Cellulose Fiber Networks Research Articles

DRIED NATA DE COCO WITH WATER ABSORPTIVITY COMPETING SILICA GEL

Nata de Coco (NDC) is a network of cellulose fibers that traps abundant of water. If a freshly made NDC is dried to remove nearly all trapped water, we will get a very hygroscopic material. This material is potential for making water adsorber that might compete the well known silica gel. NDC was prepared using standard methods and its water absorption was investigated. Dried NDC was used in this study. For comparison, we also investigated the water absorption of several commercial NDC. To determine its business prospects, the water absorption of silica gel was also investigated. The results showed that dried NDC could absorb water vapor comparable to the absorption of commercial silica gel. This suggests that dry NDC has the potential as an alternative water vapor absorber in food packaging. The advantages of the NDC compared to silica gel are safer and environmentally benign, and easily decomposed.

SANS investigation of fungal loosenins reveal substrate dependent impacts of protein 1 action on inter-fibril distance and packing order of cellulosic substrates.

Microbial expansin-related proteins include fungal loosenins, which have been previously shown to disrupt cellulose networks and enhance the enzymatic conversion of cellulosic substrates. Despite showing beneficial impacts to cellulose processing, detailed characterization of cellulosic materials after loosenin treatment is lacking. In this study, small-angle neutron scattering (SANS) was used to investigate the effects of three recombinantly produced loosenins that originate from Phanerochaete carnosa, PcaLOOL7, PcaLOOL9, and PcaLOOL12, on the organization of holocellulose preparations from Eucalyptus and Spruce wood samples. Whereas the SANS analysis of Spruce holocellulose revealed an increase in interfibril spacing of neighboring cellulose microfibrils following treatment with PcaLOOL12 and to a lesser extent PcaLOOL7, the analysis of Eucalyptus holocellulose revealed a reduction in packing number following treatment with PcaLOOL12 and to a lesser extent PcaLOOL9. Parallel SEC-SAXS characterization of PcaLOOL7, PcaLOOL9, and PcaLOOL12 indicated the proteins likely function as monomers; moreover, all appear to retain a flexible disordered N-terminus and folded C-terminal region. The comparatively high impact of PcaLOOL12 motivated its NMR structural characterization, revealing a double-psi b-barrel (DPBB) domain surrounded by three alpha-helices - the largest nestled against the DPBB core and the other two part of loops extending from the core. The SANS analysis of PcaLOOL action on holocellulose samples confirms their ability to disrupt cellulose fiber networks and suggests a progression from reducing microfibril packing to increasing interfibril distance. The most impactful PcaLOOL, PcaLOOL12, was previously observed to be the most highly expressed loosenin in P. carnosa. Its structural characterization herein reveals its stabilization through two disulfide linkages, and an extended N-terminal region distal to a negatively charged and surface accessible polysaccharide binding groove.

Valorization of Grass Clipping Waste: A Sustainable Approach to Cellulose Extraction and Paper Manufacturing

This study investigates the physical, mechanical, and structural characteristics of handmade paper samples derived from cellulose extracted from grass clippings using two distinct methods as follows: (1) alkali treatment and (2) alkali treatment followed by bleaching, coupled with the incorporation of barium sulfate as a mineral filler. Our investigation revealed that the handmade paper samples’ densities, moisture contents, and thicknesses varied within the ranges of 0.436 to 0.549 g/cm3, 5.60 to 2.51%, and 0.41 to 0.50 mm, respectively. The tensile strength and folding endurance of the papers produced through alkali treatment with barium sulfate were notably superior to those produced from bleached pulp and barium sulfate. Our analysis indicates that several critical factors, including paper density, thickness, the crystallinity index, and the microfibrillar structure of cellulose, intricately influence the mechanical and strength properties of the samples. Using Fourier transform infrared spectroscopy (FT-IR) and X-ray diffraction (XRD) techniques, we identified characteristic cellulose bonds and examined cellulose’s crystalline and amorphous phases. Additionally, the crystallinity index of the samples was determined using both the Segal and peak deconvolution methods. Scanning electron microscopy (SEM) micrographs revealed interconnected networks of cellulose fibers with varying thicknesses and lengths, along with incorporated mineral filler within the cellulose fiber structure. Variations in mineral particle retention were attributed to the presence or absence of cellulose microfibrils. These findings contribute to our understanding of the observed strength characteristics of the paper samples and underscore the potential applications of cellulose derived from grass clippings, especially when combined with barium sulfate as a mineral filler in paper production.

