Cellulose Nanofibrils Suspension Research Articles

On the thixotropy of cellulose nanofibril suspensions

The thixotropic behavior of mechanically disk refined cellulose nanofibril (CNF) aqueous suspensions with 100% fines content at 1 and 3 wt% concentrations was investigated through creep, shear-recovery, multiple-step oscillation, startup, and flow loop experiments. The CNF suspensions exhibited the key thixotropic characteristics such as reduction in viscosity over time and structure recovery after cessation of flow. The results of shear recovery and multiple-step oscillation experiments suggested that regardless of the CNF concentration, lower extents of deformation impede the ability of the suspension to recover its structure at rest and higher levels of shear rates and strain amplitudes facilitate the structure recovery. Furthermore, the results of the startup experiments indicate that CNF suspensions form structures at two different levels where the flocs erode each other during flow. The different types of loops found in the flow loop experiments performed at different shear rates and time intervals were categorized and analyzed in terms of the effects of erosion of flocs and fiber rearrangement during flow.

Rheology of Suspensions of TEMPO-Oxidised and Cationic Cellulose Nanofibrils-The Effect of Chemical Pre-Treatment.

Cellulose nanofibrils (CNFs) are particles with a high aspect ratio. Typically, chemically pre-treated CNFs (containing anionic or cationic charged groups) consist of long fibrils (up to 2 μm) with very low thickness (less than 10 nm). Derived from their high aspect ratio, CNFs form strong hydrogels with high elasticity at low concentrations. Thus, CNF suspensions appear as an interesting rheology modifier to be applied in cosmetics, paints, foods, and as a mineral suspending agent, among other applications. The high viscosity results from the strong 3D fibril network, which is related to the good fibrillation of the material, allowing the nanofibrils to overlap. The overlap concentration (c*) was found to vary from ca. 0.13 to ca. 0.60 wt.% depending on the type and intensity of the pre-treatment applied during the preparation of the CNFs. The results confirm the higher tendency for the fibres treated with (3-chloro-2-hydroxypropyl) trimethylammonium chloride (CHPTAC) and 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) to form a 3D network, resulting in the lowest c*. For the TEMPO-oxidised CNF suspensions, it was also found that aggregation is improved at acidic pH conditions due to lower charge repulsion among fibrils, leading to an increase in the suspension viscosity as well as higher apparent yield stresses. TEMPO CNF suspensions with a low content of carboxylic groups tend to precipitate at moderately acidic pH values.

Nonlinear oscillatory rheology of aqueous suspensions of cellulose nanocrystals and nanofibrils

In this work, the nonlinear rheological behavior of aqueous suspensions composed of two typical nanocellulose [rod-like cellulose nanocrystals (CNCs) and filamentous cellulose nanofibrils (CNFs)] was examined and compared by using various large-amplitude oscillatory shear (LAOS) analysis methods, such as Fourier-transform rheology, stress decomposition, Chebyshev polynomials, and the sequence of physical processes. From our analysis, the nonlinear rheological parameters of higher harmonics, dissipation ratio, strain hardening ratio, shear thickening ratio, transient modulus, and cage modulus were obtained and quantitatively analyzed. CNCs tend to assemble to form anisotropic structures in an aqueous medium while the CNFs are entangled to form gels. The CNF suspensions demonstrated a significant viscous modulus overshoot and had stronger yield stresses, but the yield of CNC suspensions was more ductile. In the case of low concentrations, the CNF suspensions demonstrated stronger intracycle shear thickening behavior in medium-amplitude oscillatory shear region and lower dissipation ratios at small strain amplitudes. Although both nanocellulose suspensions revealed the existence of four intracycle rheological transition processes (viscoplastic deformation, structural recovery, early-stage yielding, and late-stage yielding), the CNF suspensions exhibited a stronger structural recovery ability. Larger strain amplitudes did not invariably result in a broader range of intracycle rheological transitions, which are also affected by the excitation frequency. The application of the various LAOS analysis methods provided valuable intracycle nonlinear rheological insights into nanocellulose suspensions, which are of great importance for enhancing their industrial perspectives.

