions among CONs.Herein,one-dimensional silk nanofibrils(SNFs)from silkworm cocoon are designed as the nanobinder to link sulfonated CON(SCON)into robust SCON-based membrane through vacuum-filtration method.Ultrathin and large lateral-sized SCONs are synthesized via bottom-up interface-confined synthesis approach.Benefiting from high length-diameter ratio of SNF and rich functional groups in both SNF and SCON,two-dimensional(2D)SCONs are effectively connected together by physical entanglement and strong H-bond interactions.The resultant SCON/SNF membrane displays dense structure,high mechanical integrity and good stability.Importantly,the rigid porous nanochannels of SCON,high-concentration-SO3H groups insides the pores and H-bonds at SCON-SNF interfaces impart SCON/SNF membrane high-rate proton transfer pathways.Consequently,a superior proton conductivity of 365 mS cm^(-1)is achieved at 80C and 100%RH by SCON/SNF membrane.This work offers a promising approach for connecting 2D CON materials into flexible membrane as high-performance solid electrolyte for hydrogen fuel cell and may be applied in membrane-related other fields.

Application of Cellulose Nanofibril as a Wet-end Additive in Papermaking:A Brief Review

Recently,cellulose nanofibril(CNF)has emerged as a promising,sustainable reinforcement with outstanding potential in material science.Owing to the properties of CNF,it has been explored in food,cosmetic,and pharmaceutical applications,as well as in industrial applications such as paints,drill muds,packaging,and papermaking.The application of CNF in papermaking is expected to be implemented in the near future to broaden the commercial market of cellulose.Numerous studies and patents have reported on the manufacturing,properties,and applications of nanocellulose.This present paper focuses on the recent progresses in the application of CNF as a wet-end additive in papermaking.

Simultaneous Extraction of Carboxylated Celulose Nanocrystals and Nanofibrils via Citric Acid Hydrolysis--A Sustainable Route

In this study, cellulose nanocrystals(CNC) with surface carboxylic groups were prepared from bleached softwood pulp by hydrolysis with concentrated citric acid at concentrations of 60 wt%~80 wt%. The solid residues from acid hydrolysis were collected for producing cellulose nanofibrils(CNF) via post high-pressure homogenization. Citric acid could be easily recovered after hydrolysis reactions through crystallization due to its low water solubility or through precipitation as a calcium salt followed by acidification. Several important properties of CNC and CNF, such as dimension, crystallinity, surface chemistry, thermal stability, were evaluated. Results showed that the obtained CNC and CNF surfaces contained carboxylic acid groups that facilitated functionalization and dispersion in aqueous processing. The recyclability of citric acid and the carboxylated CNC/CNF give the renewable cellulose nanomaterial huge potential for a wide range of industrial applications. Furthermore, the resultant CNC and CNF were used as reinforcing agents to make sodium carboxymethyl cellulose(CMC) films. Both CNC and CNF showed reinforcing effects in CMC composite films. The tensile strength of CMC films increased by 54.3% and 85.7% with 10 wt% inclusion of CNC and CNF, respectively. This study provides detailed information on carboxylated nanocellulose prepared by critic acid hydrolysis; a sustainable approach for the preparation of CNC/CNF is of significant importance for their various uses.

Preparation and Characterization of Cellulose Nanofibril-Waterborne Polyurethane Composite Films

To improve the performance of polyurethane films,small amounts of cellulose nanofibrils(CNF)were physically blended with a waterborne polyurethane(WPU)emulsion,and then CNF/WPU composite films were prepared by cast-coating and drying.The particle size of the emulsions and the chemical structure,micromorphology,thermal stability,mechanical properties,and water resistance of the composite films were characterized using a Malvern laser particle size analyzer,Fourier transform infrared spectroscopy(FT-IR),scanning electron microscopy(SEM),thermogravimetric analysis(TGA),an electronic strength machine,water contact angle analysis(WCA),and water absorption tests,respectively.The results showed that at a low CNF content of 0.3 wt%,the particle size of the WPU emulsion and chemical structure of the film did not change significantly.In addition,the tensile strength of the composite film increased by up to 108%compared to the neat WPU film,and the thermal stability and water resistance were slightly improved.The addition of CNF greatly enhanced the tensile strength while maintaining the other original properties of the WPU film,which may greatly improve the service life and tear resistance of commercial coatings in the future.