A novel in-situ micro-mechanical testing of paper fracture and its stochastic network model

Understanding and simulating the evolution of fracture in cellulose-based paper materials is vital for many eco-sustainable applications of packaging solutions. In this work, we conduct an integrated experimental-statistical mechanics analysis to elucidate how the microstructural mechanisms govern the fracture behavior of paper. We employ in-situ tensile tests combined with confocal microscopy to observe and analyze key microstructural phenomena, such as fibers’ activation and recruitment, and progressive tensile failure of unnotched paper samples under uniaxal loading. The developed stochastic mechanics critical cross-section model to treat the cellulose fiber network is able to decouple the stochastic morphological parameters from the constitutive model of the fibers. Notably, it robustly predicts the anisotropic properties of paper materials in the machine direction (MD) and cross-machine direction (CD) as a direct consequence of the different statistical distribution of fibers’ orientation, for the same fiber constitutive model. The proposed approach is finally employed to get an insight into the role of the main morphological parameters, local/non-local fibers’ strain redistribution, and finite elasticity of fibers on the whole mechanical behavior of paper.

Bio‐inspired hierarchical bamboo‐based air filters for efficient removal of particulate matter and toxic gases

AbstractAir pollution is caused by the perilous accumulation of particulate matter (PM) and harmful gas molecules of different sizes. There is an urgent need to develop highly efficient air filtration systems capable of removing particles with a wide size distribution. However, the efficiency of current air filters is compromised by controlling their hierarchical pore size. Inspired by the graded filtration mechanisms in the human respiratory system, microporous ZIF‐67 is in situ synthesized on a 3D interconnected network of bamboo cellulose fibers (BCFs) to fabricate a multiscale porous filter with a comprehensive pore size distribution. The macropores between the BCFs, mesopores formed by the BCF microfibers, and micropores within the ZIF‐67 synergistically facilitate the removal of particulates of different sizes. The filtration capabilities of PM2.5 and PM0.3 could reach 99.3% and 98.6%, respectively, whereas the adsorption of formaldehyde is 88.7% within 30 min. In addition, the filter exhibits excellent antibacterial properties (99.9%), biodegradability (80.1% degradation after 14 days), thermal stability, and skin‐friendly properties (0 irritation). This study may inspire the research of using natural features of renewable resources to design high‐performance air‐filtration materials for various applications.

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.

Comparison of the SMLM technique and the MSSR algorithm in confocal microscopy for super-resolved imaging of cellulose fibres.

Nowadays, the use of super-resolution microscopy (SRM) is increasing globally due to its potential application in several fields of life sciences. However, a detailed and comprehensive guide is necessary for understanding a single-frame image's resolution limit. This study was performed to provide information about the structural organisation of isolated cellulose fibres from garlic and agave wastes through fluorophore-based techniques and image analysis algorithms. Confocal microscopy provided overall information on the cellulose fibres' microstructure, while techniques such as total internal reflection fluorescence microscopy facilitated the study of the plant fibres' surface structures at a sub-micrometric scale. Furthermore, SIM and single-molecule localisation microscopy (SMLM) using the PALM reconstruction wizard can resolve the network of cellulose fibres at the nanometric level. In contrast, the mean shift super-resolution (MSSR) algorithm successfully determined nanometric structures from confocal microscopy images. Atomic force microscopy was used as a microscopy technique for measuring the size of the fibres. Similar fibre sizes to those evaluated with SIM and SMLM were found using the MSSR algorithm and AFM. However, the MSSR algorithm must be cautiously applied because the selection of thresholding parameters still depends on human visual perception. Therefore, this contribution provides a comparative study of SRM techniques and MSSR algorithm using cellulose fibres as reference material to evaluate the performance of a mathematical algorithm for image processing of bioimages at a nanometric scale. In addition, this work could act as a simple guide for improving the lateral resolution of single-frame fluorescence bioimages when SRM facilities are unavailable.

