Cellulose Nanofibrils Materials Research Articles

Influence of fibril aspect ratio, chemical functionality, and volume fraction on the mechanical properties of cellulose nanofibril materials

Nanocellulose has emerged as a widely utilized building block in nanostructured materials due to its availability, sustainability, large surface area, and high stiffness and aspect ratio. The wet or dry elastoplastic properties of these materials are determined by the fibrils' stiffness, chemical properties, hemicellulose content, and the number of fibril contacts. However, the specific contributions and relative importance of each factor remain unclear. Therefore, this work was devoted to systematically comparing the material properties of gels, aerogels, and wet and dry sheets prepared from CNFs with different aspect ratios, chemical functionality, and hemicellulose content. The fibrils were prepared by chemical and mechanical processing of different pulps. By preserving the native structure as much as possible, higher aspect ratio fibrils can be obtained, which allows for the development of more mechanically robust materials. The results demonstrate that higher aspect ratios lead to more interconnected networks at a lower solids concentration, resulting in a more evenly distributed stress and longer-range stress transfer, yielding stiffer and more ductile materials. The most important finding was that the aspect ratio influences the network formation, resulting in different network topologies. The results were also compared to earlier published data and integrated into a theoretical beam-bending model for a complete elastoplastic description of the network properties, including the influence of fibril aspect ratio and chemical functionality. This information improves our understanding and description of nanofibril networks for which general models have been missing. It can be used to optimize nanofibril preparation and, hence, the resulting eco-friendly materials.

Aqueous synthesis of highly functional, hydrophobic, and chemically recyclable cellulose nanomaterials through oxime ligation

Cellulose nanofibril (CNF) materials are candidates for the sustainable development of high mechanical performance nanomaterials. Due to inherent hydrophilicity and limited functionality range, most applications require chemical modification of CNF. However, targeted transformations directly on CNF are cumbersome due to the propensity of CNF to aggregate in non-aqueous solvents at high concentrations, complicating the choice of suitable reagents and requiring tedious separations of the final product. This work addresses this challenge by developing a general, entirely water-based, and experimentally simple methodology for functionalizing CNF, providing aliphatic, allylic, propargylic, azobenzylic, and substituted benzylic functional groups. The first step is NaIO4 oxidation to dialdehyde-CNF in the wet cake state, followed by oxime ligation with O-substituted hydroxylamines. The increased hydrolytic stability of oximes removes the need for reductive stabilization as often required for the analogous imines where aldehyde groups react with amines in water. Overall, the process provides a tailored degree of nanofibril functionalization (2–4.5 mmol/g) with the possible reversible detachment of the functionality under mildly acidic conditions, resulting in the reformation of dialdehyde CNF. The modified CNF materials were assessed for potential applications in green electronics and triboelectric nanogenerators.

Fabrication and Characterization of Hydrophobic Cellulose Nanofibrils/Silica Nanocomposites with Hexadecyltrimethoxysilane.

Cellulose nanofibrils (CNFs) have attracted much attention because of their renewability and potential biocompatibility. However, CNFs are extremely hydrophilic due to the presence of a large number of hydroxyl groups, limiting their use as a water-resistant material. In this work, we controlled the adsorption behavior of silica nanoparticles on the surface of CNFs by adjusting the synthesis conditions. The silica nanoparticle size and packing efficiency on the CNF surface could be controlled by varying the ammonium hydroxide and water concentrations. In addition, hexadecyltrimethoxysilane (HDTMS) was successfully grafted onto CNF or CNF/silica nanocomposite surfaces, and the quantitative content of organic/inorganic substances in HDTMS was analyzed through XPS and TGA. The HDTMS-modified CNF/silica nanocomposites were more advantageous in terms of hydrophobicity than the HDTMS-modified CNF composites. This is because the silica nanoparticles were adsorbed on the surface of the CNFs, increasing the surface roughness and simultaneously increasing the amount of HDTMS. As a result, the HDTMS-modified CNFs showed a water contact angle (WCA) of ~80°, whereas HDTMS-modified CNF/silica nanocomposites obtained superhydrophobicity, with a WCA of up to ~159°. This study can provide a reference for the expansion of recyclable eco-friendly coating materials via the adsorption of silica nanoparticles and hydrophobic modification of CNF materials.