Water-Based Processing of Fiberboard of Acrylic Resin Composites Reinforced With Cellulose Wood Pulp and Cellulose Nanofibrils

Despite the great potential of cellulose wood pulp and cellulose nanofibrils as reinforcing filler in thermoplastics,its use is limited due to its tendency to form agglomerates and due to its high hydrophilic character.Here we describe fiberboard composites with high contents of wood pulp or cellulose nanofibrils,and a resin of poly(styrene-methyl-methacrylate-acrylic acid)used as water-based emulsion.Cellulose wood pulp and cellulose nanofibrils were used directly in the form of water suspensions.The method is based on the flocculation of the polymer emulsion followed by agglomeration of a mixture of the polymer emulsion and cellulose suspension,leading to the co-precipitation of the composite material,which can be easily separated from the water phase.Composites with acrylic polymer/cellulose fibers in the proportions of 75:25,50:50 and 25:75 wt%were prepared.Composites were characterized by scanning electron microscopy(SEM),Fourier transform infrared spectroscopy(FTIR),thermogravimetric analysis(TGA),dynamic mechanical analysis(DMA)and water absorption tests.SEM analysis revealed a very good dispersion of the fibers without evidence of agglomeration,which led to superior mechanical properties.These results showed the effectiveness of the methodology and the potential of cellulose wood pulp and CNF as reinforcement fillers in fiberboard composites and any other high fiber-content materials.

3D-Printed PLA Filaments Reinforced with Nanofibrillated Cellulose

In the current study poly(lactic acid)PLA composites with a 3 wt%and 5 wt%of nanofibrillated cellulose(NFC)were produced by 3D-printing method.An enzymatic pretreatment coupled with mechanical fibrillation in a twin screw extruder was used to produce high consistency NFC.Scanning electron microscopy(SEM)equipped with Fibermetric software,FASEP fiber length distribution analysis,Furrier transform infrared spectroscopy(FT-IR),thermogravimetric analysis(TGA),tensile tests,impact tests and differential scanning calorimetry were used to characterize NFC and PLA/NFC composites.The results of the fiber length and width measurements together with the results of the SEM analysis showed that enzymatic hydrolysis coupled with a twin screw extrusion could effectively reduce the diameter and length of cellulose fibers.The produced NFC consisted of microand nanosized fibers entangled in a characteristic 3D-network.Based on the FT-IR analysis,no new bonds were formed during the enzymatic hydrolysis or fibrillation process.The TGA analysis confirmed that produced NFC can be used in hightemperature extrusion processing without NFC degradation.During the PLA/NFC composites preparation the NFC agglomerates were formed,which negatively influenced PLA/NFC composites impact properties.The slightly improved tensile strength and elastic modulus were reported for all composites when compared to the neat PLA.The elongation at break was not affected by the NFC addition.No significant differences in thermal stability were detectable among composites nor in comparation with the neat PLA.However,the crystallinity degree of the composite containing 5 wt%NFC was increased in respect to the neat PLA.

Preparation of Cellulose Nanofibrils by Multi-Site Regioselective Oxidation

Cellulose nanofibrils(CNFs)are promising sustainable materials that can be applied to nanocomposites,as well as medical and life-sciences devices.However,methods for the preparation of these important materials are energy intensive because heating and mechanical disintegration are required to produce cellulose fibers below 100 nm in size.In this study,CNFs were prepared through the multi-site regioselective oxidation of cellulose with 2,2,6,6-tetramethylpiperidine-1-oxyl(TEMPO)and periodate at room temperature(20–25°C),without any mechanical-disintegration treatment.Transmission electron microscopy(TEM)revealed that the CNFs had the average widths of 14.1,55.4,and 81.9 nm for three different treatments.Fourier-transform infrared spectroscopy revealed that carboxyl groups were created on the surfaces of the microfibrils,while X-ray diffraction studies showed that the cellulose I structure was maintained after oxidation,and that the cellulose nanofibril crystallinity index exceeded 70%.These results demonstrate that CNFs can be prepared by multi-site regioselective oxidation at room temperature in the absence of mechanical disintegration.In addition,a model was developed to calculate the total content of carboxylate and aldehyde groups of CNFs prepared by the TEMPO mediate oxidation,the periodate oxidation,and the multi-site regioselective oxidation methods based on the particle width determined by TEM.The calculated values of the model were in good agreement with the total content(experimental value)of carboxylate and aldehyde groups of CNFs prepared by the TEMPO-mediated oxidation and the multi-site regioselective oxidation methods.However,the model was not valid for CNFs prepared by the periodate oxidation method.