Nano-captured water affects the wettability of cellulose nanofiber films

In this study, we report that the wettability of cellulose nanofiber films varies with their thickness, and this variation is attributed to the amount of water captured within the hydrogel-like film. To investigate this, we conducted water contact angle measurements on cellulose nanofiber films with different thicknesses. The wettability of the films was found to change from hydrophilic (approximately 20°) to that of the underlying silicon substrate (approximately 80°) by decreasing the mean film thickness within a range of 150 nm or less. Transmission electron microscope observations revealed that even under high-vacuum conditions (< 10−5 Pa), water was captured in regions where the film was thick enough to form a dense, three-dimensional network. However, in regions where the film was thin, the network structure became sparse and two-dimensional, and no water was observed. We propose that the wettability of cellulose nanofiber films changes based on the area ratio of water captured in thick 3D network regions, the underlying substrate, and the cellulose nanofibers. Furthermore, we quantitatively evaluated the relationship between the area ratio and the wetting state of the composite surface based on the Cassie-Baxter equation, then determined the minimum thickness at which water is retained within the cellulose fiber network.

Mulch from lignocellulose as agricultural plastic alternative for sustained-release of photosensitive pesticide

Extensively used agricultural mulch fabricated from nonbiodegradable polyolefin plastic causes tremendous environmental pollution. In this work, a paper-based mulch, composed of the cellulose fiber networks incorporated with Emamectin benzoate (EB)@sodium lignosulfonate (SL), has been developed with facile papermaking/coating methods. The spherical microcapsule loaded with pesticide EB has a desirable core-shell structure for better protection and sustained release of photosensitive EB. The loading rate and encapsulation efficiency reached 78.5 % and 52.3 %, respectively. Furthermore, microcapsules exhibited excellent slow-release behavior and resistance to photolysis. Natural carnauba wax was coated on the surface of the paper-based mulch to form a hydrophobic layer and increase the physical intertwinement of fibers in the mulch, thereby exhibiting superior performance, such as enhanced tensile strength, excellent hydrophobicity, high air permeability, and high light transmittance at reasonable level. Moreover, unlike conventional polyethylene mulch film, the functionalized paper-based mulch almost completely biodegraded after 75 days in the soil. Thus, multifunctional, eco-friendly mulch from lignocellulose is an innovative approach to obtaining the sustained release of agrochemicals, and it provides an excellent alternative to conventional agricultural plastic mulch.

Evaluation of elasto-plastic properties of bacterial cellulose-hemicellulose composite films

Bacterial cellulose (BC) is a natural biopolymer of β-(1,4)-linked β-D-glucopyranose that forms a homogeneous network of cellulose fibres with high chemical purity and modifiability. Plasticizers of the BC fibre network allow to reduce its brittleness and improve flexibility by reducing the intermolecular forces and increasing the chain mobility, while the opposite effect was observed for the antiplasticizing additives. Therefore, the aim of the current study was to investigate the effect of hemicellulose addition on the elasto-plastic response of BC-hemicellulose composite films depending on the specific type of hemicellulose and its concentration. BC-hemicellulose composite films were produced by K.xylinum bacteria strain in the hemicellulose-modified medium. The presence of xylan and arabinoxylan in the culturing medium resulted in an increase in the plastic deformation of the composite films, its maximum stress and maximum strain, which was opposite to the effects of glucomannan and xyloglucan. Spectral studies revealed that the deformation of the hemicellulose polysaccharides played a minor role in opposing of applied loads. The contribution of the hydrogen bond network in opposing of applied loads was comparable to that of the glycosidic bonds. Stretching vibrations of the structural bonds of BC-hemicellulose composite films determined elastic deformation most, compared to other bonds.