Characterization of Porous Structures of Cellulose Nanofibrils Loaded with Salicylic Acid.

Bleached and unbleached pulp fibers were treated with 2,2,6,6-tetramethylpyperidine-1-oxyl (TEMPO) mediated oxidation to obtain cellulose nanofibrils (CNFs). The resulting bleached and unbleached CNFs were mixed with salicylic acid (0, 5, 10, 20 wt%) before casting and freeze-drying or 3D-printing. A series of methods were tested and implemented to characterize the CNF materials and the porous structures loaded with salicylic acid. The CNFs were characterized with atomic force microscopy and laser profilometry, and release of salicylic acid was quantified with UV-visible absorbance spectroscopy, conductivity measurements, and inductive coupled plasma mass spectrometry (ICP-MS). Fourier-transform infrared spectroscopy (FTIR) complemented the analyses. Herein, we show that aerogels of bleached CNFs yield a greater release of salicylic acid, compared to CNF obtained from unbleached pulp. The results suggest that biodegradable constructs of CNFs can be loaded with a plant hormone that is released slowly over time, which may find uses in small scale agricultural applications and for the private home market.

Preparation and thermal stability evaluation of cellulose nanofibrils from bagasse pulp with differing hemicelluloses contents

In this work, cellulose nanofibrils (CNFs) are produced from bagasse pulps with differing hemicelluloses contents by ultrafine grinding and high-pressure homogenization. The results showed that hemicelluloses content in the range of 9.7–21.7 wt.% led to nanofibrils with average diameter. A decrease in hemicelluloses content can enhance the crystallinity and improve the thermal stability of the CNFs. The activation energy of the CNF samples with hemicelluloses contents of 9.7 wt.%, 12.72 wt.%, 15.7 wt.%, 18.76 wt.%, and 21.7 wt.% are 713.03, 518.93, 462.62, 421.78, and 211.11 kJ/mol, respectively, when the conversion rate is increased from 30%–90%. These results demonstrate that hemicelluloses content has a considerable influence on the properties of CNFs. This work provides a theoretical basis for high-value utilization of CNFs, and enriches useful information on the application of CNF materials.

Antimicrobial Cellulose Nanofibril Porous Materials Obtained by Supercritical Impregnation of Thymol.

This study presents the impregnation in supercritical carbon dioxide (scCO2) of nanocellulose-based structures with thymol as a natural antimicrobial molecule to prepare bioactive, biosourced materials. First, cellulose nanofibrils (CNFs) were used to produce four types of materials (nanopapers, cryogels from water or tert-butyl alcohol suspensions, and aerogels) of increasing specific surface area up to 160 m2·g-1, thanks to the use of different processes, namely, vacuum filtration, freeze-drying, and supercritical drying. Second, these CNF-based structures were impregnated with thymol in the scCO2 medium using a relatively low temperature and pressure of 40 °C and 100 bar during 1 h. The amount of impregnated thymol in the different CNF materials was investigated by fluorescence spectroscopy, 13C NMR analysis, and gas chromatography. All three methods consistently showed that the amount of impregnated thymol increases with the specific surface area of the material. The antimicrobial activity of the impregnated CNF-based materials was then measured against three reference strains of microorganisms: the Gram-negative Escherichia coli and Gram-positive Staphylococcus epidermidis bacteria, and the yeast Candida albicans using the disk diffusion test method. The latter revealed the leaching of thymol in sufficient amounts to generate antimicrobial activity against the three strains in the case of the cryogel derived from a tert-butyl alcohol suspension and the aerogel, which are the two materials exhibiting the highest specific surface areas. The proposed strategy, therefore, enabled us to precisely steer the amount of active molecule loading and the related antimicrobial activity by adjusting the specific surface area of the biosourced material impregnated in green supercritical conditions. These results are very promising and confirm that supercritical impregnation of active molecules onto nanocellulose three-dimensional (3D) structures can be an interesting solution for the design of active medical devices such as wound dressings.