Reinforcing Paper Strength by Dual Treatment of a Cationic Water-soluble Polymer and Cellulose Nanofibril

Cellulose nanofibril(CNF)was used as the anionic component of two dual strengthening systems wherein polyamidopolyamine epichlorohydrin resin(PAE)or cationic starch(CS)was used as the cationic component.Their strengthening effects were investigated for lowbasis-weight(30 g/m2)paper composed of a mixture of fully bleached softwood and hardwood pulp in a 4:1 mass ratio.Using the PAE/CNF or CS/CNF dual system,it was generally easier to achieve higher wet and dry tensile strengths of paper compared to the paper using the single PAE or CS system.For example,the paper using the PAE(0.4%)/CNF(0.3%)dual system exhibited 89%higher wet tensile strength than the paper using the single PAE(0.4%)system,and the paper using CS(1.3%)/CNF(0.3%)dual treatment showed 21%higher dry strength than that using the single CS(1.3%)system.However,the PAE/CNF system only showed small improvement in the dry strength of paper(11%higher than that of paper using the single PAE system),so did the CS/NFC system on wet strength improvement(only 17%higher than that of paper using the single CS system).

Nanofibrillation of a Bleached Acacia Pulp by Grinding with Carboxymethylation Pretreatment

In this study,carboxymethylation,which introduces carboxyl groups to hydroxyl sites in pulp fibers,was used as a pretreatment before mechanical nanofibrillation.The carboxyl group content of the pulp fibers was greatly affected by the dosage of chloroacetic acid and the reaction temperature.During the following fibrillation process,it was found that pulp fibers with higher carboxyl group content exhibited higher water holding capacities and smaller dimensions.A more homogenous structure with a higher amount of individual fibrils was also observed in FE-SEM images of pulp fibers with high carboxyl group content.This can be explained by a high ionic group content in the fiber wall resulting in lower delamination resistance,making the fibrils easier to separate.Carboxymethylation pretreatment as a facilitator of fibrillation in cellulosic pulps is an efficient way to obtain cellulose nanofibrils and consequently decrease the energy consumption of the process.

Preparation and Performance of Salt Tolerance and Thermal Stability Cellulose Nanofibril Hydrogels and Their Application in Drilling Engineering

The poor salt tolerance,thermal stability,and environmental performance of petrochemicals can severely limit their applications in drilling engineering.In this study,cellulose nanofibril(CNF)hydrogels with improved salt tolerance and thermal stability were prepared,and their filtration performance was evaluated.The hydrogels were prepared through the simultaneous grafting of 2-acrylamido-2-methylpropane sulfonic acid(AMPS)and butyl acrylate(BA)onto the CNF surface through ceric ammoniumnitrate-induced radical polymerization.The modified and original CNF samples were characterized using Fourier Transform infrared spectroscopy(FT-IR)and rheological measurements.The FT-IR analysis results showed that both AMPS and BA were grafted onto the CNF backbone,affirming the successful preparation of the grafted CNFs.The rheological analysis results showed that the modified CNF hydrogels exhibited significantly improved salt tolerance,thermal stability,and“salt-thickening”effect.Moreover,the results of the fluid loss test showed that the modified CNF hydrogels exhibited a much better fluid loss control than the original CNF hydrogels.In addition,after adding 2%modified CNF hydrogels as a filtrate reducer in the drilling fluids prepared with a 6%combined salt solution,the filtrate loss was significantly reduced even after aging for 72 h at 160℃.

An Alternative Strategy to Obtain Cellulose Nanofibrils from Parenchyma Cellulose of Bagasse Pith and the Performance of Its Nanopaper

Cellulose nanofibrils(CNFs)were obtained through one-step mechano-partial dissolution by ball milling in N,N-dimethyl acetamide with a low concentration of LiCl from agricultural waste bagasse pith(BP).Compared with fibrous cellulose,parenchyma cellulose(PC)is less uniform in diameter and less aligned,causing PC to dissociate into CNFs during this process without pretreatment.The results showed that the CNFs prepared from PC of BP had a diameter of 30-200 nm and a length of several micrometers.The as-obtained CNFs,along with dissolved cellulose,formed a wet-stable and highly transparent nanopaper in a sorbitol aqueous solution bath,which exhibited a high strain of 101%and a low Young's modulus of 4.3 MPa owing to the addition of the plasticizer sorbitol.This type of nanopaper with favorable transparency,high tensile property,and low Young's modulus has great potential for use as electronic skin and medical dressing material.