Fast transport diffusion of bound water in cellulose fiber network

AbstractA remarkable property of cellulose-based materials is that they can absorb huge amounts of water (25% of the dry mass) from ambient vapor, in the form of bound water confined at a nanoscale in the amorphous regions of the cellulose structure. The control of the dynamics of sorption and desorption of bound water is a major stake for the reduction of energy consumption and material or structure damages, but in the absence of direct observations this process is still poorly known. Here we present measurements of bound water transport thanks to Nuclear Magnetic Resonance relaxometry and Magnetic Resonance Imaging measurements. We show that the bound water is transported along the fibers and throughout the network of fibers in contact. For each material a single transport diffusion coefficient value allows to represent the processes over the whole range of saturation. The dependence of the transport diffusion coefficient on the fiber density and orientation is then analyzed to deduce the (elementary) transport diffusion coefficient of bound water along a cellulose fiber axis. This constitutes fundamental physical data which may be compared with molecular simulations, and opens the way to the prediction and control of sorption dynamics of all cellulosic materials or other hygroscopic materials.

Cell repelling agar@paper interface assisted probing of the tumor spheroids infiltrating natural killer cells

Scaffold-based culture is one of the effective methods to resemble three-dimensional (3D) cells model in vitro. An agar@lens paper hybrid scaffold was prepared by one-pot dip-coating. The lens paper's cellulose fiber networks are the scaffold's backbone. The agar gel seized the gaps between the fibrous structures that can improve the paper scaffold's optical transparency and prevent cells from spreading on the scaffold. The SEM and light microscope images showed that the agar gel on the bottom of the paper and the cellulose fiber of the paper formed micro-well structures. Without staining, the cells growing on the agar@paper scaffold can be directly observed under a light microscope. Cells aggregated between the cellulose fibers and formed spheroids within 24 h. The cell spheroids can be non-enzymatically retrieved from the agar@paper scaffold because of the cell-repelling property of agar. The agar@paper scaffold was applied for co-culturing tumor cells (MDA-MB-231, DU 145) and natural killer cells (NKs, NK-92). Using the agar@paper scaffolds, the tumor-infiltrating NKs can be separated from floating NKs that did not attack the tumor spheroids. The effect of NKs infiltrating on tumor spheroids size was characterized. The results showed that NKs attacking the spheroids grown on agar@paper scaffold can be readily tracked because of the improved optical transparency. Higher NKs: tumor cells ratio resulted in a high percentage of tumor infiltrating NKs. The separated NKs can be further tested to reveal their biological characteristics. Both agar and lens paper is accessible for most biological labs, highlighting the potential of agar@paper scaffold in 3D culture.

Chemical Gradients in Polymer-Modified Paper Sheets—Towards Single-Layer Biomimetic Soft Robots

Biomimetic actuators are typically constructed as functional bi- or multilayers, where actuating and resistance layers together dictate bending responses upon triggering by environmental stimuli. Inspired by motile plant structures, like the stems of the false rose of Jericho (Selaginella lepidophylla), we introduce polymer-modified paper sheets that can act as soft robotic single-layer actuators capable of hygro-responsive bending reactions. A tailored gradient modification of the paper sheet along its thickness entails increased dry and wet tensile strength and allows at the same time for hygro-responsiveness. For the fabrication of such single-layer paper devices, the adsorption behavior of a cross-linkable polymer to cellulose fiber networks was first evaluated. By using different concentrations and drying procedures fine-tuned polymer gradients throughout the thickness can be achieved. Due to the covalent cross-linking of polymer with fibers, these paper samples possess significantly increased dry and wet tensile strength properties. We furthermore investigated these gradient papers with respect to a mechanical deflection during humidity cycling. The highest humidity sensitivity is achieved using eucalyptus paper with a grammage of 150 g m-2 modified with the polymer dissolved in IPA (~13 wt%) possessing a polymer gradient. Our study presents a straightforward approach for the design of novel hygroscopic, paper-based single-layer actuators, which have a high potential for diverse soft robotic and sensor applications.