Identifying Juncus plant as viable source for the production of micro- and nano-cellulose fibers: Application for PVA composite materials development

With the aim of identifying new, renewable and sustainable sources for the production of bio-nano-materials, cellulose microfibers (CMF) and cellulose nanofibrils (CNF) were successfully produced from the widely available Juncus plant. CMF with average microfibers diameter of 3.5 μm were produced by conventional alkaline and bleaching treatments with a yield of around 36 %. CNF with average nanofibrils diameter of 2.5 nm were isolated from CMF by a combination of TEMPO-oxidation and mechanical disintegration processes. The morphology and physico-chemical properties of raw Juncus plant stems, CMF, TEMPO-oxidized CMF (T-CMF) and CNF were evaluated using several characterization techniques. It was found that the applied chemical treatments were effective in producing pure CMF and CNF materials having typical cellulose I structure, high crystallinity and good thermal stability. The as-extracted CNF were utilized to develop CNF-reinforced PVA nanocomposite films, and their transparency, thermal stability and mechanical properties were investigated and compared with the CMF and T-CMF reinforced PVA composite materials. It was found that the PVA nanocomposite material containing 5 wt% CNF exhibited a tensile modulus and strength of 3.3 GPa and 110 MPa, respectively, which are higher than those observed for neat PVA and PVA composites reinforced with 5 wt% CMF or T-CMF (modulus of 1.9 and 3.1 GPa and strength of 52 and 97 MPa, respectively). In contrast to CMF and T-CMF reinforced PVA composites, that displayed a reduced optical transmittance (ca. 57–70 % at 600 nm), the CNF-reinforced PVA nanocomposite material maintained the same transmittance of the neat PVA film (ca. 90 % at 600 nm), suggesting the good dispersion of CNF at the nanometric scale. These newly developed CNF could be considered as a potential nanofiller candidate for the preparation of PVA-based nanocomposite materials of high transparency and good mechanical properties.

Highly absorbent cellulose nanofibrils aerogels prepared by supercritical drying

In this paper, strictly speaking aerogels of cellulose nanofibrils (CNFs) and TEMPO-oxidized CNFs (TO-CNFs) were obtained from an optimized supercritical drying processes and cryogels were prepared after freeze-drying. The cryogels and aerogels were characterized and the influence of the preparation process on the resulting properties was studied. Significant differences were observed in the micro- and nanoscale organization of the porous structures. In addition, the specific surface areas measured varied from 25 to 160 m² g−1 for CNF materials, depending on the preparation process. Very high specific surface areas up to 482 m² g−1 among the highest reported for pure cellulose nanofibrils porous materials were achieved for TO-CNF aerogels. Finally, in order to evaluate their aptitudes for wound dressings applications, the capillary water uptake capacities were assessed on skin mimicking layers. From this study, it was revealed that TO-CNF aerogels can absorb almost 120 times their own weight of water.

Ultrapure Wood Nanocellulose-Assessments of Coagulation and Initial Inflammation Potential.

Using a lepirudin-based human whole blood model, we evaluated the initial inflammatory and coagulation responses of dense and porous ultrapure (<50 endotoxin units/grams) cellulose nanofibrils (CNF), of carboxylated grade. The CNF was compared to the wound dressing AquaCel because it is a potential wound-healing material. The porous CNF aerogels induced the strongest coagulation potential measured as prothrombin factor 1.2 (PTF1.2). AquaCel induced the strongest complement response by terminal complement complex (TCC) and surface C3c. All materials activated leukocytes CD11b, while the levels of only 3 of 27 cytokines were significantly changed, limited to (i) an elevation of the monocyte chemoattractant protein-1 (MCP-1/CCL) by the CNF aerogel, (ii) a reduction of eosinophil chemotactic proteins (eotaxin/CCL11) by the CNF aerogel, and (iii) a reduction of platelet-derived growth factor BB (PDGF-BB) by all CNF materials. In conclusion, the CNF materials and AquaCel differently activate coagulation, complement, and cytokines, improving the selection possibilities in various treatment situations of wound healing.