Airborne Nanoparticles Filtration by Means of Cellulose Nanofibril Based Materials

Nanoparticles in air are of particular concern for public health and employee exposure in work-places. Therefore, it is very important to prepare effective filters for their removal. In this work filters were prepared from nanocellulose, i.e. cellulose nanofibrils (CNF). CNF was produced using two methods giving two different qualities of CNF. One quality had negative charges on the fibril surfaces while the other was neutral, and had in addition thinner fibrils compared to the other qualities. Filter samples were produced from water dispersions of CNF, by removal of the water by freeze drying. The performance of the CNF based filters was assessed and compared with filters based on synthetic polymer fibres. The ability to collect NaCl particles with a broad size distribution, ranging from nanometer to micrometer scale, was determined. CNF filters showed quality values comparable with the synthetic polymer based filters. Filters based on both the two CNF qualities had very good filtration efficiency for a given pressure drop across the filter.

Okara Cellulose Nanofibrils Produced by Pretreatment with Sustainable Deep Eutectic Solvent Coupled with Various Mechanical Treatments

In this study,a green,environmentally friendly method for rapid cellulose nanofribril(CNF)preparation with a significant cost advantage was developed.Pretreatment with a deep eutectic solvent(DES)synthesized from oxalic acid dihydrate and choline chloride(ChCl-O)was combined with various mechanical treatment methods to produce okara CNFs from agricultural waste,with different diameter distributions.The results showed that high-speed stirring produced CNFs with an average diameter of 27 nm.This method was advantageous because it consumed about 94%less energy than traditional high-pressure homogenization method.The DES recovery rate was more than 90%,and DES served as a highly effective treatment,indicating that DES pretreatment is an economical,convenient,and effective strategy for okara CNF preparation.

Injectable self-healing nanocellulose hydrogels crosslinked by aluminum:Cellulose nanocrystals vs.cellulose nanofibrils

With excellent biocompatibility and unique physiochemical properties,nanocelluloses including cellulose nanocrystals(CNCs)and cellulose nanofibrils(CNFs)are promising candidates for preparing biomedical hydrogels.CNCs and CNFs are different in morphology and surface charges.Herein,CNCs and two CNFs(CNFs-C,Carboxylated CNFs;CNFs-P,Phosphorylated CNFs)were synthesized and applied to fabricate hydrogels through metal crosslinking.Aluminum crosslinking was found to be the best choice for enhancing the strength.This study systematically compared the morphologies,storage modulus,loss factor,continuous shear ramp,self-healing,swelling,in vitro degradation and injectable properties of the fabricated hydrogels,Further,a radar chart is summarized as guidelines to direct the rational selection to meet the specific requirements of further biomedical applications.At the same nanocellulose concentration and after Al^(3+)crosslinking,CNCs hydrogels had strong water holding capacity twice as much as that of CNFs hydrogels.While CNFs hydrogels showed higher hardness and stronger resistance to degradation than that of CNCs.These results provide detailed insights into nanocellulose hydrogels,making it possible to use these guidelines to select hydrogels for desired performance.

N,P co-doped porous graphene with high electrochemical properties obtained via the laser induction of cellulose nanofibrils

Cellulose and its derivatives are natural materials with high carbon contents, but it is challenging to convert their carbon into high value-added carbonaceous materials(e.g., graphene). Here, an approach to convert the carbon in cellulose into N, P co-doped porous graphene(LIG) materials via laser induction is proposed. Cellulose nanofibrils(CNFs), a cellulose derivative with high dispersion uniformity and abundant surface hydroxyl groups, were easily formed on a bulk substrate(thickness ≥5 mm) containing ammonium polyphosphate(APP). Then, a 10.6 μm CO2 laser was used to scribe for 1–5 passes on the CNFs/APP substrate under an ambient environment to produce N, P co-doped porous LIG. Upon increasing the number of laser scribing passes, the IG/IDof LIG first increased and then decreased, reaching a maximum of 1.68 at 4 passes. The good pore structure and low resistance also showed that 4 laser passes were ideal. Besides, the N, P co-doped LIG also showed excellent electrochemical performance, with a specific capacitance of 221.4 FF·g^(-1) and capacitance retention of 89.9%. This method exploits the advantages of nanocellulose and overcomes the difficulties associated with directly compounding cellulosic materials, providing a method for the further development of biomass nanomaterials.