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.

Comparison of Nanofibrillated Cellulose and Hydroxyethyl Cellulose in Improving the Storage Stability of Waterborne Coatings

Waterborne coatings often delaminate and settle during long-term storage,requiring the addition of thickeners.The effects of nanofibrillated cellulose(NFC)and the commonly used thickener,hydroxyethyl cellulose(HEC),on the storage stability of waterborne coatings were compared in this study.The morphology of NFC was characterized using infrared spectroscopy(FT-IR)and scanning electron microscopy(SEM).The rotational viscosity and rheological properties of the waterborne coatings with NFC and HEC were tested.Stationary settling experiments were also conducted at different temperatures to compare the difference of NFC and HEC on improving the storage stability of the waterborne coatings.The results showed that the waterborne coating with NFC exhibited pseudoplastic fluid characteristics;a small addition of NFC can achieve the same improvement effect on the storage stability of waterborne coatings as HEC.Further,the improvement effect of NFC was not affected by temperature.The waterborne coating with NFC still exhibited good storage stability at high temperatures,which was significantly superior to that of HEC.Therefore,NFC is a feasible agent for improving the prolonged storage stability and warming-induced delamination of waterborne coatings.

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.

Flexible Nanopaper Composed of Wood-Derived Nanofibrillated Cellulose and Graphene Building Blocks

Nanopaper has attracted considerable interest in the fields of films and paper research.However,the challenge of integrating the many advantages of nanopaper still remains.Herein,we developed a facile strategy to fabricate multifunctional nanocomposite paper(NGCP)composed of wood-derived nanofibrillated cellulose(NFC)and graphene as building blocks.NFC suspension was consisted of long and entangled NFCs(10–30 nm in width)and their aggregates.Before NGCP formation,NFC was chemically modified with a silane coupling agent to ensure that it could interact strongly with graphene in NGCP.The resulting NGCP samples were flexible and could be bent repeatedly without any structural damage.Within the NGCP samples,the high aspect ratio of NFC made a major contribution to its high mechanical strength,whereas the sheet-like graphene endowed the NGCP with electrical resistance and electrochemical activity.The mechanical strength of the NGCP samples decreased as their graphene content increased.However,the electrical resistance and electrochemical activity of the NGCP samples both rose with increasing content of graphene.The NGCPs still kept advantageous mechanical properties even at high temperatures around 300℃ because of the high thermal stability of NFCs and their strong entangled web-like structures.In view of its sustainable building blocks and multifunctional characteristics,the NGCP developed in this work is promising as low-cost and high-performance nanopaper.

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.

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.

Cellulose Nanopaper:Fabrication,Functionalization,and Applications

Cellulose nanopaper has shown great potential in diverse fields including optoelectronic devices,food packaging,biomedical application,and so forth,owing to their various advantages such as good flexibility,tunable light transmittance,high thermal stability,low thermal expansion coefficient,and superior mechanical properties.Herein,recent progress on the fabrication and applications of cellulose nanopaper is summarized and discussed based on the analyses of the latest studies.We begin with a brief introduction of the three types of nanocellulose:cellulose nanocrystals,cellulose nanofibrils and bacterial cellulose,recapitulating their differences in preparation and properties.Then,the main preparation methods of cellulose nanopaper including filtration method and casting method as well as the newly developed technology are systematically elaborated and compared.Furthermore,the advanced applications of cellulose nanopaper including energy storage,electronic devices,water treatment,and high-performance packaging materials were highlighted.Finally,the prospects and ongoing challenges of cellulose nanopaper were summarized.

Microfibrillated Cellulose from Sugarcane Bagasse as a Biorefinery Product for Ethanol Production

Research involving the preparation of microfibrillated cellulose(MFC)from sugarcane bagasse is a relevant topic to the production of new nanomaterials and more accessible cellulose substrates for the production of second generation ethanol.Regarding the transformation of cellulose into glucose,the precursor of second generation ethanol,this nanosized cellulosic substrate represents a more appropriate material for the chemical hydrolysis process.The high aspect ratio of MFC improves hydrolysis,requiring mild conditions and decreasing the generation of by-products.Here,MFC was prepared from sugarcane bagasse by ultrasound defibrillation.This material was oxidized with 2,2,6,6-tetramethylpiperidine-N-oxyl(TEMPO)to produce negatively charged high defibrillated MFC.The MFC was characterized by Fourier transform infrared spectroscopy(FTIR),X-ray diffraction(XRD),scanning electron microscopy(SEM)and viscosity measurements.

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.

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.

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.