Printing and mechanical characterization of cellulose nanofibril materials

Cellulose nanofibrils (CNF) are a promising building block of structural materials because they are biodegradable, can be made into optically transparent bulk materials, and have exceptional specific strength and stiffness compared to common synthetic polymers. The manufacturing of bulk materials from CNFs is a challenge because CNFs form networks in solution at low solids concentration, which can result in long processing times as well as large residual stresses and distortion upon water removal. Here, a method to form materials from CNF suspensions via direct ink writing, a type of additive manufacturing, is demonstrated. Multilayer printing of CNFs provides a route to control drying time by depositing thin layers one at a time. A printing system with a pressure-controlled dispensing system was used to deposit aqueous CNF suspensions onto a temperature-controlled substrate. The geometry, roughness, and mechanical properties of the printed structures were characterized. The shape of the printed line profile is controlled by a combination of the wettability of the substrate, dispense rate, printing speed, and temperature of the substrate. Spatial variation of the elastic modulus of printed CNF structures was assessed with nanoindentation and the average percent difference was found to be small at ± 2.6% of the mean over the area of the printed lines. Through multilayer printing freestanding films with thicknesses greater than 60 μm were achieved. Tensile specimens were printed and characterized; a tensile strength of 72.6 MPa ± 7.4 MPa and a Young’s modulus of 10.2 GPa ± 1.2 GPa were measured.

Toward Semistructural Cellulose Nanocomposites: The Need for Scalable Processing and Interface Tailoring

Cellulose nanocomposites can be considered for semistructural load-bearing applications where modulus and strength requirements exceed 10 GPa and 100 MPa, respectively. Such properties are higher than for most neat polymers but typical for molded short glass fiber composites. The research challenge for polymer matrix biocomposites is to develop processing concepts that allow high cellulose nanofibril (CNF) content, nanostructural control in the form of well-dispersed CNF, the use of suitable polymer matrices, as well as molecular scale interface tailoring to address moisture effects. From a practical point of view, the processing concept needs to be scalable so that large-scale industrial processing is feasible. The vast majority of cellulose nanocomposite studies elaborate on materials with low nanocellulose content. An important reason is the challenge to prevent CNF agglomeration at high CNF content. Research activities are therefore needed on concepts with the potential for rapid processing with controlled nanostructure, including well-dispersed fibrils at high CNF content so that favorable properties are obtained. This perspective discusses processing strategies, agglomeration problems, opportunities, and effects from interface tailoring. Specifically, preformed CNF mats can be used to design nanostructured biocomposites with high CNF content. Because very few composite materials combine functional and structural properties, CNF materials are an exception in this sense. The suggested processing concept could include functional components (inorganic clays, carbon nanotubes, magnetic nanoparticles, among others). In functional three-phase systems, CNF networks are combined with functional components (nanoparticles or fibril coatings) together with a ductile polymer matrix. Such materials can have functional properties (optical, magnetic, electric, etc.) in combination with mechanical performance, and the comparably low cost of nanocellulose may facilitate the use of large nanocomposite structures in industrial applications.

Pulping and Pretreatment Affect the Characteristics of Bagasse Inks for Three-dimensional Printing

Bagasse is an underutilized agro-industrial residue with great potential as raw material for the production of cellulose nanofibrils (CNF) for a range of applications. In this study, we have assessed the suitability of bagasse for production of CNF for three-dimensional (3D) printing. First, pulp fibers were obtained from the bagasse raw material using two fractionation methods, i.e. soda and hydrothermal treatment combined with soda. Second, the pulp fibers were pretreated by TEMPO-mediated oxidation using two levels of oxidation for comparison purposes. Finally, the CNF were characterized in detail and assessed as inks for 3D printing. The results show that CNF produced from fibers obtained by hydrothermal and soda pulping were less nanofibrillated than the corresponding material produced by soda pulping. However, the CNF sample obtained from soda pulp was cytotoxic, apparently due to a larger content of silica particles. All the CNF materials were 3D printable. We conclude that the noncytotoxic CNF pro...

