Anisotropic Cellulose Research Articles

Hierarchical Incorporation of Reduced Graphene Oxide into Anisotropic Cellulose Nanofiber Foams Improves Their Thermal Insulation.

Anisotropic cellulose nanofiber (CNF) foams represent the state-of-the-art in renewable insulation. These foams consist of large (diameter >10 μm) uniaxially aligned macropores with mesoporous pore-walls and aligned CNF. The foams show anisotropic thermal conduction, where heat transports more efficiently in the axial direction (along the aligned CNF and macropores) than in the radial direction (perpendicular to the aligned CNF and macropores). Here we explore the impact on axial and radial thermal conductivity upon depositing a thin film of reduced graphene oxide (rGO) on the macropore walls in anisotropic CNF foams. To obtain rGO films on the foam walls we developed liquid-phase self-assembly to deposit rGO in a layer-by-layer fashion. Using electron and ion microscopy, we thoroughly characterized the resulting rGO-CNF foams and confirmed the successful deposition of rGO. These hierarchical rGO-CNF foams show lower radial thermal conductivity (λr) across a wide range of relative humidity compared to CNF control foams. Our work therefore demonstrates a potential method for improved thermal insulation in anisotropic CNF foams and introduces versatile self-assembly for postmodification of such foams.

Efficient preparation of anisotropic cellulose sponge from cotton stalks: An excellent material for separation applications

Water pollution and solid waste resource reuse demand immediate attention and research. Here, we present a method to create anisotropic cellulose sponges from cotton stalk waste. Using the inherent structure of cotton stalks, we selectively remove lignin and hemicellulose via acid and alkali pretreatment. This process yields cellulose sponges with a natural pore structure. Our findings demonstrate that these sponges retain the original pore configuration of cotton stalks, providing excellent connectivity and compressibility due to their unique anisotropic three-dimensional structure. Moreover, these sponges exhibit exceptional super-hydrophilic and underwater super-oleophobic properties, with underwater oil contact angles exceeding 150° for all tested oils. External pressure can reduce the pore size of the cellulose sponge, facilitating the gravity-driven separation and removal of dyes and emulsions. Remarkably, removal efficiencies for Methylene Blue (MB), Congo Red (CR), water-in-oil (w/o) emulsions, and oil-in-water (o/w) emulsions exceed 99 %, 97 %, 99 %, and 99 %, respectively, highlighting superior removal and recyclability. Further investigation into the mechanisms of dye and emulsion removal employs X-ray photoelectron spectroscopy (XPS) characterization and molecular dynamics (MD) simulation. These insights lay the groundwork for the efficient recycling and resource utilization of waste cotton stalks, offering promising applications in water purification.

Wood-inspired anisotropic hydrogel electrolyte with large modulus and low tortuosity realizing durable dendrite-free zinc-ion batteries

While aqueous zinc-ion batteries exhibit great potential, their performance is impeded by zinc dendrites. Existing literature has proposed the use of hydrogel electrolytes to ameliorate this issue. Nevertheless, the mechanical attributes of hydrogel electrolytes, particularly their modulus, are suboptimal, primarily ascribed to the substantial water content. This drawback would severely restrict the dendrite-inhibiting efficacy, especially under large mass loadings of active materials. Inspired by the structural characteristics of wood, this study endeavors to fabricate the anisotropic carboxymethyl cellulose hydrogel electrolyte through directional freezing, salting-out effect, and compression reinforcement, aiming to maximize the modulus along the direction perpendicular to the electrode surface. The heightened modulus concurrently serves to suppress the vertical deposition of the intermediate product at the cathode. Meanwhile, the oriented channels with low tortuosity enabled by the anisotropic structure are beneficial to the ionic transport between the anode and cathode. Comparative analysis with an isotropic hydrogel sample reveals a marked enhancement in both modulus and ionic conductivity in the anisotropic hydrogel. This enhancement contributes to significantly improved zinc stripping/plating reversibility and mitigated electrochemical polarization. Additionally, a durable quasi-solid-state Zn//MnO2 battery with noteworthy volumetric energy density is realized. This study offers unique perspectives for designing hydrogel electrolytes and augmenting battery performance.