Reinforcement and Deacidification for a Textile Scroll Painting (AD 1881) Using the CNF and MgO Suspensions.

The scroll paintings for ancestor trees have been used to inherit the spirit of ancestor worship as a historical record of family development since the late Ming Dynasty in China. A severely degraded scroll painting of an ancestor tree (made of cotton textiles) needs intervention and conservation treatment to mitigate further deterioration. On the basis of the previously reported characterization results for the painting, in this paper, a suspension that is composed of 0.6% cellulose nanofibril (CNF) and nanosized 0.15% MgO in aqueous solvent (denoted as the CNF-MgO susairpension) was prepared. Conventional characterization methods were used to assess the properties of model samples before and after treatment with the CNF-MgO suspension, as well as before and after degradation under two sets of conditions. The results show that the treated model samples are slightly alkaline, given the deposit of alkaline particles, and demonstrate good mechanical properties before and after degradation due to the increase in fiber-to-fiber bond and mitigation of acid-catalyzed hydrolysis. In spite of the non-transparency of CNF and MgO nanoparticles, they have little impact on the optical properties of textiles, as verified by transmittance data and the determination of color changes. This suspension was then used to reinforce and restore the scroll painting in a practical conservation process. The application of CNF and MgO nanoparticles on textile objects investigated in this study would expand our understanding of the conservation of such objects, especially for those that have already become acidic and degraded.

Effect of hemicellulose hydrolysate addition on the dehydration and redispersion characteristic of cellulose nanofibrils

Nanocellulose, owing to its environmentally friendly and unique attributes, is gaining traction in various industries. However, commercialization of nanocellulose faces challenges due to structural alterations during drying process, leading to irreversible aggregation. This study, inspired by wood's natural structure, introduces a cellulose nanofibril (CNF) drying system using hemicellulose hydrolysate (HH) as a capping agent. The addition of only 1 wt% of HH to the CNF suspension not only prevents aggregation among CNFs during dehydration and drying but also dramatically enhances the redispersion rate and dispersion stability of the dried CNFs. The redispersed CNF/HH suspension exhibits physicochemical properties comparable to the original CNF suspension before drying. This confirms that HH inhibits irreversible hydrogen bonding among CNFs, leading to the restoration of the nanostructure during redispersion. Moreover, HH in the CNF suspension after redispersion can be easily removed through a simple water rinsing process, highlighting HH as a highly suitable candidate for preventing aggregation of CNFs.

Characterization of spray dried cellulose nanofibrils produced by a disk refining process at different fineness levels

Three types of wood pulp feedstocks including bleached softwood kraft, unbleached softwood kraft and old corrugated containers were disk refined to produce cellulose nanofibrils at different fineness levels ranging from 50 to 100%, and the resulting aqueous suspensions of cellulose nanofibrils were spray dried. The spray drying experiments were carried out to examine different processing conditions for the different CNF feedstock types and fines level at various suspension concentrations to produce dry samples with free-flowing powder morphologies. The fineness levels and solids contents of CNF suspensions were set to 80% or more and 1.8% or less, respectively. If the solids content of the CNF solutions was high and the fibrillation level was low, plugging was experienced in the spray head because of the high viscosity of the suspensions, resulting in production of poor-quality powders. In terms of reduction in processing energy, even if the CNF suspension solids content was increased to 1.5 wt.%, the powder quality and the production yields were excellent. It was confirmed that high-quality powder under 20 µm were produced at a 90% fibrillation level of all CNF feedstocks. The resulting dry CNF powders were characterized to determine particle size distributions and morphological properties via a scanning electron microscope and a laser diffraction particle size analyzer. The particle sizes were smaller at higher fibrillation levels and lower solids content of the CNF suspensions. The CNF suspension derived from bleached kraft pulp, the average particle size decreased by 43% and 33% with the lowered solids contents from 1.8 to 1%, and the increased fineness levels from 80 to 100%, respectively.