Dispersive Ability of Carboxylated Cellulose Nanofibrils for Aqueous Monolayer Montmorillonite Dispersion:Influence of Na^(+) and Ca^(2+) Concentrations

Carboxylated cellulose nanofibrils(CNFs)have emerged as effective green dispersants for monolayer montmorillonite(MMT)dispersions.However,their dispersion capability is sensitive to the metal ion concentration in aqueous solutions.Hence,this study investigated the effects of Na^(+) and Ca^(2+) concentrations on the dispersive ability of carboxylated CNFs for monolayer MMTs in water.Quartz crystal microbalance with dissipation monitoring(QCM-D)and atomic force microscopy(AFM)were utilized to explore the interfacial interactions between the carboxylated CNFs and monolayer MMTs under different Na^(+) and Ca^(2+) concentrations.When the concentration of Na^(+) reached 0.1 mmol/L,the adhesion mass of carboxylated CNFs on MMT-coated wafer peaked at 24.47 mg/m^(2),higher than control sample(carboxylated CNF-dispersed monolayer MMT dispersion without metal ions,16.03 mg/m^(2)).Moreover,the electrostatic shielding effect promoted a better dispersion of monolayer MMTs by carboxylated CNF dispersant.With a further increase in the Na^(+) concentration,the surface charge of CNFs and MMTs would be reversed resulting from the improved electrostatic shielding effect,which weaken the dispersive ability of carboxylated CNFs.The addition of Ca^(2+) reduced the dispersive ability of carboxylated CNFs for monolayer MMTs,because Ca^(2+) required a lower concentration for the onset of charge reversal compared to Na^(+).This study provides interfacial scale insights into the influence of metal ion concentration on carboxylated CNF-dispersed monolayer MMT dispersions.It also provides a strategy to enhance the dispersive ability of carboxylated CNFs for monolayer MMTs.

Effect of Ultra-Turrax on Nanocellulose Produced by Acid Hydrolysis and Modified by Nano ZnO by Sol-Gel Method

Cellulose nanocrystals (NCC) and cellulose nanofibrils (CNF) were obtained by a single step process, with synergy between 64% sulfuric acid hydrolysis and high shear from ultra-turrax stirring, which is an advantageous process for disintegrating cellulose microcrystalline and also may improve the hydrolysis process. The surface modification on the cellulose was performed by the sol-gel process, in which the sulfate groups from hydrolysis were replaced by nanoparticles of zinc oxide, which led to the increase of up to 54°C Tonset, according to thermogravimetric analysis (TGA) results. The morphology and crystallinity degree were characterized by Helium Ion Microscopy (HIM), atomic force microscopy (AFM) and X-ray diffraction. In addition, the ZnO band was observed in Fourier transform infrared spectroscopy, furthermore, the change in the zeta potential confirmed the cellulose modification. The changes in the values of proton spin-spin relaxation time for the systems showing the confined hydrogen in the rigid domains, confirmed the results observed with the aforementioned techniques, for both cellulose after hydrolysis and ZnO modified cellulose, suggesting that ZnO disrupted crystal formation in cellulose.

A fast ionic transport copolymeric network for stable quasi-solid lithium metal battery

Solid-state lithium(Li) metal batteries overwhelm the lithium-ion batteries by harvesting high energy from Li metal anode with ultrahigh capacities and gaining excellent safety from solid electrolytes.However,the uncontrollable solvents in solid electrolytes usually aggravate poor interfacial contact with lithium metal anode and deteriorate Li^(+) pathways.Here a copolymeric network-structured ion conductor by rationally integrating cellulose nanofibril as a two-in-one functional material is employed to anchor the solvent.Taking advantages of tightly anchoring of cellulose nanofibril to solvent,the asconstructed quasi-solid polymer-based electrolyte offers rapid Li^(+) transport channels and realizes effective Li-dendrite suppression,which enables high ionic conductivity of 1.93 × 10^(-3)S cm^(-1) at room temperature,long-term Li plating/stripping over 1900 h,and high capacity retention of 99%.This work provides a fresh strategy for creating solid electrolytes that meet both high ionic conductivity and interfacial stability requirements for practical solid-state lithium metal battery.

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.

Optical and Mechanical Properties of CMCNF-dispersed MMT/CMC-Na Nanocomposite Films: Influence of the Degree of Substitution of CMCNFs

Carboxymethylated cellulose nanofibril(CMCNF)is an effective green dispersant to prepare well-dispersed monolayer montmorillonites(MMTs)in water,thereby facilitating the preparation of a high-performance MMT/polymer nanocomposite film.However,not enough attention has been paid to correlating the degree of substitution(DS)of CMCNFs with the mechanical and optical properties of the final nanocomposite films.In this study,a series of homogeneous monolayer MMT nanoplatelet dispersions was prepared initially using CMCNFs with different DS as a dispersant,and the as-prepared CMCNF-dispersed MMT dispersions were then mixed with sodium carboxymethyl cellulose(CMC-Na)to fabricate nacre-like nanocomposite films with different contents of MMTs through self-assembly.The layered nanostructure and optical and mechanical properties of the asprepared CMCNF-dispersed MMT/CMC-Na nanocomposite films were investigated,which demonstrated that CMCNFs with lower DS have a positive effect on their optical and mechanical properties.This study sheds light on the preparation of MMT-based nanocomposite films with superior optical and mechanical properties.