Modeling and simulation of anisotropic cross-linked cellulose fiber networks with an out-of-plane topography

Non-woven cellulose fiber networks of low areal density are widely used in many industrial applications and consumer products. A discrete element method (DEM) modeling framework is advanced to simulate the formation of strongly anisotropic cellulose fiber network sheets in the dilute limit with simplified hydrodynamic and hydroelastic interactions. Our modeling accounts for in-plane fiber orientation and viscous drag indirectly by using theories developed by Niskanen (2018 Fundamentals of Papermaking, Trans. 9th Pulp and Paper Fundamental Research Symp. Cambridge, 1989 (FRC) pp 275–308) and Cox (1970 J. Fluid Mech. 44 791–810) respectively. Networks formed on a patterned and flat substrate are simulated for different fiber types, and their tensile response is used to assess the influence of the out-of-plane topographical pattern, specifically, on their stiffness and strength. Sheets with the same grammage and thickness, but composed with a higher fraction of softwood fiber (longer fibers with large diameter), have higher strength and higher strain to failure compared to sheets made from hardwood fibers (short fibers with small diameter). However, varying the fiber fraction produces only an insignificant variation in the initial sheet stiffness. The above simulation predictions are confirmed experimentally for sheets comprised of fibers with different ratios of Eucalyptus kraft and Northern Bleached Softwood Kraft fibers. Sheets with out-of-plane topography show an unsymmetric mass distribution, lower tensile stiffness, and lower tensile strength compared to those formed on a flat substrate. The additional fiber deformation modes activated by the out-of-plane topography, such as bending and twisting, explain these differences in the sheet mechanical characteristics.

Solidified water at room temperature hosting tailored fluidic channels by using highly anisotropic cellulose nanofibrils

Highly anisotropic cellulose nanofibrils can solidify liquid water, creating self-supporting structures by incorporating a tiny number of fibrils. These fibrillar hydrogels can contain as much as 99.99 wt% water. The structure and mechanical properties of fibrillar networks have so far not been completely understood, nor how they solidify the bulk water at such low particle concentrations. In this work, the mechanical properties of cellulose fibrillar hydrogels in the dilute regime from a wt% perspective have been studied, and an elastoplastic model describing the network structure and its mechanics is presented. A significant insight from this work is that the ability of the fibrils to solidify water is very dependent on particle stiffness and the number of contact points it can form in the network structure. The comparison between the experimental results and the theoretical model shows that the fibrillar networks in the dilute regime form via a non-stochastic process since the fibrils have the time and freedom to find contact points during network formation by translational and rotational diffusion. The formed, dilute fibrillar network deforms by sliding fibril contacts upon straining the network beyond its elastic limit. Our results also show that before macroscopic failure, the fibril contacts are restored once the load is released. The exceptional properties of this solidified water are exploited to host fluidic channels, allowing directed fluid transportation in water. Finally, the microfluidic channels formed in the hydrogels are tailored by the layer-by-layer technique to be interactive against external stimuli, a characteristic envisioned to be useful in biomedical applications.

Efficient fabrication of anisotropic regenerated cellulose films from bamboo via a facile wet extrusion strategy

Bamboo, featuring fast growth rate and high cellulose content, is considered to be one of the most attractive feedstocks for degradable bio-materials as a substitute for plastics. However, those was limited to the fields of bamboo structural materials mainly by physical processes. Herein, we report a facile continuous wet extrusion strategy for scalable manufacturing of anisotropic regenerated cellulose films in alkali/urea aqueous solution for the first time. The bamboo cellulose solution was regenerated in H2SO4/Na2SO4/ZnSO4 aqueous solution to facilitate the construction of dense fibrils networks. Moreover, under the synergistic effect of shear orientations and stretching processes in wet extrusion molding, the cellulose networks promoted further orientated assembly into aligned fibrils. Therefore, these anisotropic cellulose hydrogels exhibited good mechanical properties, and the tensile strength was increased from 1.67 MPa of anisotropic cellulose hydrogel with 1.0 of stretching ration (ACH-1.0) to 2.13 MPa of ACH-1.4 with increasing stretching ratio from 1.0 to 1.4, which was about 1.34 times higher than that of the isotropic hydrogel fabricated by tape-casting. Moreover, ACH-1.4 exhibited commendable thermal stability and air barrier properties. This work demonstrated a simple and continuous bottom-up approach for fabrication of anisotropic bamboo-based cellulose hydrogels and films with excellent mechanical properties.

