Combining and concentrating nanocelluloses for cryogels with remarkable strength and wet resilience.

Cellulose cryogels are promising eco-friendly materials that exhibit low density, high porosity, and renewability. However, the applications of these materials are limited by their lower mechanical and water resistance compared to petrochemical-based lightweight materials. In this work, nanocelluloses were functionalized with cationic and anionic groups, and these nanomaterials were combined to obtain strong and water-resilient cryogels. To prepare the cryogels, anionic and cationic micro- and nanofibrils (CNFs) were produced at three different sizes and combined in various weight ratios, forming electrostatic complexes. The complex phase was concentrated by centrifugation and freeze-dried. Porous and open cellular structures were assembled in all compositions tested (porosity >90 %). Compressive testing revealed that the most resistant cryogels (1.7 MPa) were obtained with equivalent amounts of negatively and positively charged CNFs with lengths between 100 and 1200 nm. The strength at this condition was achieved as CNF electrostatic complexes assembled in thick cells, as observed by synchrotron X-ray tomography. In addition to mechanical strength, electrostatic complexation provided remarkable structural stability in water for the CNF cryogels, without compromising their biodegradability. This route by electrostatic complexation is a practical strategy to combine and concentrate nanocelluloses to tailor biodegradable lightweight materials with high strength and wet stability.

Cellulose nanocrystals-reinforced core-shell hydrogels for sustained release of fertilizer and water retention.

Core-shell (CS) hydrogels show great potential for the controlled release of fertilizers. In this work, we prepared an alginate-coated gelatin-cellulose nanocrystals (CNCs) hydrogel by a simple layer-by-layer process. CNCs were prepared from cotton linter fibers by the sulfuric acid process. They were incorporated into the gelatin hydrogel, and an external alginate membrane was applied to the inner membrane. Compared to neat gelatin hydrogel, the compressive modulus of the nanocomposite with 5.0 wt% CNCs was enhanced by 288 %. In addition, the CS hydrogel showed a slow-release property and better water retention capacity than neat gelatin hydrogel. The main results of this work are listed below: compression test revealed that the addition of the CNC increases the mechanical properties of the hydrogel, and ii) the addition of a second layer of alginate to CNC-reinforced gelatin hydrogel increase the water retention and improve the sustained release of fertilizer. Our study provides easy and green routes to produce CS hydrogels for potential agricultural applications.

How lignin sticks to cellulose-insights from atomic force microscopy enhanced by machine-learning analysis and molecular dynamics simulations.

Elucidating cellulose-lignin interactions at the molecular and nanometric scales is an important research topic with impacts on several pathways of biomass valorization. Here, the interaction forces between a cellulosic substrate and lignin are investigated. Atomic force microscopy with lignin-coated tips is employed to probe the site-specific adhesion to a cellulose film in liquid water. Over seven thousand force-curves are analyzed by a machine-learning approach to cluster the experimental data into types of cellulose-tip interactions. The molecular mechanisms for distinct types of cellulose-lignin interactions are revealed by molecular dynamics simulations of lignin globules interacting with different cellulose Iß crystal facets. This unique combination of experimental force-curves, data-driven analysis, and molecular simulations opens a new approach of investigation and updates the understanding of cellulose-lignin interactions at the nanoscale.

Tailoring strength of nanocellulose foams by electrostatic complexation.

Supramolecular assembly of biobased components in water is a promising strategy to construct advanced materials. Herein, electrostatic complexation was used to prepare wet-resilient foams with improved mechanical property. Small-angle X-ray scattering and cryo-transmission electron microscopy experiments showed that suspensions with oppositely charged cellulose nanofibers are a mixture of clusters and networks of entangled fibers. The balance between these structures governs the colloidal stability and the rheological behavior of CNFs in water. Foams prepared from suspensions exhibited maximum compressive modulus at the mass composition of 1:1 (ca 0.12 MPa), suggesting that meaningful attractive interactions happen at this point and act as stiffening structure in the material. Besides the electrostatic attraction, hydrogen bonds and hydrophobic contacts may also occur within the clustering, improving the water stability of cationic foams. These results may provide a basis for the development of robust all- cellulose materials prepared in water, with nontoxic chemicals.

A novel green approach for the preparation of cellulose nanowhiskers from white coir.

The aim of this work was to optimize the extraction of cellulose nanowhiskers (CNW) from unripe coconut husk fibers (CHF). The CHF was delignified using organosolv process, followed by alkaline bleaching (5% (w/w) H2O2+4% (w/w) NaOH; 50°C, 90 min). The CHF was subsequently hydrolyzed with 30% (v/v) sulfuric acid (60°C, 360 min). The process yielded a partially delignified acetosolv cellulose pulp and acetic black liquor, from which the lignin was recovered. The CNW from the acetosolv pulp exhibited an average length of 172±88 nm and a diameter of 8±3 nm, (aspect ratio of 22±8). The surface charge of the CNW was -33 mV, indicating a stable aqueous colloidal suspension. The nanocrystals presented physical characteristics close to those extracted from cellulose pulp made by CHF chlorine-pulping. This approach offers the additional advantage of extracting the lignin as an alternative to eradication.

Improvement of polyvinyl alcohol properties by adding nanocrystalline cellulose isolated from banana pseudostems.

Cellulose nanocrystals (CNCs) isolated from banana pseudostems fibers (BPF) of the Pacovan variety were used as fillers in a polyvinyl alcohol (PVOH) matrix to yield a nanocomposite. The fibers from the external fractions of the BPF were alkaline bleached and hydrolyzed under acidic conditions (H2SO4 62% w/w, 70 min, 45 °C) to obtain CNCs with a length (L) of 135.0 ± 12.0 nm and a diameter (D) of 7.2 ± 1.9 nm to yield an aspect ratio (L/D) of 21.2. The CNCs were applied to PVOH films at different concentrations (0%, 1%, 3%, and 5% w/w, dry basis). With higher concentrations of CNCs, the water-vapor barrier of the films increased, while the optical properties changed very little. Increasing the concentration of the CNCs up to 3% significantly improved the mechanical properties of the nanocomposite.