Cellulose fiber network as reinforcement of thermoplastic paraffin films

Cellulose fiber network as reinforcement of thermoplastic paraffin films

Dendrite‐Free 3D Lithium Metal Anode Formed in a Cellulose Based Separator for Lithium‐Metal Batteries

AbstractLithium metal is the best candidate anode for high specific energy density batteries because of its high specific capacity and low negative potential. However, lithium dendrite formation and growth during the lithium plating and stripping cycles have hindered the use of lithium metal as the anode for practical batteries. Here, a mechanism for the suppression of lithium dendrite formation and growth in a composite separator of Kimwipe paper (KW) and porous polyethylene (PE) for various electrolytes was examined. The Li/KW/PE electrode in an electrolyte of 1 m Li(CFSO3)2N (LiFSI) in 1,4, dioxane (DX)‐1,2 dimethoylethane (DME) (1 : 2 v/v) with a wide electrochemical window was successfully cycled without lithium dendrite short‐circuiting at 5 mA cm−2 and 25 °C for 10 h over 25 cycles. Lithium was deposited into the cellulose fiber network during the lithium plating process, which resulted in the formation of a three‐dimensional (3D) lithium electrode. Whereas, the composite separator of KW and PE was not effective to suppress the lithium dendrite formation and growth with the conventional carbonate based electrolyte of 1 m LiPF6 in ethylene carbonate‐dimethyl carbonate.

Living materials made by 3D printing cellulose-producing bacteria in granular gels.

Bacterial cellulose is an attractive resource for the manufacturing of sustainable materials, but it is usually challenging to shape it into elaborate three-dimensional structures. Here, we report a manufacturing platform for the creation of complex-shaped cellulose objects by printing inks loaded with bacteria into a silicone-based granular gel. The gel provides the viscoelastic behavior necessary to shape the bacteria-laden ink in three dimensions and the gas permeability required to sustain cellular growth and cellulose formation after the printing process. Using Gluconacetobacter xylinus as model cellulose-producing bacteria, we study the growth and the mechanical properties of cellulose fiber networks obtained upon incubation of the printed inks. Diffusion processes within the ink were found to control the growth of the cellulose structures, which display mechanical properties within the range expected for conventional hydrogels. By keeping the bacteria alive in the printed object, we produce living materials in complex geometries that are able to self-regenerate their cellulose fiber network after damage. Such living hydrogels represent an enticing development towards functional materials with autonomous self-healing and self-regenerating capabilities.

Humidity dependence of fracture toughness of cellulose fibrous networks

Cellulose-based materials are increasingly finding applications in technology due to their sustainability and biodegradability. The sensitivity of cellulose fiber networks to environmental conditions such as temperature and humidity is well known. Yet, there is an incomplete understanding of the dependence of the fracture toughness of cellulose networks on environmental conditions. In the current study, we assess the effect of moisture content on the out-of-plane (i.e., z-dir.) fracture toughness of a particular cellulose network, specifically Whatman cellulose filter paper. Experimental measurements are performed at 16% RH along the desorption isotherm and 23, 37, 50, 75% RH along the adsorption isotherm using out-of-plane tensile tests and double cantilever beam (DCB) tests. Cohesive zone modeling and finite element simulations are used to extract quantitative properties that describe the crack growth behavior. Overall, the fracture toughness of filter paper decreased with increasing humidity. Additionally, a novel model is developed to capture the high peak and sudden drop in the experimental force measurement caused by the existence of an initiation region. This model is found to be in good agreement with experimental data. The relative effect of each independent cohesive parameter is explored to better understand the cohesive zone-based humidity dependence model. The methods described here may be applied to study rupture of other fiber networks with weak bonds.