Anisotropic Electronic Skin for Neurofeedback

AbstractNeurofeedback training based on brain rhythm is appealing for both cognitive neuroscience and disorder treatment. However, electrodes that can integrate dual functions of recording and feedback without signal compromise still lack. Herein, an anisotropic cellulose carbon sponge (CCS) electrode by tailoring conductivity through the temperature that has the dual ability to record electrophysiological signals and sense pressures as feedback is developed. The electrode is fabricated via a gradient temperature annealing on CCS, which involves lower (300 °C) and higher (1000 °C) temperature treatments, namely CCS‐LT and CCS‐HT. CCS‐LT exhibits perpendicular resilience to the alignment direction of CCS, and CCS‐HT possesses lower sheet resistance (≈13 Ω sq−1) parallel to the alignment direction. As a pressure sensor, CCS‐LT can achieve excellent sensitivity (1.04 kPa−1), fast response time (27 ms), and reliable stability for 1000 cycles. CCS‐HT can serve as skin electrodes for electrophysiological sensing. The anisotropic functionality of annealed CCS allows it to be used in one sensing and regulation closed‐loop system driven by nerves, achieving accurate acquisition of human brain rhythm and machine movement information simultaneously. This not only helps rapid tracking of brain activity but also facilitates feedback regulation to enhance human brain function, having great potential applications in neurofeedback and disease rehabilitation.

Devisable pore structures and tunable thermal management properties of aerogels composed of carbon nanotubes and cellulose nanofibers with various aspect ratios

The anisotropic cellulose nanofiber (CNF)/carbon nanotube (CNT) aerogels hold a great promise in directional applications due to their distinct xylem-like aligned penetrating pore structures. The aspect ratio of CNF plays a crucial role in the pore structures of aerogels, directly dominating the final macroscopic properties of materials. Herein, three types of CNF with different aspect ratios were extracted through the 2,2,6,6-tetrmethylpiperidine-1-oxyl radical (TEMPO) oxidation process by changing the doses of oxidant. The corresponding anisotropic CNF/CNT aerogels were prepared by the unidirectional freeze-drying method and then their pore morphologies and properties were investigated in detail. The resulting aerogel with the shortest aspect ratio of CNF exhibited the densest porous structure, thereby obtaining the highest compressive strength of 110 kPa and elastic modulus of 383 kPa, while that containing the longest CNF possessed the highest thermal conductivity coefficient of 0.17 W m−1 K−1 and the worst thermal insulation. This research explored the relationship between the properties of the CNF/CNT aerogels and devisable pore structures caused by various aspect ratios of CNF, thus providing a new insight into the development of CNF/CNT aerogels with tunable performances.

Light scattering properties of cellulose microcrystals from multiple angles under a magnetic field

Cellulose is a promising sustainable material due to its flexibility and high strength. The light scattering characteristics of anisotropic cellulose crystals from various angles with magnetic orientation were experimentally clarified in this study. The intensity of the light scattered from cellulose crystals is reduced by the application of a magnetic field. Therefore, it was suggested that switching the magnetic field would allow the light intensity to be controlled similarly to an attenuator.

Anisotropic cellulose nanocrystalline sponge sheets with ultrahigh water fluxes and oil/water selectivity