Dry-Spun Neat Cellulose Nanofibril Filaments: Influence of Drying Temperature and Nanofibril Structure on Filament Properties

Cellulose nanofibrils (CNF) were spun into filaments directly from suspension without the aid of solvents. The influence of starting material properties and drying temperature on the properties of filaments produced from three different CNF suspensions was studied. Refiner-produced CNF was ground using a microgrinder at grinding times of 50 and 100 minutes. Filament spinning was performed using a syringe pump-heat gun setting at three drying temperatures of 210 °C, 320 °C and 430 °C. The structure of starting CNF materials was first evaluated using a combination of optical and atomic force microscopy (AFM) techniques. Surface free energy analysis and attenuated total reflectance—Fourier transform infrared spectroscopy (ATR–FTIR) were used to study changes in hydrophobicity due to grinding. Morphology of the filaments was studied using SEM micrographs. The influence of different drying temperatures and grinding times on mechanical properties of the CNF filaments were further investigated through tensile tests and results were compared using statistical analysis .It was observed that drying temperature did not significantly influence the tensile properties of the filaments while cellulose nanofiber suspension type (grinding time) had a significant influence and improved mechanical properties. FTIR results confirmed an increase in crystallinity index and decrease in hydroxyl group availability due to grinding.

Bacterial adhesion to polyvinylamine-modified nanocellulose films

Cellulose nanofibril (CNF) materials have been widely studied in recent years and are suggested for a wide range of applications, e.g., medical and hygiene products. One property not very well studied is the interaction between bacteria and these materials and how this can be controlled. The current work studies how bacteria adhere to different CNF materials modified with polyelectrolyte multilayers. The tested materials were TEMPO-oxidized to have different surface charges, periodate-oxidized to vary the water interaction and hot-pressed to alter the surface structure. Then, multilayers were constructed using polyvinylamine (PVAm) and polyacrylic acid.Both the material surface charge and water interaction affect the amount of polymer adsorbed to the surfaces. Increasing the surface charge decreases the adsorption after the first PVAm layer, possibly due to conformational changes. Periodate-oxidized and crosslinked films have low initial polymer adsorptions; the decreased swelling prevents polymer diffusion into the CNF micropore structure.Microscopic analysis after incubating the samples with bacterial suspensions show that only the materials with the lowest surface charge enable bacteria to adhere to the surface because, when adsorbing up to 5 layers PVAm/PAA, the increased anionic surface charge appears to decrease the net surface charge. Both the amounts of PVAm and PAA influence the net surface charge and thus the bacterial adhesion. The structure generated by the hot-pressing of the films also strongly increases the number of bacteria adhering to the surfaces. These results indicate that the bacterial adhesion to CNF materials can be tailored using polyelectrolyte multilayers on different CNF substrates.

Triboelectric nanogenerators and power-boards from cellulose nanofibrils and recycled materials

This paper reports the implementation of renewable, biodegradable, and abundant cellulose nanofibrils (CNFs) in triboelectric nanogenerator (TENG) development. Flexible and transparent CNF thin films are triboelectric positive material with nanoscale surface roughness. They are paired with FEP (fluorinated ethylene propylene) to assemble TENG devices, which exhibit comparable performance to the reported TENG devices built on synthetic polymers. CNF-based TENG is further integrated within a fiberboard made from recycled cardboard fibers using a chemical-free cold pressing method. The fiberboard produces up to ~30V and ~90μA electric outputs when subjected to a normal human step. This development shows great promises in creating large-scale and environmentally sustainable triboelectric board for flooring, packaging and supporting infrastructures from CNF and other natural wood-extracted materials.

Fibril orientation redistribution induced by stretching of cellulose nanofibril hydrogels

The mechanical performance of materials reinforced by cellulose nanofibrils is highly affected by the orientation of these fibrils. This paper investigates the nanofibril orientation distribution of films of partly oriented cellulose nanofibrils. Stripes of hydrogel films were subjected to different amount of strain and, after drying, examined with X-ray diffraction to obtain the orientation of the nanofibrils in the films, caused by the stretching. The cellulose nanofibrils had initially a random in-plane orientation in the hydrogel films and the strain was applied to the films before the nanofibrils bond tightly together, which occurs during drying. The stretching resulted in a reorientation of the nanofibrils in the films, with monotonically increasing orientation towards the load direction with increasing strain. Estimation of nanofibril reorientation by X-ray diffraction enables quantitative comparison of the stretch-induced orientation ability of different cellulose nanofibril systems. The reorientation of nanofibrils as a consequence of an applied strain is also predicted by a geometrical model of deformation of nanofibril hydrogels. Conversely, in high-strain cold-drawing of wet cellulose nanofibril materials, the enhanced orientation is promoted by slipping of the effectively stiff fibrils.