Characterization of CNC Nanoparticles Prepared via Ultrasonic-Assisted Spray Drying and Their Application in Composite Films.

The ultrasonic-assisted spray dryer, also known as a nano spray dryer and predominantly used on a lab scale in the pharmaceutical and food industries, enables the production of nanometer-sized particles. In this study, the nano spray dryer was applied to cellulosic materials, such as cellulose nanofibrils (CNFs) and cellulose nanocrystals (CNCs). CNC suspensions were successfully dried, while the CNF suspensions could not be dried, attributable to their longer fibril lengths. The nano spray drying process was performed under different drying conditions, including nebulizer hole sizes, solid concentrations, and gas flow rates. It was confirmed that the individual particle size of nano spray-dried CNCs (nano SDCNCs) decreased as the nebulizer hole sizes and solid contents of the suspensions decreased. The production rate of the nano spray dryer increased with higher solid contents and lower gas flow rates. The resulting nano SDCNCs were added to a polyvinyl alcohol (PVA) matrix as a reinforcing material to evaluate their reinforcement behavior in a plastic matrix using solvent casting. After incorporating the 20 wt.% nano SDCNCs into the PVA matrix, the tensile strength and tensile modulus elasticity of the neat PVA nanocomposite film increased by 22% and 32%, respectively, while preserving the transparency of the films.

Rheological behavior of cellulose nanofibril suspensions with varied levels of fines and solid content

The rheological behavior of mechanically disk refined cellulose nanofibril (CNF) aqueous suspensions with 50, 60, 70, 80, 90, 100 % fines contents at 1 and 3 wt% solid concentrations was studied by conducting various dynamic and steady-state rheological experiments, including oscillatory shear, flow sweep, startup, flow loop, and three-step oscillation experiments. All the samples exhibited a gel-like behavior in oscillatory shear tests and samples, with 50 % fines showed the highest levels of dynamic moduli for both solid contents. Suspensions with higher concentrations of CNFs showed higher values for viscosity, complex viscosity, and dynamic moduli. A critical shear rate of 10 s−1 independent of the solid contents of the suspensions was found for varying fines levels, where viscosity measurements above this critical shear rate converged and viscosity measurements below it diverged. All samples exhibited yield in shear flow and yield stresses exhibited a decreasing trend followed by a plateau as fines levels increased. The level of yield stress for 3 wt% suspensions was higher than that of 1 wt% suspensions. The lowest structure recovery was observed for samples containing 50 % fines content. Moreover, a rheopectic-thixotropic transition was observed for samples with high fines content (90 and 100 %) at low solid content (1 wt%).

Rheology of cellulose nanocrystal and nanofibril suspensions

Nanocellulose is a sustainable nanomaterial and a versatile green platform that has attracted increasing attention. Although the wide applications of its aqueous suspensions are closely related to rheology, comprehensive studies of their rheological behavior, especially the yielding behavior, are still limited. Herein, to investigate the relationship between structure and rheological properties, the viscoelasticity, thixotropy and yielding behavior of two commonly used nanocelluloses, rod-shaped cellulose nanocrystals (CNCs) and filamentous cellulose nanofibrils (CNFs), were systematically investigated. The viscosity, viscoelasticity and thixotropic behavior of the suspensions were analyzed by steady-state shear, frequency sweep, creep-recovery, hysteresis loop, and three-interval thixotropic recovery tests. The yielding behaviors were evaluated through creep, steady-state shear, step shear rate, stress ramps, amplitude sweep, and large amplitude oscillatory shear tests. The rheological properties of the two typical suspensions showed a strong dependence on concentration and time. However, compared to CNC suspensions, CNF suspensions exhibited stronger thixotropy and higher yield stress due to the higher aspect ratio of CNF and the stronger structural skeleton of the suspensions as supported by Simha's equation and micromorphology analysis. This work provides a theoretical rheology basis for the practical applications of nanocellulose suspensions in various fields.