Oily sewage caused by oil spill accidents has become a severe problem in the last decades. Hence, two-dimensional sheet-like filter materials for oil/water separation have received widespread attention. Porous sponge materials were developed using cellulose nanocrystals (CNCs) as raw materials. They are environmentally friendly and easy to prepare, with high flux and separation efficiency. The 1,2,3,4-butane tetracarboxylic acid cross-linked anisotropic cellulose nanocrystalline sponge sheet (B-CNC) exhibited ultrahigh water fluxes driven by gravity alone, depending on the aligned structure of channels and the rigidity of CNCs. Meanwhile, the sponge gained superhydrophilic/underwater superhydrophobic wettability with an underwater oil contact angle of up to 165.7° due to its ordered micro/nanoscale structure. B-CNC sheets displayed high oil/water selectivity without additional material doping or chemical modification. For oil/water mixtures, high separation fluxes of approximately 100,000 L·m−2·h−1 and separation efficiencies of up to 99.99 % were obtained. For a Tween 80-stabilized toluene-in-water emulsion, the flux reached >50,000 L·m−2·h−1, and the separation efficiency was above 99.7 %. B-CNC sponge sheets showed significantly higher fluxes and separation efficiencies than other bio-based two-dimensional materials. This research provides a facile and straightforward fabrication method of environmental-friendly B-CNC sponges for rapid, selective oil/water separation.

Highly transparent, hydrophobic, and durable anisotropic cellulose films as electronic screen protectors

Cellulose films have attracted extensive interest in the field of burgeoning electronic devices. However, it remains a challenge to simultaneously address the difficulties including facile methodology, hydrophobicity, optical transparency, and mechanical robustness. Herein, we reported a coating-annealing approach to fabricate highly transparent, hydrophobic, and durable anisotropic cellulose films, where poly(methyl methacrylate)-b-poly(trifluoroethyl methacrylate) (PMMA-b-PTFEMA) as low surface energy chemicals was coated onto regenerated cellulose films via physical (hydrogen bonds) and chemical (transesterification) interactions. The resultant films with nano-protrusions and low surface roughness exhibited high optical transparency (92.3 %, 550 nm) and good hydrophobicity. Moreover, the tensile strength of the hydrophobic films was 198.7 MPa and 124 MPa in dry and wet states, respectively, which also showed excellent stability and durability under various conditions, such as hot water, chemicals, liquid foods, tape peeling, finger pressing, sandpaper abrasion, ultrasonic treatment, and water jet. This work provided a promising large-scale production strategy for the preparation of transparent and hydrophobic cellulose-based films for electronic device protection as well as other emerging flexible electronics.

Anisotropic double-network hydrogels integrated superior performance of strength, toughness and conductivity for flexible multi-functional sensors

Conductive hydrogels have attracted extensive attention in the field of flexible electronics due to its inherent outstanding properties. However, how to solve the contradictory relationship among conductivity, strength and toughness of hydrogel was still a huge challenge. Inspired by the muscle architecture, an anisotropic cellulose nanofiber (CNF) based double-network conductive hydrogel containing oriented MXenes was successfully fabricated, in which the asymmetric double network structure contributed to excellent strength and toughness, while the conductivity of the hydrogel was enhanced by the ion nanochannels derived from aligned MXenes. Consequently, the resulting hydrogel integrated superior performance of strength, toughness and conductivity, which were 3.33 MPa, 1106 % and 13.08 S/m respectively, surpassing the most reported hydrogels. Profiting from the superior conductivity and mechanical performance, the anisotropic hydrogel could be assembled into multi-functional flexible electronics, such as a flexible touch panel, a flexible strain/pressure sensor with high sensitivity and stability. Together with the superior compatibility for human–computer interaction, the obtained hydrogel wearable sensor showed a promising application potential for the real-time wireless monitoring of human motion and the real-time control of a robot.

Metal oxide cluster-assisted assembly of anisotropic cellulose nanocrystal aerogels for balanced mechanical and thermal insulation properties.

Cellulose nanocrystal (CNC) materials grant abundant possibilities for insulation, however, their extensive application is hindered by the intrinsic tradeoff between their thermal insulating performance and mechanical properties. Here, we show that CNC aerogels with balanced thermal and mechanical performance can be fabricated via a 1 nm metal oxide cluster (phosphotungstic acid, PTA)-assisted unidirectional freeze-drying processing. The as-prepared hybrid aerogels with hierarchical porous structures consisting of layer-by-layer CNC nanosheets enable the decoupling of the strengthening of mechanical properties and the enhancement of thermal insulating capabilities. Within layered structures, the surface-doped nanosized PTA clusters with negative charges behave as dynamic physical cross-linking points, and continuous networks of PTA-doped CNC can be formed via multiple supramolecular interactions (e.g., electrostatic attractions and hydrogen bonds). The afforded stable three-dimensional network structures are able to withstand externally applied forces and large deformations, endowing the aerogels with excellent mechanical performance. Moreover, the inter-layer gap is dominated by nanopores, endowing much lower thermal conductivities along the radial direction in comparison to the axial direction. The addition of PTA clusters also contributes to the obvious enhancements of the fire-retardant properties. Our discoveries provide a facile approach for the design and scalable production of CNC-based insulation materials with optimized mechanical properties and additional fire-retardant properties.