3D cellulose fiber networks modified by PEDOT:PSS/graphene nanoplatelets for thermoelectric applications

Organic materials have attracted considerable attention for thermoelectric (TE) applications. Given their potential as wearable power generators, there is an urgent need to develop organic TE materials that possess superior electronic properties as well as excellent mechanical and environmental stability. Here, we develop paper-based TE materials using the poly(3,4-ethylenedioxythiophene): polystyrenesulfonate (PEDOT:PSS), graphene nanoplatelets (GNPs), and a starch-based biopolymer as a binder for GNPs. The device fabrication consists of spraying the biopolymer/GNP ink onto the cellulose paper followed by spraying the PEDOT:PSS solution. Further enhancement of TE properties was obtained by adding an ionic liquid (IL), bis(trifluoromethane)sulfonimide lithium salt to the PEDOT:PSS solution. Upon addition of the IL, the electrical conductivity of as-fabricated PEDOT:PSS films increased nearly two orders of magnitude. The electrical conductivity increases with GNPs' content due to formation of an effective electrical percolation network. Interestingly, incorporating GNPs simultaneously improves the Seebeck coefficient. Raman measurements suggest that the concurrent enhancement of the Seebeck coefficient and electrical conductivity might be related to the chemical bonding between the conducting polymer chains and the filler. In addition, these composites display remarkable flexibility at various bending angles and environmental stability without losing their original conductivity after three months of exposure to ambient conditions.

Towards unraveling the moisture-induced shape memory effect of wood: the role of interface mechanics revealed by upscaling atomistic to composite modeling

The moisture-induced shape memory effect (SME) is one of the most intriguing phenomena of wood, where wood can stably retain a certain deformed shape and, upon moisture sorption, can recover the original shape. Despite the long history of wood utilization, the SME is still not fully understood. Combining molecular dynamics (MD) and finite-element (FE) modeling, a possible mechanism of the SME of wood cell walls is explored, emphasizing the role of interface mechanics, a factor previously overlooked. Interface mechanics extracted from molecular simulations are implemented in different mechanical models solved by FEs, representing three configurations encountered in wood cell walls. These models incorporate moisture-dependent elastic moduli of the matrix and moisture-dependent behavior of the interface. One configuration, denoted as a mechanical hotspot with a fiber–fiber interface, is found to particularly strengthen the SME. Systematic parametric studies reveal that interface mechanics could be the source of shape memory. Notably, upon wetting, the interface is weak and soft, and the material can be easily deformed. Upon drying, the interface becomes strong and stiff, and composite deformation can be locked. When the interface is wetted again and weakened, the previously locked deformation cannot be sustained, and recovery occurs. The elastic energy and topological information stored in the cellulose fiber network is the driving force of the recovery process. This work proposes an interface behaving as a moisture-induced molecular switch.

Electro-Active and Photo-Active Vanadium Oxide Nanowire Thermo-Hygroscopic Actuators for Kirigami Pop-up.

Emerging technologies such as soft robotics, active biomedical devices, wearable electronics, haptic feedback systems, and healthcare systems require high‐fidelity soft actuators showing reliable responses under multi‐stimuli. In this study, the authors report an electro‐active and photo‐active soft actuator based on a vanadium oxide nanowire (VONW) hybrid film with greatly improved actuation performances. The VONWs directly grown on a cellulose fiber network increase the surface area up to 30‐fold and boost the hydrophilicity owing to the presence of oxygen‐rich functional groups in the nanowire surfaces. Taking advantage of the high surface area and hydrophilicity of VONWs, a soft thermo‐hygroscopic VONW actuator capable of being controlled by both light and electric sources shows greatly enhanced actuation deformation by almost 70% and increased actuation speed over 3 times during natural convection cooling. Most importantly, the proposed VONW actuator exhibits a remarkably improved blocking force of up to 200% compared with a bare paper actuator under light stimulation, allowing them to realize a complex kirigami pop‐up and to accomplish repeatable shape transformation from a 2D planar surface to a 3D configuration.