Influence of residual lignin on Acacia mearnsii De Wild nanofibrillated cellulose suspensions and films

Influence of residual lignin on Acacia mearnsii De Wild nanofibrillated cellulose suspensions and films

Preprocessing considerations for floc reduction in cellulose nanofibril suspensions

Preprocessing considerations for floc reduction in cellulose nanofibril suspensions

Dried water-redispersible bacterial nanocellulose with sorbitol as capping agent

In view of the economic and technical limitations associated with diluted aqueous suspensions of cellulose nanofibrils, in the present contribution sorbitol was assayed as capping agent in the drying of bacterial nanocellulose (BNC) for the first time. The effect of different sorbitol:BNC mass ratios (1:1, 3:1 and 5:1), drying strategies (freeze-drying versus oven-drying), and redispersion methods (high-speed homogenization and mechanical stirring) on the water redispersibility of dried BNC was studied. Sedimentation, specific surface area and rheology assays all demonstrated the suitability of sorbitol for significantly limiting irreversible hydrogen bonding between adjacent cellulose nanofibrils during dehydration, leading to redispersed BNC suspensions with characteristics similar to those of never-dried ones. In the case of freeze-dried samples, results showed that the lowest sorbitol:BNC mass ratio assayed (i.e., 1:1) was enough to prevent irreversible hydrogen bonding between adjacent cellulose fibrils, whereas for oven-dried BNC samples full redispersion was achieved by mechanical stirring when sorbitol:BNC mass ratios of at least 3:1 were used. The feasibility of easily removing sorbitol from the dried product upon redispersion was also verified.

Endoglucanase effects on energy consumption in the mechanical fibrillation of cellulose fibers into nanocelluloses

Enzymatic processing is considered a promising approach for advancing environmentally friendly industrial processes, such as the use of endoglucanase (EG) enzyme in the production of nanocellulose. However, there is ongoing debate regarding the specific properties that make EG pretreatment effective in isolating fibrillated cellulose. To address this issue, we investigated EGs from four glycosyl hydrolase (GH) families (5, 6, 7, and 12) and examined the roles of the three-dimensional structure and catalytic features, with a focus on the presence of a carbohydrate binding module (CBM). Using eucalyptus Kraft wood fibers, we produced cellulose nanofibrils (CNFs) through mild enzymatic pretreatment, followed by disc ultra-refining. Comparing the results with the control (without pretreatment), we observed that GH5 and GH12 enzymes (without CBM) reduced fibrillation energy by approximately 15 %. The most significant energy reduction, 25 and 32 %, was achieved with GH5 and GH6 linked to CBM, respectively. Notably, these CBM-linked EGs improved the rheological properties of CNF suspensions without releasing soluble products. In contrast, GH7-CBM exhibited significant hydrolytic activity, resulting in the release of soluble products, but did not contribute to a reduction in fibrillation energy. This discrepancy can be attributed to the large molecular weight and wide cleft of GH7-CBM, which led to the release of soluble sugars but had little impact on fibrillation. Our findings suggest that the improved fibrillation observed with EG pretreatment is primarily driven by efficient enzyme adsorption on the substrate and modification of the surface viscoelasticity (amorphogenesis), rather than hydrolytic activity or release of products.

Surface modification of cellulosic nanofibrils by spray drying: Drying yield and microstructural, thermal and chemical characterization

This study investigated the effect of the addition of cationic surfactant cetyltrimethylammonium bromide (CTAB) in cellulose nanofibril suspensions (CNF) on the efficiency of the spray drying process, as well as on the properties of the dried microparticles and on their water redispersibility. The results indicated that CNF pretreated with 10% sodium silicate and modified with surfactant resulted in higher drying yields. The particle sizes formed by drying depended on the characteristics of the precursor CNF, in general, the particles were smaller than 8 µm. The crystalline fraction of all particles produced was higher than that of never dried (ND) CNF, furthermore the powders were thermostable at elevated temperatures (>200 °C), which provides good evidence for applications in composites. Water stability showed that the rehydrated cellulose solutions were influenced by the treatments and the drying process. The addition of surfactant proves attractive to increase the spray drying yield of CNF, bringing prospects regarding cost reduction and expansion of CNF commercialization. Furthermore, the results provide fundamental insights into the relationship between the surface modification of CNF associated with the drying process with the characteristics of the spray-dried material.