Vertical aligned solid‐state electrolyte templated by nanostructured “upright” cellulose film layers for advanced cell performance

AbstractIn this work, an “upright” cellulose layered template, which can be precisely controlled by the fiber orientation and thickness of anisotropic cellulose film, was first developed to prepare vertically aligned Li7La3Zr2O12 (LLZO) ceramic membrane with low tortuosity and uniform porosity. The flexible composite solid‐state electrolytes (CSEs) were synthesized by incorporating poly(ethylene oxide) (PEO) polymer into LLZO architecture, and exhibited distinguished mechanical strength, elevated ionic conductivity (2.1 × 10−4 S cm−1) and excellent interface compatibility with lithium anodes. The assembled LiFePO4/lithium full cells assembled with as‐obtained CSEs can reach large discharge capacities of 172.3 mAh g−1 with coulombic efficiencies of above 99% and capacity retention of 93.1% even after 200 cycles. These results clearly demonstrate that the sophisticated design of vertical aligned cellulose layered template with fine‐scale size and exquisite architecture is a promising and practical approach in fabricating flexible LLZO@PEO‐LiTFSI CSEs with high‐safety and high‐performance.image

Anisotropic cellulose nanofibril aerogels fabricated by directional stabilization and ambient drying for efficient solar evaporation

Anisotropic aerogels, mimicking natural porous materials such as wood and bone, always exhibit distinctive properties due to their aligned channels, which, however, generally require complicated ice templating configuration and costly freeze-drying. In this work, we develop a novel, facile, low-cost, and scalable method combining directional stabilization and ambient drying to prepare anisotropic aerogels. The frozen aqueous TEMPO-oxidized cellulose nanofibrils (TOCNFs) monolith embedded in a mold is directly immersed in ethanol/Fe3+ bath. The ice crystals directionally dissolve in ethanol, and simultaneously the TOCNFs are directionally stabilized due to the electrostatic complexation between their carboxyl groups and Fe3+ ions. The obtained anisotropic nanocellulose aerogel (NCA) after ambient drying exhibits an ordered porous structure, which is tunable by adjusting the contents of carboxyl groups on TOCNFs. The NCAs reveal distinct anisotropy, excellent mechanical compressibility in the radial direction, and high water-stability. To demonstrate their promising potentials for application in various advanced fields such as solar steam generation, the NCA is coated with polypyrrole (PPy) by in-situ polymerization to achieve excellent photothermal property but well maintain the original aligned channels of NCA, which endow the NCA@PPy with an efficient solar evaporation performance.

Naturally Derived Janus Cellulose Nanomaterials: Anisotropic Cellulose Nanomaterial Building Blocks and Their Assembly into Asymmetric Structures.

Naturally derived cellulose nanomaterials (CNMs) with desirable physicochemical properties have drawn tremendous attention for their versatile applications in a broad range of fields. More recently, Janus amphiphilic cellulose nanomaterial particles with asymmetric structures (i.e., reducing and nonreducing ends and crystalline and amorphous domains) have been in the spotlight, offering a rich and sophisticated toolbox for Janus nanomaterials. With careful surface and interfacial engineering, Janus CNM particles have demonstrated great potential as surface modifiers, emulsifiers, stabilizers, compatibilizers, and dispersants in emulsions, nanocomposites, and suspensions. Naturally derived Janus CNM particles offer a fascinating opportunity for scaling up the production of self-standing Janus CNM membranes. Nevertheless, most Janus CNM membranes to date are constructed by asymmetric fabrication or asymmetric modification without considering the Janus traits of CNM particles. More future research should focus on the self-assembly of Janus CNM particles into bulk self-standing Janus CNM membranes to enable more straightforward and sustainable approaches for Janus membranes. This review explores the fabrication, structure-property relationship, and Janus configuration mechanisms of Janus CNM particles and membranes. Janus CNM membranes are highlighted for their versatile applications in liquid, thermal, and light management. This review also highlights the significant advances and future perspectives in the construction and application of sustainable Janus CNM particles and membranes.