High-strength and functional nanocellulose filaments made by direct wet spinning from low concentration suspensions

Continuous filaments obtained through the wet spinning of nanocellulose have promising mechanical properties with sustainable features. To guarantee proper spinnability for wet spinning, freshly made cellulose nanofibril (CNF) suspension needs to be concentrated to have a concentration above 1 wt%, resulting in energy- and time-consuming, and inferior mechanical properties of the final filaments owing to decreasing the CNF alignment against shear flows. In this study, a CNF spinning suspension at a low concentration (0.4 wt%) can be used right after the fibrillation process without further treatments. The effects of the concentration and re-concentrating process are studied by carefully characterizing the rheological behavior and filament solidification processes, which provides more fundamental understandings on the spinnability and CNF network formation of such colloidal CNF suspensions. Combined with a post stretching process, the final dried CNF filaments have superior mechanical properties with Young's modulus and tensile strength of 35 GPa and 567 MPa, surpassing most literature data. Moreover, different functional particles can be easily incorporated to prepare functional filaments. With facile preparation and superior properties, these CNF filaments may be suitable for advanced composite filler and special textile applications.

Mandacaru cactus as a source of nanofibrillated cellulose for nanopaper production

In this work, nanofibrillated cellulose (NFC) was extracted from cactus Cereus jamacaru DC. (mandacaru) for nanopaper production. The technique adopted includes alkaline treatment, bleaching, and grinding treatment. The NFC was characterized according to its properties and scored based on a quality index. Particle homogeneity, turbidity, and microstructure of the suspensions were evaluated. Correspondingly, the optical and physical-mechanical properties of the nanopapers were investigated. The chemical constituents of the material were analyzed. The sedimentation test and the zeta potential analyzed the stability of the NFC suspension. The morphological investigation was performed using environmental scanning electron microscopy (ESEM) and transmission electron microscopy (TEM). X-ray diffraction (XRD) analysis revealed that Mandacaru NFC has high crystallinity. Thermogravimetric analysis (TGA) and mechanical analysis were also used and revealed good thermal stability and good mechanical properties of the material. Therefore, the application of mandacaru is interesting in sectors such as packaging and electronic device development, as well as in composite materials. Given its score of 72 points on a quality index, this material was presented as an attractive, facile, and innovative source for obtaining NFC.

Drying of non-chemically prepared nanofibrillated cellulose from lime residue: Effects of drying methods on fiber morphology, physicochemical properties and redispersibility

The effects of drying methods, i.e., hot air oven and spray drying, defibrillation step and use of maltodextrin as a drying aid on microstructure as well as water redispersibility of dried nanofibrillated cellulose (NFC) were investigated; NFC-to-maltodextrin ratios were varied at 1:0, 1:1, 1:1.5 or 1:2. Spray-dried NFCs possessed lower crystallinity index (CI) values than oven-dried NFC. Higher added maltodextrin content resulted in lowered CI values due to an increase in the amorphous fraction within the samples. Freshly prepared NFC suspension exhibited gel-like behavior, while suspensions prepared by redispersing any dried NFC in water lost such a behavior. High pressure (100 MPa) applied during microfluidization defibrillation is postulated to cause the degradation of pectin, leading to the loss of its capability to serve as Van der Walls interactions and hydrogen bonding formation inhibitor. Although maltodextrin could somehow help form a dispersed fibrillar structure upon water reconstitution, the extents of such a structure in all cases were still not adequate to regain the gel-like behavior.

Fabrication of conductive polyaniline nanomaterials based on redispersed cellulose nanofibrils

Dewatering or drying of diluted cellulose nanofibril suspensions is an effective way for reducing the costs of transportation and storage. In this study, poly(vinylpyrrolidone) (PVP) was introduced into a redispersing system of concentrated CNFs, and the obtained redispersed CNFs were used for fabricating CNF/PANI (polyaniline) nanomaterials by in situ polymerization method. The results showed that mechanical grinding with grinding gap of − 20 μm was an effective way to redisperse the concentrated CNFs, especially when the PVP was added in the redispersing process. The conductivity of the redispersed CNF/PANI film reached 1.08 S/cm and the specific capacitance reached 118.3 F/g (at 0.3 A/g), when the concentrated CNFs were redispersed with 5% PVP. During the polymerization process, PVP facilitated the PANI coating on the CNFs uniformly as steric stabilizer. This study provided a basis for the application of redispersed CNFs in conductive nanomaterials area.

Preparation of peanut shell cellulose nanofibrils and their superhydrophobic aerogels and their application on cotton fabrics

Nowadays, the application range of biomass materials is more and more extensive. In this work, peanut shell powder was used as the raw material. The cellulose nanofibrils was extracted from it by chemical mechanical method. Then, using the sol-gel method, methyltrimethoxysilane (MTMS) was added to the peanut shell cellulose nanofibrils suspension to modify it. Finally, the nano-cellulose superhydrophobic aerogel was prepared by freeze-drying method. The nano-cellulose aerogel and polydimethylsiloxane (PDMS) were coated on the cotton fabric by spraying method, and the superhydrophobic aerogel and superhydrophobic cotton fabric were analyzed and characterized respectively. The results shown that the prepared nanocellulose aerogel had a three-dimensional sheet-like structure with superhydrophobicity. The hydrophobic property and water contact angle (WCA) of cotton fabrics were significantly improved after superhydrophobic finishing. The WCA can reached 160°, the finished fabric has good antifouling performance and self-cleaning performance, and the oil-water separation efficiency can reach 82.2%.

Synthesis and Effect of Nanocellulose Obtained from East Java Kenaf Fiber on Mechanical Properties of Polyurethane Foam Composites as Strong and Lightweight Materials

Cellulose is a fascinating biopolymer and sustainable raw material. Cellulose particles with at least one dimension in the nanoscale are referred to as nanocellulose. Kenaf fiber is a natural fiber used in this study because it has high mechanical properties and strong interface adhesion with polymers so it provides superior properties to other natural fibers. Polyurethane (PU) foam is widely used as a core layer in sandwich composite construction to produce a lightweight material. This study presents a synthesis of cellulose nano-fibrils (CNF) extracted from East Java, Indonesia based kenaf fibers, an analysis of the effect of adding CNF as a filler and a reinforcement in PU foam composites, and a formulation of PU-CNF foam composite that provided the best mechanical properties as strong and lightweight materials in structural applications. The CNF extraction from kenaf fiber started by fiber pre-treatment including alkalization and bleaching, then mechanical treatment with an Ultra Fine Grinder to produce CNF suspension. The weight variations of CNF in PU foam were 0, 3, 5, 7, and 10 wt%. PU-CNF composite fabrication using the in-situ polymerization method. CNF characterization included TEM, XRD, and FT-IR. TEM results on CNF show that the CNF diameter is in the range of 40-70 nm. The functional group from the FT-IR results showed that the pre-treatment process on kenaf fiber was successful in reducing the lignin and hemicellulose content. XRD results showed that the CNF crystallinity was 75.22%. The PU-CNF foam composite characterization included a compressive test, 3-point bending test, and SEM. The PU foam composite with 3 wt% CNF reinforcement is the best composite which has the optimum value from the results of the compression test and the 3-point bending test. The compressive strength value increased by 20.01%, from 236.997 kPa to 284.434 kPa, the compressive modulus value increased by 29.21% from 5.67 MPa to 7.32 MPa, and the 3-point bending strength value increased 28.29% from 572.24 to 734.15 kPa. All the results expected to support that CNF was a potential reinforcement material with a high surface area for a wide variety of applications.