Superhydrophobic, elastic and anisotropic cellulose nanofiber aerogels for highly effective oil/water separation

Nanocellulose-based aerogels have gradually attracted attention in the field of oil/water separation owing to their light weight, excellent absorption properties, and environmental-friendliness. Herein, we report a facile and easily scalable method for fabricating superhydrophobic, elastic and anisotropic cellulose nanofiber (CNF) aerogels. Directional freeze-drying, soaking in polydimethylsiloxane (PDMS) solution and heat treatment were applied to obtain anisotropic and aligned CNF-PDMS aerogel sheets and blocks with superhydrophobicity and high elasticity. The CNF-PDMS aerogel sheets could realize continuous oil/water separation by filtration with a flux up to 2800 L·m−2·h−1 and a separation efficiency of 99.9%. The CNF-PDMS aerogel blocks could separate the oil/water mixture by the absorption–extrusion, and could also be applied in real-time continuous oil/water separation by vacuum suction with a flux as high as 145 L·h−1·g−1 and a separation efficiency of 99.9%. Overall, our anisotropic CNF-PDMS aerogels are the promising materials for low-cost rapid oil/water separation in multiple separation pathways.

Lightweight and anisotropic cellulose nanofibril/rectorite composite sponges for efficient dye adsorption and selective separation

Constructing lightweight and porous adsorbents which can effectively remove dye contaminants is of great significance in the field of the sewage treatment. In this work, anisotropic cellulose nanofibril (CNF) composite sponges assisted by rectorites are fabricated through directional freeze-drying. The resulted composite sponge exhibits the superior saturated adsorption capacity and removal efficiency of 120.0 mg/g and 96.1% for methylene blue (MB), respectively, which is better than the pure CNF sponge and rectorite powders. This is attributed to the strong electrostatic interaction between CNFs and MB, and good cation exchange property of rectorites inside the three-dimensional (3D) highly porous composite sponge. The MB adsorption process of the composite sponge fits to the pseudo-second-order kinetic model and the Langmuir isotherm model well, which is affected by both boundary layer and intraparticle diffusion, resulting in a theoretical maximum adsorption capacity of 214.6 mg/g. Moreover, it also possesses a selective adsorption capacity for anionic and cationic dyes, which is expected to realize the separation treatment of different dyes according to actual application requirements.

Cell twisting during desiccation reveals axial asymmetry in wall organization

Plant cell size and shape are tuned to their function and specified primarily by cellulose microfibril (CMF) patterning of the cell wall. Arabidopsis thaliana leaf trichomes are unicellular structures that act as a physical defense to deter insect feeding. This highly polarized cell type employs a strongly anisotropic cellulose wall to extend and taper, generating sharply pointed branches. During elongation, the mechanisms by which shifts in fiber orientation generate cells with predictable sizes and shapes are unknown. Specifically, the axisymmetric growth of trichome branches is often thought to result from axisymmetric CMF patterning. Here, we analyzed the direction and degree of twist of branches after desiccation to reveal the presence of an asymmetric cell wall organization with a left-hand bias. CMF organization, quantified using computational modeling, suggests a limited reorientation of microfibrils during growth and a maximum branch length limited by the wall axial stiffness. The model provides a mechanism for CMF asymmetry, which occurs after the branch bending stiffness becomes low enough that ambient bending affects the principal stresses. After this stage, the CMF synthesis results in a constant bending stiffness for longer branches. The bending vibration natural frequencies of branches with respect to their length are also discussed.

Highly Transparent, Hydrophobic, and Durable Anisotropic Cellulose Films as Electronic Screen Protectors

Highly Transparent, Hydrophobic, and Durable Anisotropic Cellulose Films as Electronic Screen Protectors